EP2403649A1 - Agglomérats hydrophobes magnétiques - Google Patents

Agglomérats hydrophobes magnétiques

Info

Publication number
EP2403649A1
EP2403649A1 EP10706247A EP10706247A EP2403649A1 EP 2403649 A1 EP2403649 A1 EP 2403649A1 EP 10706247 A EP10706247 A EP 10706247A EP 10706247 A EP10706247 A EP 10706247A EP 2403649 A1 EP2403649 A1 EP 2403649A1
Authority
EP
European Patent Office
Prior art keywords
particle
magnetic
agglomerates
hydrophobized
active substance
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.)
Granted
Application number
EP10706247A
Other languages
German (de)
English (en)
Other versions
EP2403649B1 (fr
Inventor
Imme Domke
Hartmut Hibst
Alexej Michailovski
Norbert Mronga
Werner Hartmann
Wolfgang Krieglstein
Vladimir Danov
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
Siemens AG
Original Assignee
BASF SE
Siemens 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 BASF SE, Siemens AG filed Critical BASF SE
Priority to EP10706247.3A priority Critical patent/EP2403649B1/fr
Priority to PL10706247T priority patent/PL2403649T3/pl
Publication of EP2403649A1 publication Critical patent/EP2403649A1/fr
Application granted granted Critical
Publication of EP2403649B1 publication Critical patent/EP2403649B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B03C1/015—Pretreatment specially adapted for magnetic separation by chemical treatment imparting magnetic properties to the material to be separated, e.g. roasting, reduction, oxidation

Definitions

  • the present invention relates to an agglomerate of at least one particle P, which is hydrophobized on the surface with at least one first surfactant, and at least one magnetic particle MP, which is hydrophobized on the surface with at least one second surfactant, a process for producing these agglomerates and the use of the agglomerates for separating a particle P from mixtures comprising these particles P and further components.
  • Agglomerates containing at least one magnetic particle and at least one further component are already known from the prior art.
  • US Pat. No. 4,657,666 discloses a method for enriching ores, wherein the ore in orbit is reacted with magnetic particles, whereby agglomerates form due to the hydrophobic interactions.
  • the magnetic particles are rendered hydrophobic by treatment with hydrophobic compounds on the surface, so that binding to the ore is effected.
  • the agglomerates are then separated from the mixture by a magnetic field.
  • the cited document also discloses that the ores are treated with a surface activating solution of 1% sodium ethylxanthogenate before the magnetic particle is added.
  • US 4,834,898 discloses a method for separating non-magnetic materials by contacting them with magnetic reagents coated with two layers of surfactants. US 4,834,898 further discloses that the surface charge of the non-magnetic particles to be separated may be affected by various types and concentrations of electrolyte reagents. For example, the surface charge is altered by the addition of multivalent anions, for example tripolyphosphate ions.
  • WO 2007/008322 A1 discloses a magnetic particle, which is hydrophobized on the surface, for the separation of impurities from mineral substances by magnetic separation processes.
  • a dispersant selected from sodium silicate, sodium polyacrylate or sodium hexametaphosphate can be added to the solution or dispersion.
  • the object of the present invention is to provide agglomerates of at least one magnetic particle and at least one further particle, wherein the at least one further particle is preferably a value component.
  • the agglomerates according to the invention should be distinguished by a high stability in water or polar media, but should not be stable in non-polar media.
  • these agglomerates should have a hydrophobic character.
  • a further object of the present invention is to provide corresponding agglomerates which, due to their magneticity, can be separated by a magnetic field from further, non-magnetic and non-hydrophobic components.
  • hydrophobic means that the corresponding particle can be subsequently rendered hydrophobic by treatment with the at least one surface-active substance It is also possible that a per se hydrophobic particle is additionally rendered hydrophobic by treatment with the at least one surface-active substance becomes.
  • Hydrophobic in the context of the present invention means that the surface of a corresponding "hydrophobic substance” or a “hydrophobized substance” has a contact angle of> 90 ° with water against air.
  • Hydrophobic in the context of the present invention means that the surface of a corresponding “hydrophilic substance” has a contact angle of ⁇ 90 ° with water against air.
  • At least one particle P is present, which is hydrophobized on the surface with at least one first surface-active substance.
  • the at least one particle P contains at least one metal compound and / or carbon.
  • the at least one particle P contains a metal compound selected from the group of sulfidic ores, oxidic and / or carbonate-containing ores, for example azurite [Cu 3 (CO 2 ) 2 (OI-I) 2 ], or malachite [Cu 2 [(OH) 2
  • the at least one particle P consists of said metal compounds.
  • sulfidic ores which can be used according to the invention are selected, for example, from the group of copper ores consisting of covellite CuS, molybdenum (IV) sulfide, chalcopyrite (copper gravel) CuFeS 2 , bornite Cu 5 FeS 4 , chalcocite (copper luster) Cu 2 S, sulfides iron, lead, zinc or molybdenum, ie FeS / FeS 2 , PbS, ZnS or MoS 2 and mixtures thereof.
  • copper ores consisting of covellite CuS, molybdenum (IV) sulfide, chalcopyrite (copper gravel) CuFeS 2 , bornite Cu 5 FeS 4 , chalcocite (copper luster) Cu 2 S, sulfides iron, lead, zinc or molybdenum, ie FeS / FeS 2 , PbS, ZnS or MoS 2 and mixtures thereof.
  • Suitable oxidic compounds are those of metals and semimetals, for example silicates or borates or other salts of metals and semimetals, for example phosphates, sulfates or oxides / hydroxides / carbonates and further salts, for example azurite [Cu 3 (CO 2 ) 2 (OH) 2 ], malachite [Cu 2 [(OH) 2 (CO 3 )]], barite (BaSO 4 ), monacite ((La-Lu) PO 4 ).
  • metals and semimetals for example silicates or borates or other salts of metals and semimetals, for example phosphates, sulfates or oxides / hydroxides / carbonates and further salts, for example azurite [Cu 3 (CO 2 ) 2 (OH) 2 ], malachite [Cu 2 [(OH) 2 (CO 3 )]], barite (BaSO 4 ), monacite ((La-Lu) PO 4 ).
  • Suitable noble metals are, for example, Au, Pt, Pd, Rh, etc., where Pt is mainly alloyed.
  • Suitable Pt / Pd ores are Sperrlith PtAs 2 , Cooperit PtS or Braggit (Pt, Pd, Ni) S.
  • the at least one particle P present in the agglomerate according to the invention is hydrophobicized on the surface with at least one first surface-active substance and the at least one magnetic particle MP is hydrophobicized with at least one second surface-active substance.
  • the at least one first and the at least one second surface-active substance are different.
  • the at least one first and the at least one second surface-active substance are identical.
  • surface-active substance means a substance which is capable of changing the surface of the particle P so that it becomes hydrophobic in the sense of the abovementioned definition.
  • A is selected from linear or branched C 3 -C 3 -alkyl, C 3 -C 3 o-heteroalkyl, optionally substituted C 6 -C 30 -aryl, optionally substituted C 6 -C 30 - heteroalkyl, C 6 -C 30 - Aralkyl is and
  • Z is a group with which the compound of the general formula (I) binds to the at least one particle P.
  • A is a linear or branched C 4 -C 2 -alkyl, very particularly preferably a linear C 4 - or C 8 -alkyl.
  • optionally present heteroatoms according to the invention are selected from N, O, P, S and halogens such as F, Cl, Br and I.
  • A is preferably a linear or branched, preferably linear, C 6 -C 20 -alkyl.
  • A is preferably a branched C 6 -C 4 -alkyl, wherein the at least one substituent, preferably having 1 to 6 carbon atoms, is preferably present in the 2-position, for example 2-ethylhexyl and / or 2-propylheptyl.
  • n 2 in the abovementioned formulas, then two identical or different, preferably identical, groups A are bound to a group Z.
  • compounds are used which are selected from the group consisting of xanthates AO-CS 2 " , dialkyldithiophosphate (AO) 2 -PS 2 " , dialkyldithioposphinates (A) 2 -PS 2 " and mixtures thereof, where A is independently each other is a linear or branched, preferably linear, C 6 -C 20 -alkyl, for example n-octyl, or a branched C 6 -C 4 -alkyl, where the branching is preferably present in the 2-position, for example 2-ethylhexyl and / or 2-propylheptyl.
  • Preferred counterions in these compounds are cations selected from the group consisting of hydrogen, NR 4 + where R is independently hydrogen and / or C 1 -C 8 -alkyl, alkali or alkaline-earth metals, in particular sodium or potassium.
  • Very particularly preferred compounds of general formula (I) are selected from the group consisting of sodium or potassium n-octylxanthate, sodium or potassium butylxanthate, sodium or potassium di-n-octyl dithiophosphinate, sodium or potassium di -n-octyl dithiophosphate, octanethiol and mixtures of these compounds.
  • particularly preferred surface-active substances are xanthates, thiocarbamates or hydroxamates. Further suitable surface-active substances are described, for example, in EP 1200408 B1.
  • metal oxides for example FeO (OH), Fe 3 O 4 , ZnO etc.
  • carbonates for example azurite [Cu (CO 2 ) 2 (OI-I) 2 ], malachite [Cu 2 E (OH) 2 CO 3 ]]
  • OPS octylphosphonic acid
  • EtO EtO
  • MeO MeO
  • particularly preferred surface-active substances are mono-, di- and trithiols or xanthates.
  • Z is - (X) n -CS 2 " , - (X) n -PO 2 " or - (X) n -S " where X is O and n is 0 or 1 and one Cation selected from hydrogen, sodium or potassium
  • Very particularly preferred surface-active substances are 1-octanethiol, potassium n-octylxanthate, potassium-butylxanthate, octylphosphonic acid or a compound of the following formula (IV)
  • At least one particle P is present, which is hydrophobized with at least one surface-active substance.
  • P is Cu 2 S, which is hydrophobized with the potassium salts of ethyl, butyl octyl or other aliphatic or branched xanthates or mixtures thereof.
  • the particle P is a Pd-containing alloy, preferably with the Potassium salts of ethyl, butyl octyl or other aliphatic or branched xanthates or mixtures thereof is hydrophobized, most preferably d these particles is hydrophobicized with mixtures of these Kaliumxanthate and thiocarbamates.
  • agglomerates are preferred in which the particle contains P Rh, Pt, Pd, Au, Ag, Ir or Ru.
  • the surface-active hydrophobization is adapted to the corresponding mineral surface, so that it comes to an optimal interaction between surface-active substance and the particle P, which contains Rh, Pt, Pd, Au, Ag, Ir or Ru.
  • Methods for hydrophobizing the surface of the particles P which can be used in the agglomerates according to the invention are known to the person skilled in the art, for example by contacting the particles P with the at least one first surface-active substance, for example in bulk or in dispersion.
  • the particles P and the at least one surface-active substance are added and mixed together without further dispersant in the appropriate amounts.
  • Suitable mixing apparatuses are known to the person skilled in the art, for example mills, such as ball mill (planetary vibrating mills).
  • the components are combined in a dispersion, preferably in suspension.
  • Suitable dispersants are, for example, water, water-soluble organic compounds, for example alcohols having 1 to 4 carbon atoms, and mixtures thereof.
  • the at least one first surface-active substance is generally present on the at least one particle P in an amount of 0.01 to 5% by weight, preferably 0.01 to 0.1% by weight, based on the sum of at least a first surfactant and at least one particle P.
  • the optimum content of surfactant generally depends on the size of the particles P.
  • the particles P can generally be shaped regularly, for example in a spherical, cylindrical, cuboidal, or irregular, for example splintered, shape.
  • Particle P 2 may be selected from the group referred to particle P.
  • Particle P 2 may also be selected from the group of oxidic metal or semimetal compounds, for example SiO 2 .
  • the at least one particle P which is hydrophobized on the surface with at least one first surface-active substance, generally has a diameter of 1 nm to 10 mm, preferably 10 to 100 ⁇ m. In asymmetrically shaped Particles are considered the diameter of the longest distance in the particle.
  • the agglomerate according to the invention further comprises at least one magnetic particle MP, which is hydrophobized on the surface with at least one second surface-active substance.
  • the at least one magnetic particle MP is selected from the group consisting of magnetic metals, for example iron, cobalt, nickel and mixtures thereof, ferromagnetic alloys of magnetic metals, for example NdFeB, SmCo and mixtures thereof, magnetic iron oxides, for example magnetite , Maghemite, cubic ferrites of the general formula (II)
  • M is selected from Co, Ni, Mn, Zn and mixtures thereof and x ⁇ 1,
  • the magnetic particles MP may additionally have an outer layer, for example of SiO 2 .
  • the magnetic particles MP can generally be regularly shaped, for example, spherical, cylindrical, cuboidal, or irregular, for example splinter-shaped.
  • the at least one magnetic article MP which is hydrophobized on the surface with at least one second surface-active substance, generally has a diameter of 10 nm to 1000 mm, preferably 100 nm to 1 mm, particularly preferably 500 nm to 500 ⁇ m, very particularly preferably 1 up to 100 ⁇ m, on.
  • the diameter is considered to be the longest distance in the particle.
  • Particular preference is given to using magnetic particles MP which have a similar particle size distribution as the particles P. These size distributions may be mono-, bi- or trimodal.
  • the magnetic particles MP may, if appropriate, be converted into the appropriate size prior to the use according to the invention using methods known to those skilled in the art, for example by grinding.
  • the magnetic particles MP which can be used according to the invention preferably have a BET specific surface area of from 0.01 to 50 m 2 / g, particularly preferably from 0.1 to 20 m 2 / g, very particularly preferably from 0.2 to 10 m 2 / g.
  • the magnetic particles MP which can be used according to the invention preferably have a density (measured to DIN 53193) of 3 to 10 g / cm 3 , particularly preferably 4 to 8 g / cm 3 .
  • the at least one magnetic particle MP present in the agglomerates according to the invention is hydrophobized on the surface with at least one second surface-active substance.
  • the at least one second surface-active substance is preferably selected from compounds of the general formula (III)
  • B is selected from linear or branched C 3 -C 3 -alkyl, C 3 -C 3 o-heteroalkyl, optionally substituted C 6 -C 30 aryl, optionally substituted C 6 -C 30 - heteroalkyl, C 6 -C 30 -Aralkyl and
  • Y is a group with which the compound of general formula (III) binds to the at least one magnetic particle MP.
  • a linear or branched C 6 -C C 8 -C a linear Ci is B 8 alkyl, preferably linear C2 alkyl, most preferably 2 alkyl.
  • optionally present heteroatoms according to the invention are selected from N, O, P, S and halogens such as F, Cl, Br and I.
  • Y is selected from the group consisting of - (X) n -SiHaI 3 , - (X) n -SiHHaI 2 , - (X) n -SiH 2 Hal with HaI equal to F, Cl, Br, I, and anionic groups such as - (X) n -SiO 3 3 " , - (X) n -CO 2 " , - (X) n -PO 3 2 " , - (X) n -PO 2 S 2 " , - (X) n -POS 2 2” , - (X) n -PPS 3 2 " , - (X) n -PPS 2 " , - (X) n -POS " , - (X) n -PO 2 " , - (X) n -CO 2 " , - (X) n -CS 2 " , - (X) n
  • n 2 in the abovementioned formulas, then two identical or different, preferably identical, groups B are bound to a group Y.
  • Very particularly preferred hydrophobizing substances of the general formula (III) are alkyltrichlorosilanes (alkyl group having 6-12 carbon atoms), alkyltrimethoxysilanes (alkyl group having 6-12 carbon atoms), octylphosphonic acid, lauric acid, oleic acid, stearic acid or mixtures thereof.
  • the at least one second surface-active substance is present on the at least one magnetic particle MP, preferably in an amount of from 0.01 to 0.1% by weight, based on the sum of at least one second surface-active substance and at least one magnetic particle MP.
  • the optimum amount of at least one second surface-active substance is dependent on the size of the magnetic particle MP.
  • At least one magnetic particle MP which is hydrophobicized with at least one second surface-active substance, magnetite, hydrophobed with dodecyltrichlorosilane and / or magnetite, hydrophobicized with octylphosphonic acid.
  • the magnetic particles MP rendered hydrophobic with at least one second surface-active substance can be prepared by all processes known to those skilled in the art, preferably as described with regard to the hydrophobized particles P.
  • the at least one particle P which is hydrophobized on the surface with at least one first surface-active substance
  • the at least one magnetic particle MP which is hydrophobized on the surface with at least one second surface-active substance
  • the at least one particle P lying on the surface with at least one first o surfactant is hydrophobic to 10 to 90 wt .-%, preferably 20 to 80 wt .-%, particularly preferably 40 to 60 wt .-%, and the at least one magnetic particle MP, which at the surface with at least one second surface-active substance is hydrophobed, at 10 to 90 wt .-%, preferably 20 to 80 wt .-%, more preferably 40 to 60 wt .-%, before, in each case based on the total agglomerate, wherein the sum of each 100 wt. % results.
  • the agglomerate according to the invention at least one particle P, which is hydrophobized on the surface with at least one first surface-active substance, and 50% by weight at least one magnetic particle MP, which at least with the surface a second surfactant is hydrophobized before.
  • the ratio P to MP is particularly preferred if an external magnetic field (which can be generated, for example, by a strong CoSm permanent magnet) can still magnetically deflect these particles if the agglomerates move with a flow of 300 mm / sec. at a 90 ° angle to the external magnet.
  • an external magnetic field which can be generated, for example, by a strong CoSm permanent magnet
  • it is very particularly preferred if the hydrophobic interactions between P and MP are strong enough that they are not torn apart at this flow rate.
  • the bond between the at least one particle P, which is hydrophobized on the surface with at least one first surface-active substance, and the at least one magnetic particle, which is hydrophobized on the surface with at least one second surface-active substance, takes place in the agglomerate according to the invention by hydrophobic interactions.
  • the diameter of the agglomerates according to the invention depends on the percentage of the particles P or the magnetic particles MP, the diameters of the particles P or magnetic particles MP, as well as the interspaces between the particles, which are dependent on the type and amount of the surface-active substances.
  • the agglomerates according to the invention generally have a magneticity, so that an external magnetic field, which can be generated, for example, by a strong CoSm permanent magnet, can at least still magnetically deflect these agglomerates if the agglomerates move with a flow of 300 mm / sec. at a 90 ° angle to the external magnet.
  • the hydrophobic interactions between P and MP within the agglomerates are generally strong enough that they remain stable at said flow rate, ie, are not torn apart.
  • the agglomerates according to the invention can be cleaved in a non-polar medium, for example diesel or acetone, preferably without the at least one particle P or the at least one magnetic particle MP being destroyed.
  • the agglomerates according to the invention can be prepared, for example, by contacting the particles P, which are hydrophobized with the at least one first surface-active substance, and the hydrophobized with the at least one second surface-active substance MP, for example, in bulk or in dispersion.
  • the hydrophobized particles P and the hydrophobized magnetic particles MP are added and mixed together without additional dispersant in the appropriate amounts.
  • the particles P and the magnetic particles MP are added and mixed together in the corresponding amounts in the presence of the at least one first and at least one second surface-active substance without further dispersing agent.
  • Suitable mixing apparatuses are known to the person skilled in the art, for example mills, such as ball mill.
  • Dispersants suitable for the process according to the invention are, for example, water, water-soluble organic compounds, for example alcohols having 1 to 4 carbon atoms, and mixtures thereof.
  • the present invention also relates to a method for producing agglomerates according to the invention comprising contacting the particles P hydrophobized with the at least one first surfactant, and the magnet article MP hydrophobized with the at least one second surfactant, to obtain the agglomerates.
  • the process according to the invention is generally carried out at a temperature of 5 to 50 ° C., preferably at ambient temperature.
  • the process according to the invention is generally carried out at atmospheric pressure. After the agglomerates according to the invention have been obtained, they can be separated from an optionally present solvent or dispersion medium by methods known to the person skilled in the art, for example by filtration, decanting, sedimentation and / or magnetic processes.
  • the agglomerates according to the invention can be used to separate corresponding particles P from mixtures containing these particles P and further components.
  • particle P may be an ore and the other components may be gait.
  • the agglomerates can be cleaved after separation by methods known to those skilled in the art.
  • the present invention also relates to the use of the agglomerates according to the invention for the separation of a particle P from mixtures containing these particles P and other components, for example for the separation of ores from raw ores containing the gangue.
  • the system is poured into water.
  • the hydrophobic agglomerates according to the invention are formed between the hydrophobic magnetite and the selectively hydrophobized copper sulfide. These agglomerates can by the action of a strong permanent magnet at flow rates greater than 320 mm / sec. are held perpendicular to the magnet without the hydrophobic agglomerates are destroyed.

Landscapes

  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Soft Magnetic Materials (AREA)
  • Hard Magnetic Materials (AREA)
  • Powder Metallurgy (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Compounds Of Iron (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Glanulating (AREA)

Abstract

La présente invention concerne des agglomérats constitués d'au moins une particule P, rendue hydrophobe en surface à l'aide d'au moins une première substance tensioactive, et d'au moins une particule magnétique MP, rendue hydrophobe en surface à l'aide d'au moins une deuxième substance tensioactive. L'invention concerne également un procédé de fabrication de ces agglomérats et leur utilisation.
EP10706247.3A 2009-03-04 2010-03-03 Agglomérats hydrophobes magnétiques Not-in-force EP2403649B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP10706247.3A EP2403649B1 (fr) 2009-03-04 2010-03-03 Agglomérats hydrophobes magnétiques
PL10706247T PL2403649T3 (pl) 2009-03-04 2010-03-03 Magnetyczne aglomeraty hydrofobowe

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP09154285 2009-03-04
EP10706247.3A EP2403649B1 (fr) 2009-03-04 2010-03-03 Agglomérats hydrophobes magnétiques
PCT/EP2010/052667 WO2010100180A1 (fr) 2009-03-04 2010-03-03 Agglomérats hydrophobes magnétiques

Publications (2)

Publication Number Publication Date
EP2403649A1 true EP2403649A1 (fr) 2012-01-11
EP2403649B1 EP2403649B1 (fr) 2013-08-28

Family

ID=42145078

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10706247.3A Not-in-force EP2403649B1 (fr) 2009-03-04 2010-03-03 Agglomérats hydrophobes magnétiques

Country Status (17)

Country Link
US (1) US8377313B2 (fr)
EP (1) EP2403649B1 (fr)
JP (1) JP5683498B2 (fr)
CN (1) CN102341179B (fr)
AR (1) AR076077A1 (fr)
AU (1) AU2010220284B2 (fr)
BR (1) BRPI1011516A8 (fr)
CA (1) CA2752881C (fr)
EA (1) EA020958B1 (fr)
ES (1) ES2435631T3 (fr)
MX (1) MX2011009082A (fr)
PE (1) PE20120731A1 (fr)
PL (1) PL2403649T3 (fr)
PT (1) PT2403649E (fr)
UA (1) UA103077C2 (fr)
WO (1) WO2010100180A1 (fr)
ZA (1) ZA201107236B (fr)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL2212027T3 (pl) 2007-11-19 2012-08-31 Basf Se Magnetyczne rozdzielanie substancji na podstawie ich zróżnicowanych ładunków powierzchniowych
AU2009272764B2 (en) 2008-07-18 2014-11-20 Basf Se Selective substance separation using modified magnetic particles
BRPI0922451A2 (pt) 2008-12-11 2015-12-15 Basf Se processo para separar pelo menos um primeiro material a partir de uma mistura.
WO2010084635A1 (fr) * 2009-01-23 2010-07-29 財団法人大阪産業振興機構 Dispositif et procédé de traitement de mélange
CA2753486C (fr) 2009-02-24 2016-11-01 Basf Se Separation cu-mo
CN102341178B (zh) 2009-03-04 2015-06-03 西门子公司 通过多级式调节进行有色金属矿物的磁分离
US8865000B2 (en) 2010-06-11 2014-10-21 Basf Se Utilization of the naturally occurring magnetic constituents of ores
US9376457B2 (en) 2010-09-03 2016-06-28 Basf Se Hydrophobic, functionalized particles
MX2013006028A (es) * 2010-11-29 2013-07-29 Basf Corp Recuperacion magnetica de elementos de valor a partir de escoria.
AU2012213470A1 (en) 2011-02-01 2013-08-15 Basf Corporation Apparatus for continuous separation of magnetic constituents and cleaning magnetic fraction
CA2832814C (fr) * 2011-04-12 2019-04-02 Basf Se Particules hydrophobes fonctionnalisees
US10675637B2 (en) 2014-03-31 2020-06-09 Basf Se Magnet arrangement for transporting magnetized material
WO2016083575A1 (fr) 2014-11-27 2016-06-02 Basf Se Entrée d'énergie pendant l'agglomération de séparation magnétique
CA2967215A1 (fr) 2014-11-27 2016-06-02 Basf Se Amelioration de la qualite de concentre
EP3181230A1 (fr) 2015-12-17 2017-06-21 Basf Se Ultraflottation avec des particules support magnétiquement réactives
CN106076602A (zh) * 2016-06-29 2016-11-09 昆明理工大学 一种磁介质团聚弱磁选富集氧化锌矿的方法
WO2018006959A1 (fr) * 2016-07-06 2018-01-11 Friedrich-Alexander-Universität Erlangen-Nürnberg Particule coeur-écorce
MX2020001255A (es) * 2017-08-03 2020-03-20 Basf Se Separacion de una mezcla utilizando particulas portadoras magneticas.
EP3687696B1 (fr) * 2017-09-29 2023-03-08 Basf Se Concentration de particules de graphite par agglomération avec des particules magnétiques hydrophobes
JP7152003B2 (ja) * 2018-08-22 2022-10-12 河合石灰工業株式会社 高熱伝導性無機フィラー複合粒子及びその製造方法
CN109078760B (zh) * 2018-09-27 2020-07-31 江西理工大学 用带磁性疏水颗粒提高微细粒硫化铜矿浮选回收率的方法
CN109078761B (zh) * 2018-09-27 2020-11-27 江西理工大学 一种利用磁性疏水颗粒强化难处理硫化镍矿浮选的方法
CN110216020B (zh) * 2019-04-23 2020-11-03 中南大学 一种荷电磁性疏水材料及其制备方法和应用

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS508718A (fr) * 1973-05-29 1975-01-29
WO1983001397A1 (fr) * 1981-10-26 1983-04-28 Snook, Harvey Flottation magnetique
US4643822A (en) * 1985-02-28 1987-02-17 The Secretary Of State For Trade And Industry In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Method of separation of material from material mixtures
JPS61281022A (ja) * 1985-06-06 1986-12-11 Tone Sangyo Kk 酸化鉄の不純物除去方法
US4834898A (en) 1988-03-14 1989-05-30 Board Of Control Of Michigan Technological University Reagents for magnetizing nonmagnetic materials
JPH02298284A (ja) * 1989-02-02 1990-12-10 Kunio Mori 金属表面の電気化学的表面処理法とその複合体
US5207996A (en) * 1991-10-10 1993-05-04 Minnesota Mining And Manufacturing Company Acid leaching of copper ore heap with fluoroaliphatic surfactant
CN1231650A (zh) * 1996-10-03 1999-10-13 Cytec技术有限公司 水性分散体
WO2000020470A2 (fr) * 1998-10-05 2000-04-13 Cytec Technology Corp. Dispersions aqueuses
MY137154A (en) * 2002-01-21 2008-12-31 Basf Ag Alkylglycol alkoxylates or alkyldiglycol alkoxylates, mixtures thereof with tensides and their use
US8033398B2 (en) 2005-07-06 2011-10-11 Cytec Technology Corp. Process and magnetic reagent for the removal of impurities from minerals
BRPI0814075A2 (pt) 2007-07-17 2015-02-03 Basf Se Processo para separar pelo menos um material hidrofóbico de uma mistura, e, uso de uma superfície sólida, hidrofóbica
UA97543C2 (uk) * 2007-09-03 2012-02-27 Басф Се Збагачення цінних руд за допомогою магнітних частинок
PL2212027T3 (pl) 2007-11-19 2012-08-31 Basf Se Magnetyczne rozdzielanie substancji na podstawie ich zróżnicowanych ładunków powierzchniowych
EP2090367A1 (fr) 2008-02-15 2009-08-19 Siemens Aktiengesellschaft Procédé et dispositif destinés au gain continu de minerais non magnétiques
AU2009272764B2 (en) 2008-07-18 2014-11-20 Basf Se Selective substance separation using modified magnetic particles
CN102099297B (zh) * 2008-07-18 2015-02-25 巴斯夫欧洲公司 改性氧化锌颗粒
US8434623B2 (en) 2008-07-18 2013-05-07 Basf Se Inorganic particles comprising an organic coating that can be hydrophilically/hydrophobically temperature controlled
BRPI0922451A2 (pt) * 2008-12-11 2015-12-15 Basf Se processo para separar pelo menos um primeiro material a partir de uma mistura.
CA2753486C (fr) 2009-02-24 2016-11-01 Basf Se Separation cu-mo
CN102341178B (zh) 2009-03-04 2015-06-03 西门子公司 通过多级式调节进行有色金属矿物的磁分离
US20110229384A1 (en) 2010-03-18 2011-09-22 Basf Se Concentrate quality in the enrichment of ug-2 platinum ore
US20110272623A1 (en) 2010-05-06 2011-11-10 Siemens Ag Formulation of hydrophobized magnetite
US8865000B2 (en) 2010-06-11 2014-10-21 Basf Se Utilization of the naturally occurring magnetic constituents of ores
US9376457B2 (en) 2010-09-03 2016-06-28 Basf Se Hydrophobic, functionalized particles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010100180A1 *

Also Published As

Publication number Publication date
UA103077C2 (uk) 2013-09-10
EP2403649B1 (fr) 2013-08-28
PL2403649T3 (pl) 2014-01-31
US8377313B2 (en) 2013-02-19
EA020958B1 (ru) 2015-03-31
CN102341179B (zh) 2014-08-13
US20110309003A1 (en) 2011-12-22
ZA201107236B (en) 2012-12-27
CA2752881A1 (fr) 2010-09-10
JP2012519073A (ja) 2012-08-23
AU2010220284A1 (en) 2011-09-08
CA2752881C (fr) 2017-07-04
MX2011009082A (es) 2011-09-27
PT2403649E (pt) 2013-11-07
AR076077A1 (es) 2011-05-18
EA201190196A1 (ru) 2012-06-29
CN102341179A (zh) 2012-02-01
ES2435631T3 (es) 2013-12-20
AU2010220284B2 (en) 2016-02-18
JP5683498B2 (ja) 2015-03-11
WO2010100180A1 (fr) 2010-09-10
BRPI1011516A8 (pt) 2017-10-03
PE20120731A1 (es) 2012-06-15
BRPI1011516A2 (pt) 2016-03-29

Similar Documents

Publication Publication Date Title
EP2403649B1 (fr) Agglomérats hydrophobes magnétiques
EP2190584B1 (fr) Traitement de minerais de valeur au moyen de particules magnétiques
EP2313200B1 (fr) Particules inorganiques comportant un revêtement organique pouvant être commuté hydrophile/hydrophobe sous l'effet de la température
EP2403648B1 (fr) Séparation magnétique de minerais métalliques non ferreux par conditionnement en plusieurs étapes
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
EP2376230B1 (fr) Enrichissement de minerais de valeur à partir de résidu minier (tailings)
EP2212027B1 (fr) Separation magnetique de substances sur la base de leurs charges superficielles differentes
EP2313201B1 (fr) Séparation sélective de substances au moyen de particules magnétiques modifiées
EP2171106A1 (fr) Procédé d'enrichissement de minerais au moyen de surfaces hydrophobes solides
WO2011058033A1 (fr) Procédé permettant de concentrer des composants séparés par magnétisme de suspensions de minerais et d'écluser ces composants hors d'un séparateur magnétique avec peu de pertes
EP2579987B1 (fr) Utilisation des composants magnétiques natifs de minerais
EP2841204B1 (fr) Séparation magnétique de particules comprenant un traitement en une étape d'une pâte

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: 20111004

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 MK MT NL NO PL PT RO SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SIEMENS AKTIENGESELLSCHAFT

Owner name: BASF SE

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 MK MT NL NO PL PT RO SE SI SK SM 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: AT

Ref legal event code: REF

Ref document number: 628983

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130915

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: 502010004508

Country of ref document: DE

Effective date: 20131031

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20131031

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: ES

Ref legal event code: FG2A

Ref document number: 2435631

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20131220

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

Ref country code: NO

Ref legal event code: T2

Effective date: 20130828

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20130828

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

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: 20131228

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: 20130828

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: 20130807

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: 20130828

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20130828

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: 20130828

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: 20130828

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: 20131129

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

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: 20130828

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: 20130828

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: 20130828

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: 20130828

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: 20130828

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: 20130828

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

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: 20130828

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502010004508

Country of ref document: DE

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

26N No opposition filed

Effective date: 20140530

REG Reference to a national code

Ref country code: NO

Ref legal event code: CHAD

Owner name: BASF SE, DE

REG Reference to a national code

Ref country code: PT

Ref legal event code: PC4A

Owner name: BASF SE, DE

Effective date: 20140825

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502010004508

Country of ref document: DE

Effective date: 20140530

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 502010004508

Country of ref document: DE

Owner name: BASF SE, DE

Free format text: FORMER OWNERS: BASF SE, 67063 LUDWIGSHAFEN, DE; SIEMENS AKTIENGESELLSCHAFT, 80333 MUENCHEN, DE

Effective date: 20140821

Ref country code: DE

Ref legal event code: R081

Ref document number: 502010004508

Country of ref document: DE

Owner name: BASF SE, DE

Free format text: FORMER OWNER: BASF SE, SIEMENS AKTIENGESELLSCHAFT, , DE

Effective date: 20140821

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

Owner name: BASF SE

Effective date: 20141006

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140303

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: 20140303

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20141128

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Ref country code: GB

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

Effective date: 20140303

Ref country code: CH

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

Effective date: 20140331

Ref country code: IE

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

Effective date: 20140303

Ref country code: LI

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

Effective date: 20140331

Ref country code: FR

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

Effective date: 20140331

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: 20130828

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

Ref country code: SM

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: 20130828

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

Ref country code: NO

Payment date: 20160329

Year of fee payment: 7

Ref country code: TR

Payment date: 20160303

Year of fee payment: 7

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 628983

Country of ref document: AT

Kind code of ref document: T

Effective date: 20150303

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130828

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

Ref country code: PL

Payment date: 20160224

Year of fee payment: 7

Ref country code: FI

Payment date: 20160324

Year of fee payment: 7

Ref country code: PT

Payment date: 20160218

Year of fee payment: 7

Ref country code: RO

Payment date: 20160301

Year of fee payment: 7

Ref country code: SE

Payment date: 20160329

Year of fee payment: 7

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: 20130828

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140331

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; INVALID AB INITIO

Effective date: 20100303

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

Ref country code: ES

Payment date: 20160422

Year of fee payment: 7

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: 20150303

REG Reference to a national code

Ref country code: NO

Ref legal event code: MMEP

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

Ref country code: RO

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

Effective date: 20170303

Ref country code: FI

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

Effective date: 20170303

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: SE

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

Effective date: 20170304

Ref country code: PT

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

Effective date: 20170904

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

Ref country code: NO

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

Effective date: 20170331

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

Ref country code: MK

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: 20130828

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20180703

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: 20170304

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: 20170303

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

Ref country code: DE

Payment date: 20220329

Year of fee payment: 13

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: 20170303

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502010004508

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: 20231003