EP2313200B1 - Particules inorganiques comportant un revêtement organique pouvant être commuté hydrophile/hydrophobe sous l'effet de la température - Google Patents

Particules inorganiques comportant un revêtement organique pouvant être commuté hydrophile/hydrophobe sous l'effet de la température Download PDF

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Publication number
EP2313200B1
EP2313200B1 EP09780763A EP09780763A EP2313200B1 EP 2313200 B1 EP2313200 B1 EP 2313200B1 EP 09780763 A EP09780763 A EP 09780763A EP 09780763 A EP09780763 A EP 09780763A EP 2313200 B1 EP2313200 B1 EP 2313200B1
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EP
European Patent Office
Prior art keywords
polymeric compound
temperature
substance
lcst
magnetic
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EP09780763A
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German (de)
English (en)
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EP2313200A1 (fr
Inventor
Imme Domke
Alexej Michailovski
Norbert Mronga
Hartmut Hibst
Jürgen Tropsch
Susanne Stutz
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BASF SE
Siemens AG
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BASF SE
Siemens AG
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Priority to PL09780763T priority patent/PL2313200T3/pl
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/44—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/0036—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
    • H01F1/0045—Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use
    • H01F1/0054—Coated nanoparticles, e.g. nanoparticles coated with organic surfactant

Definitions

  • the present invention relates to a process for the separation of at least one first substance from a mixture containing said first material and at least one second substance, wherein the mixture to be separated is first contacted with at least one selective hydrophobizing agent so that the at least one hydrophobizing agent and forming at least one first material an adduct, then contacting said adduct with at least one magnetic particle functionalized at the surface with at least one polymeric compound having a LCST (Lower Critical Solution Temperature) at a temperature at which the polymeric compound hydrophobic character, so that the adduct and the at least one functionalized magnetic particle agglomerate, this agglomerate is separated by applying a magnetic field, and the agglomerate is finally cleaved by a temperature is set at de the polymeric compound has a hydrophilic character.
  • LCST Lower Critical Solution Temperature
  • 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.
  • mixtures of substances for example ores
  • substances to be separated for example sulphidic compounds
  • a selective hydrophobizing agent in order to hydrophobize them on the surface.
  • These hydrophobized substances can then be separated by means of magnetic particles functionalized on the surface with a polymeric compound having an LCST.
  • These polymeric compounds have hydrophobic character above the LCST and hydrophilic character below the LCST, or vice versa.
  • the present invention relates to a method for enriching ores in the presence of gait.
  • WO 02/0066168 A1 relates to a process for the separation of ores from mixtures containing them, in which suspensions or slurries of these mixtures are treated with particles which are magnetic and / or buoyant in aqueous solutions. After addition of the magnetic and / or buoyant particles, a magnetic field is applied so that the agglomerates are separated from the mixture.
  • the degree of attachment of the magnetic particles to the ore and the strength of the bond is not sufficient to perform the process with sufficiently high yield and effectiveness.
  • US 4,657,666 discloses a method for enrichment of ores where the ginger ore is reacted with magnetic particles to form agglomerates due to the hydrophobic interactions.
  • the magnetic particles are hydrophobized by treatment with hydrophobic compounds on the surface, so that a connection to the value ore takes place.
  • 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. Separation of ore and magnetic particles occurs in this process by destroying the surface-activating substance which has been applied to the ore in the form of the surface-activating solution.
  • a disadvantage of this method is that, if necessary, a surface-activating substance is added, the degradation products of which remain in the ore and may possibly interfere with further process steps.
  • US 4,834,898 discloses a method of separating non-magnetic materials by contacting them with magnetic reagents having two layers are enveloped by surface-active substances.
  • the attachment of the thus modified magnetic reagents to the non-magnetic materials is based on an interaction of the coating of the magnetic particles with the non-magnetic materials.
  • thermosensitive polymers that are homogeneously in solution below the Lower Critical Solution Temperature (LCST), while when this temperature is exceeded, a heterogeneous biphasic mixture forms. Furthermore, applications of these targeted drug delivery polymers are disclosed.
  • LCST Lower Critical Solution Temperature
  • Crespy et al., Polymer International (2007), 56 (12), 1461-1468 also disclose polymers which show hydrophilic or hydrophobic behavior depending on the ambient temperature. Furthermore, the use of these polymers in textiles and for the targeted release of pharmaceutically active substances is disclosed.
  • EP 1 316 599 A discloses a process for the preparation of magnetic particles having on its surface polymers having an UCST (Upper Critical Solution Temperature). These functionalized particles can be used for purification, detection or concentration of nucleic acids or enzymes or as separation reagents. As examples of substances which can be separated by the magnetic particles, there are mentioned avidin, avidinylated enzymes or biotinylated enzymes.
  • DE 195 16 323 A1 discloses a process for preparing magnetizable dispersions and their use. According to page 4, from line 28 these are iron-containing particles which are functionalized on the surface with various compounds. These compounds are attached, for example via a carboxylic acid functionality to the iron-containing particles. Subsequently, the compounds have 2 to 6 units of ethylene oxide. The other end of the polymeric compound has either a hydroxy or a carboxylic acid group.
  • the object of the present invention is to provide a method by which at least one first substance can be efficiently separated from mixtures comprising these at least one first substance and at least one second substance. Furthermore, it is an object of the present invention to provide a method in which it is possible to be able to split the agglomerate of magnetic particles and the first material to be separated in the meantime easily and as completely as possible. Furthermore, the bond between the first material to be separated and magnetic particles should be sufficiently stable to ensure a high yield of first material upon separation.
  • the at least one first substance and the at least one second substance can be separated from one another by the method according to the invention, since according to the invention at least one between hydrophobic and hydrophilic switchable functionalized magnetic particles is added under conditions to the mixture, among which at least one first hydrophobized material and the at least one functionalized magnetic particle forms an agglomerate which can be separated by applying a magnetic field.
  • the method according to the invention generally serves to separate at least one first substance from a mixture comprising this at least one first substance and at least one second substance.
  • the mixture may also contain other substances.
  • the at least one first material to be separated off is preferably a metal compound selected from the group consisting of sulfide ores, oxidic and / or carbonate ores, for example azurite [Cu 3 (CO 3 ) 2 (OH) 2 ], or malachite [Cu 2 [(OH ) 2
  • the at least one material to be separated off can be selected from the group of the noble metals and their compounds, for example Au, Pt, Pd, Rh, etc., preferably in a solid state.
  • sulfidic ores which can be used according to the invention are selected from the group of sulfide non-ferrous metals, for example copper ores such as covellite CuS, chalcopyrite CuFeS 2 , bornite Cu 5 FeS 4 , chalcocite Cu 2 S or mixtures thereof, molybdenum ores such as molybdenum (IV ) sulfide molybdenum MoS 2 , iron sulfides such as FeS / FeS 2 , nickel ores such as NiS, lead ores such as PbS, zinc ores such as ZnS or mixtures thereof:
  • copper ores such as covellite CuS, chalcopyrite CuFeS 2 , bornite Cu 5 FeS 4 , chalcocite Cu 2 S or mixtures thereof
  • molybdenum ores such as molybdenum (IV ) sulfide molybdenum MoS 2
  • iron sulfides such as FeS / FeS
  • oxidic compounds of metals and semimetals for example borates or other salts of metals and semimetals, for example phosphates, sulfates or oxides / hydroxides / carbonates and further salts, may be present in the ore mixtures to be treated according to the invention, for example azurite [Cu 3 (CO 3 ) 2 (OH) 2 ], malachite [Cu 2 [(OH) 2 (Co 3 )]].
  • untreated ore mixtures are preferably used, which are obtained from mine deposits.
  • the mixture containing at least one first substance and at least one second substance in step (A) is in the form of particles having a size of 100 nm to 100 ⁇ m, see for example US 5,051,199 , In a preferred embodiment, this particle size becomes obtained by grinding. Suitable methods and devices are known to the person skilled in the art, for example wet milling in a ball mill.
  • the mixture containing at least one first substance and at least one second substance before or during step (A) to particles having a size of 100 nm to 500 .mu.m, preferably 100 nm to 100 microns milled.
  • Preferably usable ore mixtures have the highest possible content of sulfidic minerals.
  • 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 method according to the invention comprises contacting the mixture containing the at least one first substance and at least one second substance with at least one selective hydrophobizing agent in a suitable suspending agent, so that the at least one hydrophobizing agent and the at least one first substance but not forms with the at least one second substance, an adduct.
  • the first step of the process according to the invention serves to hydrophobize the at least one first substance on the surface so that in the following step (B) it agglomerates with the at least one functionalized magnetic particle.
  • hydrophobing agent means a substance which is capable of hydrophobizing the surface of the at least one first substance in the presence of the other particles which are not to be separated, ie of modifying the surface of the hydrophobized one at least one first substance has a contact angle of> 90 ° with water against air.
  • “Selective” in the context of the present invention means that the distribution coefficient of the hydrophobing agent between the surface of the at least one first substance and the surface of the at least one second substance, in general> 1, preferably> 100, particularly preferably> 10000, d. h., That the hydrophobizing agent preferably on the surface of the at least one first substance, and not on the surface of the at least one second substance, attached.
  • A is a linear or branched C 6 -C 16 -alkyl, for example 2-propyl-heptyl.
  • heteroatoms according to the invention are selected from N, O, P, S and halogens such as F, Cl, Br and I.
  • the anions mentioned and the corresponding cations form neutral charged compounds of the general formula (I) according to the invention.
  • Dithiophosphinat [- (X) n] 2 P 2 -, - [(X) n] 2 POS - or dithiophosphate [- (X) n] 2 PO 2 - are present at these functional groups attached two radicals A, the, in the context of the above meanings may be the same or different, preferably equal and selected from C 6 -C 30 , more preferably C 6 -C 16 alkyl.
  • Z is [- (X) n] 2 P 2 -, - (X) n -CS 2 -, - [(X) n] 2 PO 2 -, or - (X) n -S - where X is O and n is 0 or 1 and a cation selected from hydrogen, sodium or potassium.
  • hydrophobizing agents are mono-, di- and trithiols or 8-hydroxyquinolines, for example described in US Pat EP 1200408 B1 ,
  • metal oxides for example FeO (OH), Fe 3 O 4 , ZnO etc.
  • carbonates for example azurite [Cu (CO 3 ) 2 (OH) 2 ], malachite [Cu 2 [(OH) 2 CO 3 ]]
  • C 6 -C 16 -alkylphosphonic acids for example octylphosphonic acid (OPS), mono- and dialkyl esters of phosphoric acid with a C 6 -C 20 -alkyl radical, hydroxamates, and long-chain carboxylic acids (fatty acids).
  • OPS octylphosphonic acid
  • particularly preferred water repellents are mono-, di- and trithiols, xanthates, dithiophosphinates or mono-, di- or tri-C 6 -C 30 -alkyl esters of thiophosphoric acids of the general formula (VII) in which R independently of one another denote hydrogen or C 6 -C 30 -alkyl and X independently of one another denote S or O, where one to three of the XS present and the remaining O mean
  • Very particularly preferred surface-active substances are 1-octanethiol, potassium octylxanthate, octylphosphonic acid, phosphoric acid monooctyl ester or a compound of the general formula (IV) with the meanings given above for A.
  • step (A) of the process according to the invention can be carried out by all methods known to the person skilled in the art.
  • the mixture to be treated, the at least one hydrophobing agent and the suspending agent in the appropriate amounts are added together and mixed.
  • the mixing can be done for example by wet milling. Suitable mixing apparatuses are known to the person skilled in the art, for example mills, such as ball mill.
  • the suspending agent is generally added in step (A) in an amount such that the suspension obtained has a solids content of from 0.1 to 80% by weight, preferably from 20 to 40% by weight.
  • suspending agents known to those skilled in the art can be used in the process according to the invention, i. H. Suspending agents in which the mixture of step (A) is not completely soluble.
  • the suspending agent is an aqueous mixture, i. H. a mixture containing at least 80% by weight, preferably at least 95% by weight, of water.
  • the suspending agent in step (A) is water.
  • the suspending agent may contain, in addition to water, other components, for example selected from the group consisting of water-soluble organic compounds such as alcohols having 1 to 4 carbon atoms, ketones such as acetone and mixtures thereof, soluble salts such as NaCl, KCl, MgCl 2 , CaCl 2 , Na 2 CO 3 , K 2 CO 3 , MgCO 3 , inorganic acids and bases such as NaOH, KOH, Ca (OH) 2 , HCl, H 2 SO 4 , HNO 3 , organic acids and bases such as formic acid or acetic acid, etc.
  • water-soluble organic compounds such as alcohols having 1 to 4 carbon atoms, ketones such as acetone and mixtures thereof
  • soluble salts such as NaCl, KCl, MgCl 2 , CaCl 2 , Na 2 CO 3 , K 2 CO 3 , MgCO 3
  • inorganic acids and bases such as NaOH, KOH, Ca (OH) 2 , HCl
  • Step (A) of the process according to the invention is generally carried out at a temperature of 1 to 80 ° C, preferably at 40 to 60 ° C.
  • the at least one water repellent is generally used in an amount sufficient to achieve the desired effect.
  • the at least one hydrophobizing agent is in an amount from 0.01 to 5 wt .-%, in each case based on the present in the mixture at least one first material.
  • step (A) is a mixture in suspension before containing an adduct of at least a first material and at least one hydrophobizing agent, and at least one second material.
  • Step (B) of the process of the invention comprises contacting the adduct of step (A) with at least one magnetic particle functionalized on the surface with at least one polymeric compound having a lower critical solution temperature (LCST) at a temperature, wherein the polymeric compound has hydrophobic character such that the adduct of step (A) and the at least one functionalized magnetic particle agglomerate.
  • LCST critical solution temperature
  • magnetic particles it is generally possible to use all magnetic particles known to the person skilled in the art which satisfy the requirements of the process according to the invention, for example suspensibility in the optionally used suspending agent and ability to be functionalized with the at least one polymeric compound.
  • the magnetic particle should have a sufficiently high saturation magnetizability, for example 25-300 emu / g, and a low remanence, so that the adduct can be separated from the suspension in a sufficient amount in step (D) of the process according to the invention.
  • the at least one magnetic particle is magnetite Fe 3 O 4 or cobalt ferrite Co 2+ x Fe 2+ 1-x Fe 3+ 2 O 4 with x ⁇ 1, for example CO 2 .25 Fe 2, 75 o 4 .
  • the size of the magnetic particles used according to the invention is preferably from 10 nm to 1 .mu.m.
  • the at least one magnetic particle is functionalized on the surface with at least one polymeric compound.
  • the polymeric compounds used according to the invention are characterized in that they have a transition temperature LCST (Lower Critical Solution Temperature). Below this LCST, the polymeric compound has a hydrophilic character since the polymer chain has a hydration shell, for example due to addition of water molecules. Above the LCST, the polymeric compound has a hydrophobic character, since the polymer chain is no longer surrounded by a hydrate shell, for example. Depending on the polymeric compound, the reverse case is also possible, namely that the polymeric compound below the LCST has a hydrophobic character and has a hydrophilic character above the LCST.
  • LCST Lower Critical Solution Temperature
  • the polymeric compound When such a polymeric compound is heated from below the LCST to a temperature above the LCST, the polymeric compound switches from hydrophilic to hydrophobic in the LCST, or vice versa.
  • the polymers which can be used according to the invention depending on the temperature, have a hydrophilic or hydrophobic character.
  • the change of the polymeric compound from hydrophobic to hydrophilic or vice versa corresponds to a phase transition, which takes place in a closed system generally in a narrow temperature range, for example 0.5 ° C.
  • the phase transition may extend over a broader range of, for example, 15 ° C, by changing the concentration of the present components, for example, polymers and / or impurities, varying the pH and / or pressure.
  • the temperature range at which the transition occurs generally increases with increasing chain length.
  • the properties described for the polymeric compounds which can be used according to the invention are essentially correspondingly also present in the case of the particles modified with these polymeric compounds, in particular magnetic particles.
  • the polymeric compound above the LCST is hydrophobic and hydrophilic below the LCST.
  • polymer means a, preferably organic, compound having a molecular weight of at least 500 g / mol, preferably 500 to 10000 g / mol, particularly preferably 1000 to 7000 g / mol.
  • the at least one polymeric compound is selected from the group consisting of polyvinyl ethers, for example polyvinylmethylethers, poly-N-alkylacrylamides, for example poly-NC 1 -C 6 -alkylacrylamides, in particular polyvinylethers.
  • Suitable polymeric compounds and processes for their preparation are, for example, in Li et al., International Journal of Pharmacology (2006), 2 (5), 513-519 , and Crespy et al., Polymer International (2007), 56 (12), 1461-1468 , called. These polymeric compounds have hydrophobic character below the LCST and hydrophobic character above the LCST.
  • polymeric compounds which have an LCST are bound by functional groups to the corresponding magnetic particles.
  • These functional groups can be present in said polymeric compounds per se, or the functional groups can be introduced into the polymeric compounds by methods known to those skilled in the art, ie the polymeric compounds are functionalized.
  • Suitable functional groups are those which ensure a sufficiently strong bond between magnetic particle and polymeric compound, for example selected from the group consisting of thiol group -SH, carboxylic acid group -CO 2 H, optionally at least partially esterified phosphonic acid group -PO 3 R ' 2 with R' same Hydrogen or C 1 -C 6 -alkyl (Va), optionally at least partially esterified phosphoric acid group -O-PO 3 R " 2 with R "equal to hydrogen or C 1 -C 6 -alkyl (Vb), hydroxamate group (Vc), xanthate group (Vd) and mixtures thereof, more preferably selected from the group consisting of thiol group -SH, carboxylic acid group -CO 2 H, optionally at least partially esterified phosphonic acid group -PO 3 R ' 2 with R' equal to hydrogen or C 1 -C 6 -alkyl (Va), optionally at least partially esterified phosphoric acid group -O-PO 3
  • F represents a functional group which selectively binds to the at least one magnetic particle.
  • the choice of this functional group depends on the at least one magnetic particle to which the functional group is to bind. It is preferable to form a dissociation-stable bond between the at least one magnetic particle and the at least one polymeric compound of general formula (III).
  • F is selected from the group consisting of carboxylic acid group -CO 2 H, optionally at least partially esterified phosphonic acid group -PO 3 R ' 2 with R' equal to hydrogen or C 1 -C 6 alkyl (Va), optionally at least partially esterified Phosphoric acid group -O-PO 3 R “ 2 with R” equal to hydrogen or C 1 -C 6 -alkyl (Vb), hydroxamate group (Vc), xanthogenate group (Vd) and mixtures thereof, particularly preferably an optionally at least partially esterified phosphonic acid group (Va) or an optionally at least partially esterified phosphoric acid group (Vb).
  • the binding of the functional groups Va to Vd to the polymer preferably takes place via lone-pair electrons.
  • B represents an alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, propyl, butyl, for example, n-butyl, pentyl, hexyl.
  • the polymeric compounds of the general formula (III) have an LCST which is generally in each case dependent on the amount of the individual alkylene oxides, ie. H. Ethylene oxide, propylene oxide and / or butylene oxide, is dependent in the polymer.
  • a polymeric compound composed solely of propylene oxide has an LCST of ⁇ -10 ° C.
  • a polymeric compound which is composed exclusively of ethylene oxide, for example, has an LCST of> 120 ° C.
  • the LCST of the polymeric compound used in the process according to the invention is -10 to 100 ° C, more preferably 5 to 45 ° C, most preferably 20 to 40 ° C.
  • the LCST of a polymeric compound is in a temperature range of about 5 to 15 ° C.
  • the width of this area is generally dependent on uniformity, i. H. the monodispersity, the polymeric compound used. The higher the monodispersity, the narrower the range of the LCST.
  • the functionalization of the at least one magnetic particle with the at least one polymeric compound can be carried out by all methods known to the person skilled in the art.
  • the at least one magnetic particle is functionalized with the at least one polymeric compound by first preparing the magnetic particle itself by known methods. Then, this magnetic particle is modified by contacting a solution of the functionalized polymeric compound, in particular compounds of the general formula (III), in water or in an organic solvent, for example low molecular weight alcohols or ketones, and the product obtained is used to remove excess polymeric compound washed with an appropriate solvent.
  • step (B) The contacting of the adduct from step (A) with at least one functionalized magnetic particle in step (B) can be carried out by all methods known to the person skilled in the art.
  • the at least one functionalized magnetic particle is added to the mixture of step (A).
  • step (B) is carried out in a mill, more preferably in the same mill in which step (A) has been carried out.
  • the heat generated when milling the components in step (B) is used to achieve the temperature necessary for step (A) in the mixture, preferably in the case where the polymeric compound is hydrophobic above its LCST.
  • Step (B) of the process according to the invention is carried out at a temperature at which the polymeric compound used has a hydrophobic character so that the switchably functionalized magnetic particle and the hydrophobized at least one first material agglomerate.
  • this temperature may be above or below the LCST, preferably the temperature is above the LCST.
  • step (B) is conducted at a temperature greater than the LCST of the polymeric compound and less than the boiling point of the suspending agent used. More preferably, step (B) is carried out at a temperature which is 1 to 20 ° C above the LCST. Thus, in a preferred embodiment, step (B) is carried out at a temperature of 6 to 65 ° C, more preferably 21 to 60 ° C.
  • step (B) of the inventive method is carried out at a temperature which is above the melting temperature of the suspending agent used and below the LCST of the polymeric compound.
  • step (B) is carried out at a temperature which is 1 to 20 ° C below the LCST.
  • step (B) is thus preferably carried out at a temperature of from -15 to 44.degree. C., more preferably from 0 to 39.degree.
  • Step (B) of the process according to the invention is preferably carried out until a sufficient amount of agglomerate of at least one hydrophobized first material and switchable functionalized magnetic particles is formed, for example in a proportion of 80 to 100%, preferably completely (100%).
  • agglomerates of magnetic particles functionalized on the surface with at least one polymeric compound and at least one hydrophobicized first substance are present in addition to at least one second substance and optionally further substances in a suspending agent.
  • the optional step (C) of the process of the invention comprises (C) the addition of further suspending agent to the mixture obtained in step (B).
  • Step (C) is preferably carried out when, in step (A), a suspension has been provided whose solids content is too high for the following steps (D) and (E), such that, for example, the mobility of those formed in step (B) Agglomerates in the suspension is not sufficient.
  • step (C) of the process according to the invention all suspending agents which have already been mentioned with regard to step (A) are suitable as suspending agents.
  • an aqueous mixture i. H. a mixture containing at least 80% by weight, preferably at least 95% by weight, of water.
  • the aqueous mixture may additionally contain the components referred to in step (A).
  • water is added in step (C) of the process according to the invention.
  • Step (C) of the process according to the invention is generally carried out at a temperature at which the agglomerate formed in step (B) from at least one hydrophobized substance and the functionalized magnetic particle is not cleaved.
  • step (C) is carried out at a temperature greater than the LCST of the polymeric compound and less than the boiling point of the suspending agent used is. More preferably, step (C) is carried out at a temperature which is 1 to 20 ° C above the LCST. Thus, in a preferred embodiment, step (C) is carried out at a temperature of 6 to 65 ° C, more preferably 21 to 60 ° C.
  • step (C) of the inventive method is carried out at a temperature which is above the melting temperature of the suspending agent used and below the LCST of the polymeric compound.
  • step (C) is carried out at a temperature which is 1 to 20 ° C below the LCST.
  • step (C) is thus preferably carried out at a temperature of -15 to 44 ° C, more preferably 0 to 39 ° C.
  • the amount of suspending agent according to the invention can be chosen so that in step (C) a suspension is obtained which is easy to stir and / or convey.
  • a suitable suspending agent is added so that a solids content of the resulting suspension of 0.1 to 80 wt .-%, particularly preferably 0.1 to 40 wt .-% results.
  • Step (D) of the process according to the invention comprises separating the agglomerate present in the suspension from step (B) or (C) by applying a magnetic field.
  • Step (D) may be carried out in a preferred embodiment by introducing a permanent magnet into the reactor in which the suspension from step (B) or (C) is located.
  • a permanent magnet In a preferred embodiment is located between the permanent magnet and the mixture to be treated, a partition wall of non-magnetic material, such as the wall of the reactor.
  • an electrically switchable magnet is used in step (D) which is magnetic only when an electric current flows. Suitable devices are known in the art.
  • Step (D) of the process according to the invention is generally carried out at a temperature at which the agglomerate formed in step (B) from at least one hydrophobized substance and the functionalized magnetic particle is not cleaved.
  • step (D) is preferably carried out at a temperature which is greater than the LCST of the polymeric compound and less than the boiling point of the suspending agent used. Particularly preferably, step (D) is carried out at a temperature which is 1 to 20 ° C above the LCST. Thus, in a preferred embodiment, step (D) is carried out at a temperature of 6 to 65 ° C, more preferably 21 to 60 ° C.
  • step (D) of the inventive method is carried out at a temperature which is above the melting temperature of the suspending agent used and below the LCST of the polymeric compound.
  • step (D) is carried out at a temperature which is 1 to 20 ° C below the LCST.
  • step (D) is thus preferably carried out at a temperature of -15 to 44 ° C, particularly preferably 0 to 39 ° C.
  • steps (B), (C) and (D) can be carried out at the same temperature, it is according to the invention also possible that the steps at different temperatures, in the specified ranges, are performed.
  • step (D) the mixture is mixed, preferably permanently, with a suitable device.
  • step (D) the components remaining in the suspension after treatment with a magnet may optionally be separated by any means known to those skilled in the art, for example by draining the portions of the suspension which are not captured by the magnet from the bottom valve of step by step (D) used reactor or pumping the not captured by the at least one magnet portions of the suspension.
  • the agglomerate formed in step (B) of the process according to the invention consists of at least one functionalized magnetic particle and the at least one hydrophobized first substance on the magnet or on a wall which is located between magnet and adduct.
  • the adduct may be removed from the magnet by shutting off the electrical current so that there is no more magnetic field gradient. If there is a wall between the magnet and the suspension, then the adduct can be removed by methods known to those skilled in the art.
  • Step (E) of the process of the present invention comprises cleaving the agglomerate separated in step (D) by adjusting a temperature at which the polymeric compound has a hydrophilic character to obtain the at least one first substance.
  • step (E) of the process according to the invention is set.
  • step (E) of the process of the invention is carried out at a temperature which is above the melting temperature of the suspending agent employed and below the LCST of the polymeric compound.
  • step (E) is carried out at a temperature which is 1 to 20 ° C below the LCST.
  • step (E) is thus preferably carried out at a temperature of -15 to 44 ° C, particularly preferably 0 to 39 ° C.
  • step (E) is carried out at a temperature which is greater than the LCST of the polymeric compound and less than the boiling point of the suspending agent used. Particularly preferably, step (E) is carried out in this case at a temperature which is 1 to 20 ° C above the LCST. Thus, in a preferred embodiment, step (D) is carried out at a temperature of 6 to 65 ° C, more preferably 21 to 60 ° C.
  • the polymeric compound has hydrophilic character, i. there can be no hydrophobic interactions between the polymeric compound on the surface of the at least one magnetic particle and the hydrophobized first material, so that the agglomerates are cleaved.
  • Step (E) of the process according to the invention is carried out until the agglomerates present are cleaved as completely as possible, for example to a proportion of 70 to 99%, preferably 80 to 98%.
  • the at least one functionalized magnetic particle and the at least one hydrophobized first substance are suspended Form before. These two substances can be separated from one another and from the suspending agent by all methods known to those skilled in the art.
  • the at least one magnetic particle is preferably separated from the suspension containing this at least one magnetic particle and the at least one first material by a permanent or switchable magnet. Details of this separation are analogous to step (D) of the method according to the invention. Preferably, after this separation, the at least one first substance is present in suspended form, while the at least one magnetic particle adheres to the magnet.
  • the first material to be separated is separated from the suspending agent by distilling off the suspending agent or filtration.
  • the first substance thus obtained can be purified by further methods known to the person skilled in the art.
  • the suspending agent may, optionally after purification, be recycled back to the process of the invention.
  • the at least one magnetic particle is recycled in step (A) of the process according to the invention.
  • P generally denotes a particle containing at least one metal or semimetal, preferably in oxidic or sulfidic form.
  • particles which contain at least one metal in oxidic form are, for example, selected from the group consisting of secondary or main group metal oxides, for example CuO, ZnO, Cr 2 O 3 , Fe 2 O 3 , TiO 2 , SiO 2 , CeO 2 , Titanates, for example BaTiO 3 , SrTiO 3 and mixtures thereof.
  • secondary or main group metal oxides for example CuO, ZnO, Cr 2 O 3 , Fe 2 O 3 , TiO 2 , SiO 2 , CeO 2 , Titanates, for example BaTiO 3 , SrTiO 3 and mixtures thereof.
  • Examples of particles containing at least one metal in sulfidic form are, for example, selected from the group consisting of subgroup metal sulfides, for example CuS, Zn 1-x Mn x S with 0 ⁇ x ⁇ 0.22, chalcopyrite (copper pyrites) CuFeS 2 , bornite Cu 5 FeS 4 , chalcocite Cu 2 S or mixtures thereof, molybdenum (IV) sulfide molybdenum MoS 2 , iron sulfides such as FeS / FeS 2 , nickel sulfide such as NiS, lead sulfide such as PbS, zinc sulfide such as ZnS, CdS, CdSe, CdTe or mixtures thereof.
  • subgroup metal sulfides for example CuS, Zn 1-x Mn x S with 0 ⁇ x ⁇ 0.22
  • chalcopyrite (copper pyrites) CuFeS 2 , bornit
  • metals contained in the particle P are platinum and coin metals such as copper, silver, gold, iron, cobalt, nickel and their alloys.
  • semiconducting materials selected from the group consisting of Ge, Si, ⁇ -Sn, C, for
  • P is selected from the group consisting of magnetite Fe 3 O 4 , cobalt ferrite Co 2+ x Fe 2+ 1-x Fe 3+ 2 O 4 with x ⁇ 1, for example Co 0.25 Fe 2.75 O 4 , and mixtures thereof.
  • the size of the particle present in the adduct of the general formula (IV) according to the invention is preferably from 5 nm to 100 ⁇ m, more preferably from 10 nm to 50 ⁇ m.
  • F is a functional group which, preferably selectively, binds to the particle P.
  • F is for example selected from the group consisting of thiol group -SH, carboxylic acid group -CO 2 H, optionally at least partially esterified phosphonic acid group -PO 3 R ' 2 with R' equal to hydrogen or C 1 -C 6 alkyl (Va), optionally at least partially esterified phosphoric acid group -O-PO 3 R " 2 with R” equal to hydrogen or C 1 -C 6 -alkyl (Vb), hydroxamate group (Vc), xanthate group (Vd) and mixtures thereof, particularly preferably an optionally at least partially esterified phosphonic acid group (Va) or optionally at least partially esterified phosphoric acid group (Vb).
  • oxidic particles P especially functional groups selected from carboxylic acid group -CO 2 H, optionally at least partially esterified phosphonic acid group -PO 3 R ' 2 with R' is hydrogen or C 1 -C 6 alkyl (Va), optionally at least partially esterified phosphoric acid group - O-PO 3 R “ 2 with R” equal to hydrogen or C 1 -C 6 alkyl (Vb) or hydroxamate (Vc) suitable.
  • sulfidic particles P in particular functional groups selected from thiol group -SH and xanthate group (Vd) are suitable.
  • B in the compound of the general formula (VI) denotes an alkyl radical having 1 to 6 carbon atoms, for example methyl, ethyl, propyl, butyl, for example n-butyl, pentyl or hexyl.
  • q in the compound of general formula (VI) is an integer of 1 to 1 x 10 15 , preferably 1 x 10 3 to 1 x 10 12 .
  • q in the general formula (VI) describes the number of molecules of the polymeric compound bound to a particle P. These values correspond to a maximum occupation density of the particle P of 1.67 ⁇ 10 -6 mol / m 2 , preferably 1 to 100% of the maximum occupation density.
  • the number of polymer molecules attached to a particle P can be controlled by the amount of polymeric compound in the manufacturing process.
  • the number of polymer molecules per particle P can be determined by methods known to the person skilled in the art, for example electron resonance analysis.
  • Functionalized particles of the general formula (VI) can be prepared by processes known to those skilled in the art, for example by contacting a solution of the polymeric compound of the general formula (III) in water or an organic solvent, preferably water, low molecular weight alcohols or ketones and washing the resulting Product with the appropriate solvent to remove excess polymeric compound.
  • Functionalized particles according to the general formula (VI) can be used to separate at least one first substance from a substance mixture comprising the at least one first substance and at least one second substance, for example by the process according to the invention.
  • the present invention therefore also relates to the use of a functionalized particle according to the general formula (VI) for the separation of mixtures of substances. With respect to the mixtures and the other parameters of the separation of substances, the above applies.
  • the functionalizing agent is prepared by reacting an alkoxylate of the formula n-Bu- (PO) 22 -OH (Pluriol A1350P, BASF SE) with polyphosphoric acid (ThermPhos) by methods known to the person skilled in the art.
  • the transition range from hydrophilic to hydrophobic is found at 15-26 ° C.
  • the alkoxylate n-Bu- (PO) 22 -OH used has an OH number (OHN) of 46.3 and a molecular weight of 1213 g / mol.
  • Alkoxylate and polyphosphonic acid are reacted at 80 ° C. for 31.7 h. After 29 h, a conversion of 72% is determined by means of titration, the acid number is 102 mg KOH / g.
  • a suspension of 100 mg of the product obtained in Example 1 in 10 ml of water (about 10 ° C) is prepared. 2 g of magnetite (Magnetic Black 345, BASF, 0 4 ⁇ m) are stirred with the suspension for 15 minutes, filtered off, washed with 50 ml of cold water (T ⁇ 10 ° C.) and dried in vacuo at 80 ° C.
  • magnetite Magnetic Black 345, BASF, 0 4 ⁇ m
  • a suspension of 54 g of quartz powder (SiO 2 , Microsil type S8 from Euroquarz), 2 g of Cu 2 S, (325 mesh, Aldrich) and 1000 g of process water is placed in a beaker with stirring. 0.13 g of potassium 1-octylxanthate and 0.08 g of Shellsol 40 are added to the suspension. The suspension is stirred for 1 h with a paddle stirrer (35 rpm) and then heated to 45 ° C. with stirring. 2 g of the hydrophilic / hydrophobic switchable magnetite from Example 2 are added with stirring. The suspension is stirred for a further 30 minutes at 45.degree.
  • the suspension is guided past several permanent magnets behind glass.
  • the magnetic components are held on the magnet, the remainder of the suspension is collected, filtered off, dried and analyzed for Cu content (fraction A1).
  • the magnetic components After removal of the permanent magnets, the magnetic components are suspended in cold water (10 ° C.) and redirected past the magnet. The effluent is collected, filtered off, dried and analyzed for Cu content (fraction A2).

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Abstract

L'invention concerne un procédé de séparation d'au moins une première substance contenue dans un mélange renfermant cette ou ces premières substances et au moins une deuxième substance. Le procédé comporte les étapes suivantes : (A) mise en contact du mélange renfermant la ou les premières substances et au moins une deuxième substance, avec au moins un agent hydrophobant sélectif en présence d'un agent de suspension, de telle manière qu'un adduit se forme à partir du ou des agents hydrophobants et de la ou des premières substances, et non à partir de la ou des deuxièmes substances; (B) mise en contact de l'adduit de l'étape (A) avec au moins une particule magnétique fonctionnalisée à sa surface avec au moins un composé polymère présentant une température de transition LCST (température critique de solubilité inférieure), à une température à laquelle le composé polymère a un caractère hydrophobe, de telle manière que l'adduit de l'étape (A) et la ou les particules magnétiques fonctionnalisées s'agglomèrent; (C) addition éventuelle d'un autre agent de suspension au mélange obtenu à l'étape (B); (D) séparation de l'agglomérat contenu dans la suspension de l'étape (B) ou (C) par application d'un champ magnétique; et (E) division de l'agglomérat séparé à l'étape (D) par réglage d'une température à laquelle le composé polymère a un caractère hydrophile afin d'obtenir la ou les premières substances.

Claims (10)

  1. Procédé de séparation d'au moins une première substance choisie dans le groupe constitué par les minerais sulfurés, les minerais oxydiques et/ou carbonatés et leurs mélanges ou les métaux nobles et leurs composés, d'un mélange contenant cette ou ces premières substances et au moins une seconde substance, comprenant les étapes suivantes :
    (A) la mise en contact du mélange contenant la ou les premières substances et au moins une seconde substance avec au moins un agent d'hydrophobation sélectif en présence d'un agent de suspension, de manière à ce qu'un adduit se forme à partir du ou des agents d'hydrophobation et de la ou des premières substances, mais toutefois pas avec la ou les secondes substances,
    (B) la mise en contact de l'adduit de l'étape (A) avec au moins une particule magnétique, qui est fonctionnalisée sur la surface avec au moins un composé polymère, qui présente une température de transition LCST (Lower Critical Solution Temperature) à une température à laquelle le composé polymère présente un caractère hydrophobe, de manière à ce que l'adduit de l'étape (A) et la ou les particules magnétiques fonctionnalisées s'agglomèrent,
    (C) éventuellement l'ajout d'un agent de suspension supplémentaire au mélange obtenu à l'étape (B),
    (D) la séparation de l'agglomérat présent dans la suspension de l'étape (B) ou (C) par application d'un champ magnétique,
    (E) le clivage de l'agglomérat séparé à l'étape (D) par ajustement d'une température à laquelle le composé polymère présente un caractère hydrophile, afin d'obtenir la ou les premières substances.
  2. Procédé selon la revendication 1, caractérisé en ce que le ou les composés polymères sont choisis dans le groupe constitué par les éthers de polyvinyle, les poly-N-alkyl-acrylamides, les poly-N-vinyl-caprolactames, les copolymères à base d'oxydes d'alkylène et leurs mélanges.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le ou les composés polymères sont un composé de formule générale (III)

            F-[(EO)x-(PO)y-(BuO)z]-B     (III)

    dans laquelle
    F signifie un groupe fonctionnel qui se lie sélectivement à la ou les particules magnétiques,
    B signifie un radical alkyle de 1 à 6 atomes de carbone,
    EO signifie oxyde d'éthylène,
    PO signifie oxyde de propylène,
    BuO signifie oxyde de butylène,
    x signifie un nombre entier ou fractionnaire de 0 à 130,
    y signifie un nombre entier ou fractionnaire de 0 à 130, et
    z signifie un nombre entier ou fractionnaire de 0 à 130,
    avec 1 ≤ x+y+z ≤ 130.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la ou les secondes substances sont choisies dans le groupe constitué par les composés oxydiques de métaux, les composés hydroxydiques de métaux et leurs mélanges.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la ou les particules magnétiques sont choisies dans le groupe constitué par les métaux magnétiques, les alliages ferromagnétiques de métaux magnétiques, les oxydes de fer magnétiques, les ferrites cubiques de formule générale (II)

            M2+ xFe2+ 1-xFe3+ 2O4     (II)

    dans laquelle
    M est choisi parmi Co, Ni, Mn, Zn et leurs mélanges et
    x ≤ 1,
    les ferrites hexagonales et leurs mélanges.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la LCST du composé polymère utilisé est de -10 à 100 °C.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'étape (B) est réalisée à une température qui est supérieure à la LCST du composé polymère et inférieure au point d'ébullition de l'agent de suspension utilisé.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que l'étape (E) est réalisée à une température qui est supérieure à la température de fusion de l'agent de suspension utilisé et inférieure à la LCST du composé polymère.
  9. Particules fonctionnalisées de formule générale (VI)

            P-{F-[(EO)x-(PO)y-(BuO)z]-B}q     (VI)

    dans laquelle
    P signifie une particule contenant au moins un métal ou semi-métal,
    F signifie un groupe fonctionnel,
    B signifie un radical alkyle de 1 à 6 atomes de carbone,
    EO signifie oxyde d'éthylène,
    PO signifie oxyde de propylène,
    BuO signifie oxyde de butylène,
    x signifie un nombre entier ou fractionnaire de 0 à 130,
    y signifie un nombre entier ou fractionnaire de 0 à 130,
    z signifie un nombre entier ou fractionnaire de 0 à130, avec 1 ≤ x+y+z ≤ 130, et
    q signifie un nombre entier de 1 à 1*1015.
  10. Utilisation d'une particule fonctionnalisée selon la revendication 9 pour la séparation de mélanges.
EP09780763A 2008-07-18 2009-07-17 Particules inorganiques comportant un revêtement organique pouvant être commuté hydrophile/hydrophobe sous l'effet de la température Not-in-force EP2313200B1 (fr)

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EP09780763A EP2313200B1 (fr) 2008-07-18 2009-07-17 Particules inorganiques comportant un revêtement organique pouvant être commuté hydrophile/hydrophobe sous l'effet de la température
PL09780763T PL2313200T3 (pl) 2008-07-18 2009-07-17 Cząstki nieorganiczne z powłoką organiczną o właściwościach hydrofilowych/hydrofobowych, które mogą ulegać zmianie pod wpływem temperatury

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EP08160685 2008-07-18
PCT/EP2009/059215 WO2010007157A1 (fr) 2008-07-18 2009-07-17 Particules anorganiques comportant un revêtement organique pouvant être réglé hydrophile/hydrophobe sous l'effet de la température
EP09780763A EP2313200B1 (fr) 2008-07-18 2009-07-17 Particules inorganiques comportant un revêtement organique pouvant être commuté hydrophile/hydrophobe sous l'effet de la température

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2714248A1 (fr) * 2011-05-25 2014-04-09 CiDRA Corporate Services, Inc. Séparation minérale utilisant des filtres et des membranes fonctionnalisés

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7981688B2 (en) 2007-03-08 2011-07-19 University Of Washington Stimuli-responsive magnetic nanoparticles and related methods
WO2010007075A1 (fr) * 2008-07-18 2010-01-21 Basf Se Séparation sélective de substances au moyen de particules magnétiques modifiées
PE20120524A1 (es) 2008-12-11 2012-04-28 Basf Se Enriquecimiento de minerales a partir de desechos mineros
CN102421529B (zh) 2009-02-24 2015-08-12 巴斯夫欧洲公司 Cu-Mo分离
EA020958B1 (ru) 2009-03-04 2015-03-31 Басф Се Магнитные гидрофобные агломераты и способ их получения
MX2011009055A (es) 2009-03-04 2011-09-21 Siemens Ag Separacion magnetica de minerales de metal no ferroso mediante acondicionamiento de multiples etapas.
US8426214B2 (en) 2009-06-12 2013-04-23 University Of Washington System and method for magnetically concentrating and detecting biomarkers
US9080933B2 (en) 2009-11-09 2015-07-14 University Of Washington Through Its Center For Commercialization Stimuli-responsive polymer diagnostic assay comprising magnetic nanoparticles and capture conjugates
US20110117668A1 (en) * 2009-11-09 2011-05-19 University Of Washington Through Its Center For Commercialization Self-powered smart diagnostic devices
PL2579987T3 (pl) * 2010-06-11 2020-08-24 Basf Se Zastosowanie naturalnie występujących składników magnetycznych z rud
US8865000B2 (en) 2010-06-11 2014-10-21 Basf Se Utilization of the naturally occurring magnetic constituents of ores
WO2012072615A1 (fr) 2010-11-29 2012-06-07 Basf Se Récupération magnétique de matériaux de valeur à partir de scories
CA2825446A1 (fr) 2011-02-01 2012-08-09 Basf Se Appareil pour la separation en continu de constituants magnetiques et la purification d'une fraction magnetique
US9731221B2 (en) 2011-05-25 2017-08-15 Cidra Corporate Services, Inc. Apparatus having polymer surfaces having a siloxane functional group
GB201115823D0 (en) 2011-09-13 2011-10-26 Novel Polymer Solutions Ltd Mineral processing
US9216420B2 (en) 2012-05-09 2015-12-22 Basf Se Apparatus for resource-friendly separation of magnetic particles from non-magnetic particles
BR112014027739A2 (pt) 2012-05-09 2017-06-27 Basf Se aparelho para separar partículas magnéticas de uma dispersão, processo para separação de pelo menos uma partícula magnética de uma dispersão, e, uso de um aparelho
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
CN106132551B (zh) 2014-03-31 2019-08-27 巴斯夫欧洲公司 用于输送磁化材料的磁体装置
MX2017006699A (es) 2014-11-27 2017-08-21 Basf Se Mejora de la calidad del concentrado.
FI3223952T3 (fi) 2014-11-27 2024-03-27 Basf Se Energiansyöttö agglomeraation aikana magneettierottelua varten
EP3181230A1 (fr) 2015-12-17 2017-06-21 Basf Se Ultraflottation avec des particules support magnétiquement réactives
EP3600590A4 (fr) * 2017-03-27 2020-12-30 Cidra Corporate Services LLC Élimination de particules hydrophobes à l'aide de dioxyde de carbone
PE20210804A1 (es) * 2018-08-13 2021-04-23 Basf Se Combinacion de separacion de portador magnetico y una separacion adicional para el procesamiento de minerales
CA3208646A1 (fr) 2021-03-05 2022-09-09 Oliver Kuhn Separation magnetique de particules supportees par des tensioactifs specifiques

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3425549A (en) * 1966-03-04 1969-02-04 Petrolite Corp Flotation process
US4078993A (en) * 1975-03-06 1978-03-14 Allied Colloids Limited Processes for flotation of mineral substances
AU548500B2 (en) * 1981-10-26 1985-12-12 Denehurst Limited Magnetic flotation
GB8726857D0 (en) 1987-11-17 1987-12-23 Fospur Ltd Froth floatation of mineral fines
US4834898A (en) * 1988-03-14 1989-05-30 Board Of Control Of Michigan Technological University Reagents for magnetizing nonmagnetic materials
DE19516323C2 (de) 1995-04-27 1997-02-27 Dirk Dipl Chem Guenther Verfahren zur Herstellung von magnetisierbaren Dispersionen und deren Verwendung
JP4887530B2 (ja) * 2000-08-21 2012-02-29 独立行政法人産業技術総合研究所 磁性微粒子、およびその製造方法
AUPR319001A0 (en) 2001-02-19 2001-03-15 Ausmelt Limited Improvements in or relating to flotation
US6686202B2 (en) * 2001-08-08 2004-02-03 Placer Dome, Inc. Methods for detecting and extracting gold
US7563748B2 (en) 2003-06-23 2009-07-21 Cognis Ip Management Gmbh Alcohol alkoxylate carriers for pesticide active ingredients
EP1721161A4 (fr) * 2004-02-11 2009-04-01 Massachusetts Inst Technology Nano-agregats magnetiques recouverts de plusieurs polymeres
DE102007020220B3 (de) * 2007-04-28 2008-11-13 Forschungszentrum Karlsruhe Gmbh Verfahren zur magnetisch unterstützten Extraktion
WO2010007075A1 (fr) * 2008-07-18 2010-01-21 Basf Se Séparation sélective de substances au moyen de particules magnétiques modifiées
CN102421529B (zh) * 2009-02-24 2015-08-12 巴斯夫欧洲公司 Cu-Mo分离

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2714248A1 (fr) * 2011-05-25 2014-04-09 CiDRA Corporate Services, Inc. Séparation minérale utilisant des filtres et des membranes fonctionnalisés
EP2714248A4 (fr) * 2011-05-25 2015-04-22 Cidra Corporate Services Inc Séparation minérale utilisant des filtres et des membranes fonctionnalisés

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PE20110528A1 (es) 2011-08-11
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US20110120919A1 (en) 2011-05-26
CL2011000112A1 (es) 2011-06-24

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