EP2190584B1 - Traitement de minerais de valeur au moyen de particules magnétiques - Google Patents

Traitement de minerais de valeur au moyen de particules magnétiques Download PDF

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Publication number
EP2190584B1
EP2190584B1 EP08803482.2A EP08803482A EP2190584B1 EP 2190584 B1 EP2190584 B1 EP 2190584B1 EP 08803482 A EP08803482 A EP 08803482A EP 2190584 B1 EP2190584 B1 EP 2190584B1
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EP
European Patent Office
Prior art keywords
mixture
magnetic
process according
group
substance
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German (de)
English (en)
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EP2190584A2 (fr
Inventor
Imme Domke
Norbert Mronga
Alexej Michailovski
Hartmut Hibst
Thomas Servay
Rainer Klopsch
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BASF SE
Siemens AG
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BASF SE
Siemens AG
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Priority to PL08803482T priority Critical patent/PL2190584T3/pl
Priority to EP08803482.2A priority patent/EP2190584B1/fr
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C2201/00—Details of magnetic or electrostatic separation
    • B03C2201/18—Magnetic separation whereby the particles are suspended in a liquid

Definitions

  • the present invention relates to a process for separating at least one first substance from a mixture containing said at least one first substance and at least one second substance, wherein the first substance is first contacted with a surface-active substance for its hydrophobization, this mixture being further in contact with at least one magnetic particle is brought so that the magnetic particle and the hydrophobized first material attach and this agglomerate is separated from the at least one second material by the application of a magnetic field, and then the at least one first substance is preferably quantitatively separated from the magnetic particle, wherein Preferably, the magnetic particles can be recycled back into the process.
  • the present invention relates to a method of 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 rendered hydrophobic 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.
  • C 4 hydrophobizing agents for the ore are used in this process.
  • US 4,834,898 discloses a method of separating nonmagnetic materials by contacting them with magnetic reagents encased in 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 hydrophobized on the surface for separating impurities from mineral substances by magnetic separation techniques.
  • a dispersing agent selected from sodium silicate, sodium polyacrylate or sodium hexametaphosphate may be added to the solution or dispersion.
  • an organic solvent is selected from the group consisting of 2-hydroxy-5-nonylbenzo-Phenoneoxime, 5,8-diethyl-7-hydroxydodecan-6-oxime and others with magnetic particles added to the organic solvent in this manner to magnetize.
  • the magnetic particles may be coated with a polar surfactant. Suitable surfactants include anionic, cationic or amphoteric surfactants.
  • This magnetized organic solvent is then added to an aqueous slurry of a metal cation-containing compound, for example, copper sulfate. Under the influence of a magnetic field, this biphasic mixture is stirred to transport the copper sulfate into the organic phase. Because magnetic particles are present in the organic phase, a faster separation of the phases succeeds.
  • US 5,161,694 discloses a method for separating finely divided particles by selective hydrophobic coagulation. This process can be used to separate coal from mineral-containing mixtures. The method is based on the fact that the hydrophobic material, for example coal in an aqueous medium agglomerated by hydrophobic forces, and the agglomerates can then be separated in known ways.
  • the stable magnetic fluids consist of finely divided superparamagnetic particles in a liquid dispersant and a sufficient amount for stabilization and property modification of a mixture of surfactants chemically bonded to the surface of the magnetic particles.
  • the object of the present invention is to provide a method by which at least one first substance can be separated off efficiently from mixtures containing at least one first substance and at least one second substance. Furthermore, it is an object of the present invention to treat the first particles to be separated in such a way that the addition product between the magnetic particle and the first substance is sufficiently stable in order to ensure a high yield of first material during the separation.
  • the method according to the invention preferably serves to separate at least one first, hydrophobic substance from a mixture comprising said at least one first, hydrophobic substance and at least one second, hydrophilic substance.
  • hydrophobic means that the corresponding particle can be hydrophobized subsequently 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.
  • 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 to air.
  • the at least one first substance is at least one hydrophobic metal compound or carbon
  • the at least one second substance is preferably at least one hydrophilic metal compound.
  • the at least one first substance to be separated off is preferably a metal compound selected from the group of sulfidic ores, oxidic and / or carbonate-containing Ores, for example azurite [Cu 3 (CO 3 ) 2 (OH) 2 ], or malachite [Cu 2 [(OH) 2 [CO 3 ]]), or of the noble metals and their compounds, to which a surface-active compound is selectively added Generation of hydrophobic surface properties can attach.
  • a metal compound selected from the group of sulfidic ores, oxidic and / or carbonate-containing Ores, for example azurite [Cu 3 (CO 3 ) 2 (OH) 2 ], or malachite [Cu 2 [(OH) 2 [CO 3 ]]
  • a surface-active compound is selectively added Generation of hydrophobic surface properties can attach.
  • the at least one hydrophilic metal compound is preferably selected from the group consisting of oxidic and hydroxide metal compounds, for example silicon dioxide SiO 2 , silicates, aluminosilicates, for example feldspars, for example albite Na (Si 3 Al) O 8 , mica, for example muscovite KAl 2 [(OH , F) 2 AlSi 3 O 10 ], garnets (Mg, Ca, Fe II ) 3 (Al, Fe III ) 2 (SiO 4 ) 3 , Al 2 O 3 , FeO (OH), FeCO 3 , Fe 2 O 3 , Fe 3 O 4 and other related minerals and mixtures thereof.
  • oxidic and hydroxide metal compounds for example silicon dioxide SiO 2 , silicates, aluminosilicates, for example feldspars, for example albite Na (Si 3 Al) O 8 , mica, for example muscovite KAl 2 [(OH , F) 2 AlSi 3
  • 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 and mixtures thereof.
  • Suitable oxidic metal compounds which can be used according to the invention are preferably selected from the group consisting of silicon dioxide SiO 2 , silicates, aluminosilicates, for example feldspars, for example albite Na (Si 3 Al) O 8 , mica, for example muscovite KAl 2 [(OH, F) 2 AlSi 3 O 10 ], garnets (Mg, Ca, Fe II ) 3 (Al, Fe III ) 2 (SiO 4 ) 3 and other related minerals and mixtures thereof.
  • untreated ore mixtures which are obtained from mine deposits are preferably used in the process according to the invention.
  • 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 is obtained by grinding. Suitable methods and devices are known to the person skilled in the art, for example wet milling in a ball mill.
  • a preferred embodiment of the method according to the invention is characterized in that the mixture containing at least a first material and at least one second material before or during step (A) is ground to particles having a size of 100 nm to 100 microns.
  • Preferably usable ore mixtures have a content of sulfidic minerals of at least 0.4 wt .-%, more preferably at least 10 wt.%, On.
  • sulfidic minerals which are present in the mixtures which can be used according to the invention are those mentioned above. Additionally, in the mixtures sulphides of metals other than copper are also present, for example sulphides of iron; Lead, zinc or molybdenum, ie FeS / FeS 2 , PbS, ZnS or MoS 2 .
  • oxidic compounds of metals and semimetals for example silicates or borates or other salts of metals and semimetals, for example phosphates, sulfates or oxides / hydroxides / carbonates and further salts, for example azurite [Cu 3 (CO 3 ) 2 (OH) 2 ], malachite [Cu 2 [(OH) 2 (CO 3 )]], barite (BaSO 4 ), monacite ((La-Lu) PO 4 ).
  • noble metals for example, Au, Pt, Pd, Rh, etc., preferably in a pure state.
  • 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 at least a first substance and at least one second substance with at least one surface-active substance, if appropriate in the presence of at least one dispersing agent, wherein the surface-active substance binds selectively to the at least one first substance,
  • surface-active substance means a substance which is capable of changing the surface of the particle to be separated in the presence of the other particles which are not to be separated in such a way that an attachment of a hydrophobic particle by hydrophobic interactions to Come.
  • Surface-active substances which can be used according to the invention are deposited on the at least one first substance and thereby bring about a suitable hydrophobicity of the first substance.
  • a in formula (I) is a linear or branched C 4 -C 12 -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 in formula (I) is preferably a linear or branched, preferably linear, C 8 -C 20 -alkyl. Furthermore, A is preferably a branched C 6 -C 14 -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.
  • Z in formula (I) is selected from the group consisting of anionic groups - (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 -PO 3 2- (X) n -CO 2 - , - (X) n -CS 2 - , - (X) n -COS - , - (X) n -C (S) NHOH.
  • n 2 in the abovementioned formulas, then two identical or different, preferably identical, groups A are bound to a group Z.
  • Preferred counterions in these compounds are cations selected from the group consisting of hydrogen, NR 4 + with R being the same independently each other hydrogen and / or C 1 -C 8 alkyl, alkali or alkaline earth metals, in particular sodium or potassium before.
  • 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, and mixtures of these compounds.
  • particularly preferred surface-active substances 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 ]]
  • Particularly preferred surface-active substances octylphosphonic acid (OPS), (EtO) 3 Si-A, (MeO) 3 Si-A, with the abovementioned meanings for A.
  • OPS octylphosphonic acid
  • EtO EtO
  • MeO 3 Si-A
  • the surface-active substances used are not hydroxamates for modifying metal oxides used.
  • 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)
  • step (A) of the process according to the invention can be carried out by all methods known to the person skilled in the art.
  • Step (A) can be carried out in bulk or in dispersion, preferably in suspension, particularly preferably in aqueous suspension.
  • step (A) is carried out in bulk, ie in the absence of a dispersing agent.
  • the mixture to be treated and the at least one above-mentioned surfactant are added and mixed together without additional dispersant in the appropriate amounts.
  • Suitable mixing apparatuses are known to the person skilled in the art, for example mills, such as ball mill.
  • step (A) is carried out in a dispersion, preferably in suspension.
  • the dispersant all dispersants are suitable in which the mixture of step (A) is not completely soluble.
  • Suitable dispersants for the preparation of the slurry or dispersion according to step (B) of the process of the invention are selected from the group consisting of water, water-soluble organic compounds, for example alcohols having 1 to 4 carbon atoms, and mixtures thereof.
  • the dispersant in step (A) is water.
  • Step (A) of the process according to the invention is generally carried out at a temperature of 1 to 80 ° C, preferably at 20 to 40 ° C, more preferably at ambient temperature.
  • the at least one above-mentioned surfactant is generally used in an amount sufficient to achieve the desired effect.
  • the at least one surfactant is added in an amount of 0.01 to 5 wt .-%, each based on the total mixture to be treated.
  • step (B) of the process of the invention comprises adding at least one dispersing agent to the mixture obtained in step (A) to obtain a dispersion
  • step (A) if step (A) is carried out in bulk, the mixture obtained in step (A) contains at least one first substance and at least one second substance which has been modified on the surface with at least one surface-active substance.
  • step (B) of the method according to the invention is carried out, i. at least one suitable dispersing agent is added to the mixture obtained in step (A) to obtain a dispersion.
  • step (B) is not carried out. It is, however, also at of this embodiment, it is possible to carry out step (B), ie to add further dispersing agent to obtain a dispersion having a lower concentration.
  • Suitable dispersants are all dispersants which have already been mentioned with respect to step (A).
  • the dispersant in step (A) is water.
  • step (B) either the mixture of substance from step (A) is thus converted into a dispersion, or the mixture already present in dispersion from step (A) is converted into a dispersion of lower concentration by adding dispersing agent.
  • the amount of dispersant added in step (A) and / or step (B) may be selected according to the invention to give a dispersion which is readily stirrable and / or recoverable.
  • the amount of mixture to be treated based on the total slurry or dispersion to 100 wt .-%, particularly preferably 0.5 to 10 wt .-%.
  • step (B) is not carried out, but step (A) is carried out in aqueous dispersion, so that in step (A) directly a mixture in aqueous dispersion is obtained, which has the correct concentration to Step (C) of the method according to the invention to be used.
  • step (B) of the process according to the invention can be carried out according to the invention by all methods known to the person skilled in the art.
  • Step (C) of the process according to the invention comprises treating the dispersion from step (A) or (B) with at least one hydrophobic magnetic particle, so that the at least one first substance rendered hydrophobic in step (A) to which the at least one above-mentioned surface active substance belongs Substance is attached, and attach at least one magnetic particle.
  • the at least one magnetic particle is magnetite or cobalt ferrite Co 2+ x Fe 2+ 1-x Fe 3+ 2 O 4 with x ⁇ 1.
  • the magnetic particles used in step (C) of the process according to the invention are in a size of 100 nm to 100 .mu.m, more preferably 1 to 50 .mu.m before.
  • the magnetic particles can be converted into the appropriate size by methods known to the person skilled in the art, for example by grinding.
  • the particles produced by a precipitation reaction can be brought to this particle size by adjusting the reaction parameters (eg pH, reaction time, temperature).
  • B is a linear or branched C 6 -C 18 -alkyl, preferably linear C 8 -C 12 -alkyl, very particularly preferably a linear one C 12 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 -SiHal 3 , - (X) n -SiHHal 2 , - (X) n -SiH 2 Hal where Hal is 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 -CO 2 -
  • 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.
  • step (C) of the process according to the invention can be carried out by all methods known to the person skilled in the art.
  • the at least one magnetic particle is dispersed in a suitable dispersing agent.
  • Suitable dispersants are all dispersants in which the at least one magnetic particle is not completely soluble.
  • Suitable dispersants for dispersion according to step (C) of the process according to the invention are selected from the group consisting of water, water-soluble organic compounds and mixtures thereof, more preferably water. Particularly preferably, in step (C), the same dispersing agent is used as in step (B).
  • the amount of dispersant for predispersing the magnetic particles may be selected according to the invention so as to obtain a slurry or dispersion which is readily stirrable and / or recoverable.
  • the amount of mixture to be treated, based on the total slurry or dispersion is up to 60% by weight.
  • the dispersion of the magnetic particles can be prepared by all methods known to the person skilled in the art.
  • the magnetic particles to be dispersed and the corresponding amount of dispersing agent or dispersing agent mixture in a suitable reactor such as a glass reactor, combined and stirred with known in the art devices, for example in a glass pan with a mechanically operated paddle, for example at a temperature of 1 to 80 ° C, preferably at room temperature.
  • the treatment of the dispersion from step (B) with at least one hydrophobic magnetic particle is generally carried out so that both components are combined by methods known to the person skilled in the art.
  • a dispersion of the at least one magnetic particle is added to the mixture previously treated with at least one surfactant.
  • the magnetic particle may be added in solid form to a dispersion of the mixture to be treated.
  • both components are present in dispersed form.
  • Step (C) is generally carried out at a temperature of 1 to 80 ° C, preferably 10 to 30 ° C.
  • step (C) the at least one magnetic particle attaches to the hydrophobic substance of the mixture to be treated.
  • the bond between the two components is based on hydrophobic interactions. There is generally no binding interaction between the at least one magnetic particle and the hydrophilic portion of the mixture, so that no attachment takes place between these components.
  • step (C) addition products of the at least one hydrophobic substance and the at least one magnetic particle are thus present in the mixture in addition to the at least one hydrophilic substance.
  • Step (D) of the process according to the invention comprises separating the addition product from step (C) from the mixture 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 mixture from step (C) is located.
  • a permanent magnet for example, the glass 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 may be carried out at any suitable temperature, for example 10 to 60 ° C.
  • step (D) the mixture is preferably stirred continuously with a suitable stirrer, for example a Teflon stirring bar or a paddle stirrer.
  • a suitable stirrer for example a Teflon stirring bar or a paddle stirrer.
  • step (D) the adduct of step (C) may optionally be separated by any method known to those skilled in the art, for example by draining the liquid with the hydrophilic portion of the suspension from the bottom valve from the reactor used for step (D) or pumping it off held by the at least one magnet portions of the suspension through a hose.
  • Step (E) of the process according to the invention comprises cleaving the separated addition product from step (D) in order to obtain the at least one first substance and the at least one magnetic particle separately.
  • the cleavage in step (E) is not destructive, i. that the individual components present in the dispersion are not chemically changed.
  • the cleavage according to the invention does not take place by oxidation of the hydrophobizing agent, for example to obtain the oxidation products or degradation products of the hydrophobizing agent.
  • the splitting can be carried out by all methods known to those skilled in the art, which are suitable for splitting the addition product in such a way that the at least one magnetic particle can be recovered in reusable form.
  • the cleaved magnetic particle is used again in step (C).
  • the cleavage in step (E) of the process according to the invention is carried out by treating the addition product with a substance selected from the group consisting of organic solvents, basic compounds, acidic compounds, oxidizing agents, reducing agents, surface-active compounds and mixtures thereof.
  • suitable organic solvents are methanol, ethanol, propanol, for example n-propanol or iso-propanol, aromatic solvents, for example Benzene, toluene, xylenes, ethers, for example diethyl ether, methyl t-butyl ether, ketones, for example acetone, aromatic or aliphatic hydrocarbons, for example saturated hydrocarbons having, for example, 8 to 16 carbon atoms, for example dodecane and / or Shellsol®, diesel fuels and mixtures from that.
  • the main components of the diesel fuel are predominantly alkanes, cycloalkanes and aromatic hydrocarbons having about 9 to 22 carbon atoms per molecule and a boiling range between 170 ° C and 390 ° C.
  • step (D) is carried out by adding aqueous NaOH solution to a pH of 13, for example for the separation of OPS-modified Cu 2 S.
  • the acidic compounds may be mineral acids, for example HCl, H 2 SO 4 , HNO 3 or mixtures thereof, organic acids, for example carboxylic acids.
  • an oxidizing agent for example, H 2 O 2 can be used, for example, as a 30 wt.% Aqueous solution (perhydrol).
  • For the separation of thiols modified Cu 2 S is preferably H 2 O 2 or Na 2 S 2 O 4 used.
  • Examples of surface-active compounds which can be used according to the invention are nonionic, anionic, cationic and / or zwitterionic surfactants.
  • the addition product of hydrophobic substance and magnetic particle is cleaved with an organic solvent, particularly preferably with acetone and / or diesel. This process can also be supported mechanically. In a preferred embodiment, ultrasound is used to assist the cleavage process.
  • the organic solvent is used in an amount sufficient to cleave as much of the entire addition product as possible. In a preferred embodiment, 20 to 100 ml of the organic solvent are used per gram of hydrophobic and magnetic particle cleavage product.
  • the at least one first substance and the at least one magnetic particle are present as a dispersion in the cleavage reagent mentioned, preferably an organic solvent.
  • the at least one magnetic particle is separated from the dispersion containing this at least one magnetic particle and the at least one first substance by a permanent or switchable magnet from the solution. Details of this separation are analogous to step (D) of the method according to the invention.
  • the first material to be separated off preferably the metal compound to be separated, is separated from the organic solvent by distilling off the organic solvent.
  • the first substance obtainable in this way can be purified by further methods known to the person skilled in the art.
  • the solvent can, if appropriate after purification, be recycled back to the process according to the invention.
  • This mixture is charged with 1.506 g of magnetite which has been modified with dodecyltrichlorosilane (primary particle size: about 10 nm) in a 1 l stirred apparatus, with 580 ml of water and 0.1 g of dodecylamine (Alfa Aeser Lot: 10108955). offset and 45 min at 150 rev / min. mixed with a teflon stirring bar. Then a Co-Sm magnet (5 cm in height, 2 cm in length, 2 cm in width) was held on an outer wall of the stirring apparatus and another 30 min. at 150 rpm. touched. Thereafter, the water is removed via a hose, and the apparatus is dried for a further 10 minutes with a hot air blower. The sand, which is on the ground, is weighed back with 9.77 g. The residue on the magnet is 1.76 g (87% of the Cu 2 S used).
  • the basin is then filled with 400 ml of acetone and for 30 min at 200 U / min. touched. Then, the acetone in which the Cu 2 S is a fine particle is drained through a tube and dried. This gives 1.59 g (79% Cu 2 S).
  • Example 1 An analogous sand-Cu 2 S mixture is produced as in Example 1. Instead of 1-octanethiol, however, potassium butyl xanthate is used. The further experimental procedure is analogous to Example 1. The amount of sand on the ground is 9.64 g, the residue on Magnet 1.61 g (80.0% Cu 2 S). After separation of magnetic particles and ore by stirring in acetone, 1.44 g of Cu 2 S (71%) are obtained.
  • the quartz content of the magnet is ⁇ 0.5% by weight.
  • the assembly is flooded with 0.1 M NaOH solution, shaken gently and then the liquid is removed. After drying, 60% of the Cu 2 S are found again.
  • 0.5 g of Pd-coated ZnO are dispersed in 10 ml of demineralized water, whereupon the solution turns gray. Subsequently, 0.5 g of thiol-modified Fe 3 O 4 are added and stirred vigorously. After 1 h, a Co / Sm magnet is held to the outer wall of the vessel, whereby the solution is largely clarified. The supernatant solution is decanted off from the magnetic components and the volatiles are removed in vacuo. There are found again 0.1 gg Pd-coated ZnO, ie the rest of the ZnO is magnetically separated from the mixture.
  • the diesel phase is decanted off via a magnet in such a way that the magnetic components are retained.
  • the diesel phase with the non-magnetic constituents is subjected to filtration, and then the solid residue is dried. There are recovered 0.98 g of solid which consists of 98% Cu 2 S.
  • the content of Fe 3 O 4 is less than 0.01 g.
  • Example 7 Processing of natural copper ore from Pelambres (Chile)
  • the ore rock is comminuted dry in a hammer mill until 90% by weight of the ore in the fraction is less than 125 ⁇ m in size.
  • Magnetic Pigment 345 (BASF SE) is treated with 0.5% by weight of octylphosphonic acid in aqueous solution for 30 minutes at room temperature (RT). The solid is filtered off, washed until the conductivity of about 50 .mu.S with hot water (50 ° C) and dried at 80 ° C in a vacuum.
  • fraction A1 1 L separating material is passed through a series of stationary permanent magnets.
  • the spout is collected as fraction A1.
  • the portion held on the magnet is washed by moving the magnets with 1 L of water, collecting the discharged solid as fraction A2.
  • the fraction R retained on the magnet and fractions A1 and A2 are analyzed for Cu, Fe and Mo content.
  • 100 g of ore are conditioned in a vibrating mill (160 mL ZrO2 spheres, ⁇ 1.7-2.7 mm) with 60 mL water, 0.065 g potassium n-octyl xanthate and 0.04 g Shellsol D40 for 5 min.
  • a suspension of 3 g of hydrophobized magnetite in 3 g of isopropanol is added to the grinding vessel and conditioned again for 5 min.
  • the grinding suspension is separated from the grinding media, diluted to 1 L and subjected to the separation procedure (see above).
  • the fraction R (6.4 g) contains all the magnetite used and 92.4% of the copper and 86.1% of the molybdenum.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Compounds Of Iron (AREA)
  • Soft Magnetic Materials (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Claims (8)

  1. Procédé pour séparer au moins une première substance d'un mélange contenant cette au moins une première substance et au moins une deuxième substance, comprenant les étapes suivantes :
    (A) mise en contact du mélange contenant au moins une première substance et au moins une deuxième substance avec au moins une substance tensioactive, le cas échéant en présence d'au moins un dispersant, la substance tensioactive se liant à ladite au moins une première substance,
    (B) le cas échéant addition d'au moins un dispersant au mélange obtenu dans l'étape (A), pour obtenir une dispersion,
    (C) traitement de la dispersion de l'étape (A) ou (B) par au moins une particule magnétique hydrophobe, de manière telle que ladite au moins une première substance, à laquelle ladite au moins une substance tensioactive est liée, et ladite au moins une particule magnétique s'additionnent,
    (D) séparation du produit d'addition de l'étape (C) du mélange par application d'un champ magnétique,
    (E) dissociation du produit d'addition séparé de l'étape (D), pour obtenir ladite au moins une première substance et ladite au moins une particule magnétique séparément, la substance tensioactive étant une substance de formule générale (I)

            A-Z     (I)

    où
    A est choisi parmi C3-C30-alkyle linéaire ou ramifié, C3-C30-hétéroalkyle, C6-C30-aryle le cas échéant substitué, C6-C30-hétéroalkyle le cas échéant substitué, C6-C30-aralkyle et
    Z est un groupe avec lequel le composé de formule générale (I) se lie à ladite au moins une première substance hydrophobe.
  2. Procédé selon la revendication 1, caractérisé en ce que la première substance est un composé métallique hydrophobe ou du charbon et la deuxième substance est un composé métallique hydrophile.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que Z est choisi dans le groupe constitué par les groupes anioniques - (X)n-PO3 2-, -(X)n-PO2S2-, -(X)n-POS2 2-, -(X)n-PS3 2-, -(X)n-PS2 -, -(X)n-POS-, - (X)n-PO2 -, -(X)n-PO3 2-, -(X)n-CO2 -, -(X)n-CS2 -, -(X)n-COS-, -(X)n-C(S)NHOH, -(X)n-S-, X étant choisi dans le groupe constitué par 0, S, NH, CH2 et n = 0, 1 ou 2, avec le cas échéant des cations choisis dans le groupe constitué par l'hydrogène, NR4 + avec R représentant, indépendamment l'un de l'autre, hydrogène et/ou C1-C8-alkyle, des métaux alcalins ou alcalino-terreux.
  4. Procédé selon la revendication 2 ou 3, caractérisé en ce que ledit au moins un composé métallique hydrophobe est choisi dans le groupe constitué par les minerais de type sulfure, les minerais de type oxyde et/ou les minerais contenant du carbonate.
  5. Procédé selon l'une quelconque des revendications 2 à 4, caractérisé en ce que ledit au moins un composé métallique hydrophile est choisi dans le groupe constitué par les composés métalliques de type oxyde et hydroxyde.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que ladite au moins une particule magnétique est choisie dans le groupe constitué par les métaux magnétiques et leurs mélanges, les alliages ferromagnétiques de métaux magnétiques et leurs mélanges, les oxydes de fer magnétiques, les ferrites cubiques de formule générale (II)

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

    où
    M est choisi parmi Co, Ni, Mn, Zn et leurs mélanges et
    x ≤ 1,
    les ferrites hexagonales et leurs mélanges.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le dispersant est l'eau.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le mélange contenant au moins une première substance et au moins une deuxième substance est broyé avant ou pendant l'étape (A) en particules présentant une grosseur de 100 nm à 100 µm.
EP08803482.2A 2007-09-03 2008-09-01 Traitement de minerais de valeur au moyen de particules magnétiques Not-in-force EP2190584B1 (fr)

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PL08803482T PL2190584T3 (pl) 2007-09-03 2008-09-01 Przerób wartościowych rud z użyciem cząstek magnetycznych
EP08803482.2A EP2190584B1 (fr) 2007-09-03 2008-09-01 Traitement de minerais de valeur au moyen de particules magnétiques

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EP07115542 2007-09-03
PCT/EP2008/061503 WO2009030669A2 (fr) 2007-09-03 2008-09-01 Traitement de minerais de valeur au moyen de particules magnétiques
EP08803482.2A EP2190584B1 (fr) 2007-09-03 2008-09-01 Traitement de minerais de valeur au moyen de particules magnétiques

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Families Citing this family (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8377311B2 (en) * 2008-07-18 2013-02-19 Basf Se Selective materials separation using modified magnetic particles
AU2009324379A1 (en) 2008-12-11 2011-07-28 Basf Se Enrichment of valuable ores from mine waste (tailings)
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
UA103077C2 (uk) * 2009-03-04 2013-09-10 Басф Се Магнітні гідрофобні агломерати
EP2403648B1 (fr) 2009-03-04 2013-09-04 Basf Se Séparation magnétique de minerais métalliques non ferreux par conditionnement en plusieurs étapes
DE102009038666A1 (de) * 2009-08-24 2011-03-10 Siemens Aktiengesellschaft Verfahren zur kontinuierlichen magnetischen Erztrennung und/oder -aufbereitung sowie zugehörige Anlage
AU2010318028A1 (en) 2009-11-11 2012-05-24 Basf Se Method for concentrating magnetically separated components from ore suspensions and for removing said components from a magnetic separator at a low loss rate
CA2780562A1 (fr) 2009-11-11 2011-05-19 Basf Se Procede permettant d'augmenter le rendement lors d'un processus de separation de minerais au moyen de particules magnetiques hydrophobes par l'apport cible d'energie mecanique
US8475662B2 (en) * 2009-11-30 2013-07-02 Basf Se Modified HIMS process
WO2011138243A1 (fr) 2010-05-06 2011-11-10 Basf Se Formulation de magnétite rendue hydrophobe
PE20131009A1 (es) 2010-06-11 2013-09-19 Basf Se Proceso para separar al menos un primer material de una mezcla que comprende al menos el primer material, al menos un segundo material y particulas magneticas
US8865000B2 (en) 2010-06-11 2014-10-21 Basf Se Utilization of the naturally occurring magnetic constituents of ores
US20120132032A1 (en) * 2010-11-29 2012-05-31 Basf Corporation Magnetic recovery of valuables from slag material
EA201390789A1 (ru) * 2010-11-29 2013-12-30 Басф Се Магнитное извлечение ценных компонентов из шлакового материала
DE102010064139A1 (de) * 2010-12-23 2012-06-28 Siemens Aktiengesellschaft Verfahren und Vorrichtung zur Trennung von Öl und Wasser aus einer Öl/Wasser-Emulsion
CN103476504B (zh) 2011-02-01 2016-11-16 巴斯夫欧洲公司 用于连续分离磁性成分和清洗磁性部分的装置
US9731221B2 (en) 2011-05-25 2017-08-15 Cidra Corporate Services, Inc. Apparatus having polymer surfaces having a siloxane functional group
PE20142002A1 (es) 2011-05-25 2014-12-21 Cidra Corporate Services Inc Tecnicas para transportar perlas o burbujas sinteticas en una celda o columna de flotacion
GB201115823D0 (en) 2011-09-13 2011-10-26 Novel Polymer Solutions Ltd Mineral processing
WO2013130794A1 (fr) * 2012-02-28 2013-09-06 Cidra Corporate Services Inc. Procédé et système de séparation par flottation dans un milieu qui peut être commandé et dirigé magnétiquement
CA2869226C (fr) * 2012-04-23 2020-03-10 Basf Se Separation magnetique de particules comprenant un traitement en une etape d'une pate
US9387485B2 (en) * 2012-04-23 2016-07-12 Basf Se Magnetic separation of particles including one-step-conditioning of a pulp
PE20142378A1 (es) * 2012-05-09 2015-01-29 Basf Se Aparato para la separacion con poco uso de recursos de particulas magneticas a partir de particulas no magneticas
US9216420B2 (en) 2012-05-09 2015-12-22 Basf Se Apparatus for resource-friendly separation of magnetic particles from non-magnetic particles
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
EP3092048B1 (fr) 2014-01-08 2019-09-25 Basf Se Procédé permettant de réduire le volume d'écoulement comprenant des agglomérats magnétiques par élutriation
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
AU2016200868B2 (en) 2015-02-10 2021-05-13 Scandium International Mining Corporation Systems and processes for recovering scandium values from laterite ores
JP6690565B2 (ja) * 2017-01-31 2020-04-28 Ｊｆｅスチール株式会社 磁力選別方法及び装置
EP3600590A4 (fr) * 2017-03-27 2020-12-30 Cidra Corporate Services LLC Élimination de particules hydrophobes à l'aide de dioxyde de carbone
US11110468B2 (en) 2017-08-03 2021-09-07 Basf Se Separation of a mixture using magnetic carrier particles
CN112566725A (zh) 2018-08-13 2021-03-26 巴斯夫欧洲公司 用于矿物加工的载体-磁力分离与其他分离的组合
CN111500879B (zh) * 2020-05-28 2021-07-27 清华大学 基于磁性Janus颗粒的萃取稀土元素的方法
CN112718231B (zh) * 2020-12-15 2023-04-21 中国地质科学院郑州矿产综合利用研究所 富镁矿物的辉钼矿的选矿方法

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4094804A (en) * 1974-08-19 1978-06-13 Junzo Shimoiizaka Method for preparing a water base magnetic fluid and product
JPS56118496A (en) 1980-02-25 1981-09-17 Nippon Seiko Kk Preparation of magnetic fluid
DD235791A3 (de) 1981-06-22 1986-05-21 Adw Ddr Verfahren zur herstellung magnetischer hydrosole
US4657666A (en) * 1981-10-26 1987-04-14 W.S.R. Pty. Ltd. Magnetic flotation
US5043979A (en) 1986-09-16 1991-08-27 Hitachi, Ltd. Time-division channel arrangement
DE3709852A1 (de) * 1987-03-24 1988-10-06 Silica Gel Gmbh Adsorptions Te Stabile magnetische fluessigkeitszusammensetzungen und verfahren zu ihrer herstellung und ihre verwendung
US4834898A (en) * 1988-03-14 1989-05-30 Board Of Control Of Michigan Technological University Reagents for magnetizing nonmagnetic materials
US5043070A (en) 1989-11-13 1991-08-27 Board Of Control Of Michigan Technological University Magnetic solvent extraction
US5161694A (en) 1990-04-24 1992-11-10 Virginia Tech Intellectual Properties, Inc. Method for separating fine particles by selective hydrophobic coagulation
DE19758335C1 (de) 1997-12-22 1999-03-11 Mediport Kardiotechnik Gmbh Magnetflüssigkeit auf der Basis unpolarer Trägerflüssigkeit und Verfahren zur Herstellung
US6036857A (en) * 1998-02-20 2000-03-14 Florida State University Research Foundation, Inc. Apparatus for continuous magnetic separation of components from a mixture
AUPR319001A0 (en) 2001-02-19 2001-03-15 Ausmelt Limited Improvements in or relating to flotation
US7189198B2 (en) * 2002-07-03 2007-03-13 Stereotaxis, Inc. Magnetically guidable carriers and methods for the targeted magnetic delivery of substances in the body
US8033398B2 (en) 2005-07-06 2011-10-11 Cytec Technology Corp. Process and magnetic reagent for the removal of impurities from minerals

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CA2698216A1 (fr) 2009-03-12
US8318025B2 (en) 2012-11-27
CN101815581A (zh) 2010-08-25
PT2190584E (pt) 2013-08-28
MX2010002462A (es) 2010-03-26
AR068164A1 (es) 2009-11-04
BRPI0816189A2 (pt) 2015-04-14
PL2190584T3 (pl) 2013-11-29
US20100300941A1 (en) 2010-12-02
CN101815581B (zh) 2015-01-21
AU2008294826B2 (en) 2013-02-07
AU2008294826A1 (en) 2009-03-12
JP2010537818A (ja) 2010-12-09
EP2190584A2 (fr) 2010-06-02
ZA201002330B (en) 2011-06-29
EA017511B1 (ru) 2013-01-30
WO2009030669A2 (fr) 2009-03-12
ES2426614T3 (es) 2013-10-24
CL2008002609A1 (es) 2009-10-23
CA2698216C (fr) 2017-01-10
EA201000407A1 (ru) 2010-10-29
UA97543C2 (uk) 2012-02-27
WO2009030669A3 (fr) 2009-04-23
PE20090869A1 (es) 2009-08-08

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