EP2376230B1 - Enrichissement de minerais de valeur à partir de résidu minier (tailings) - Google Patents

Enrichissement de minerais de valeur à partir de résidu minier (tailings) Download PDF

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Publication number
EP2376230B1
EP2376230B1 EP09764861.2A EP09764861A EP2376230B1 EP 2376230 B1 EP2376230 B1 EP 2376230B1 EP 09764861 A EP09764861 A EP 09764861A EP 2376230 B1 EP2376230 B1 EP 2376230B1
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EP
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Prior art keywords
mixture
process according
magnetic
substance
group
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EP09764861.2A
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German (de)
English (en)
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EP2376230A1 (fr
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Imme Domke
Alexej Michailovski
Norbert Mronga
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BASF SE
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BASF SE
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Priority to PL09764861T priority patent/PL2376230T3/pl
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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
    • B03C1/00—Magnetic separation
    • B03C1/005—Pretreatment specially adapted for magnetic separation
    • B03C1/01—Pretreatment specially adapted for magnetic separation by addition of magnetic adjuvants

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 in an amount of from 0.001 to 1.0% by weight, based on the total mixture, and at least one second substance, the first Material is first brought to its hydrophobing with a surfactant in contact, this mixture is further brought into contact with at least one magnetic particle, so that the magnetic particles and the hydrophobized first material and attach this agglomerate of the at least one second material by the application of a Magnetic field is separated, and then the at least one first substance is preferably quantitatively separated from the magnetic particle, wherein preferably the magnetic particle can be recycled back into the process.
  • the present invention relates to a method for the enrichment of ores from mine waste, so-called tailings.
  • US 5,043,070 A discloses a method for magnetic solvent extraction.
  • the particles of a magnetic material are coated with a hydrophobic surfactant and dispersed in an organic solvent to obtain a magnetic extractant.
  • This magnetic extractant can be used to separate components from the aqueous phase by treating the aqueous phase to be treated with the magnetic extractant, dissolving the component to be separated, for example, Cu 2+ cations in the organic extraction phase and complete phase separation by applying a magnetic field can be achieved.
  • WO 02/0066168 A1 relates to a process for the separation of ores from mixtures 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 are 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.
  • 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.
  • the object of the present invention is to provide a method by which at least one first substance of mixtures containing at least one first substance and at least one second substance can be separated magnetically efficiently, in particular if this first substance is present in the mixture in a particularly low concentration.
  • the method according to the invention serves to separate the at least one first substance from mixtures containing at least one first substance in a low concentration and at least one second substance.
  • the mixtures to be treated by the process according to the invention which contain at least one first substance in low concentration in addition to at least one second substance are for example so-called "tailings", ie mine wastes which, after separation of the main proportion of ores by conventional methods known to the person skilled in the art, remain, and their content of ore for conventional methods, such as flotation, is too low. Furthermore, the leftover ore particles due to their small diameter, for example less than 10 microns, are not separated by conventional methods.
  • inventive process it is also possible, but not preferred, for the inventive process to treat mixtures which naturally occur with the low concentration of ores of the invention.
  • 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.
  • a mixture containing the at least one first material and the at least one second material is treated, wherein the surface properties of said substances differ so that the at least one first material, preferably a metal compound as ore, selectively in the presence the at least one second substance, preferably a further metal compound which is not an ore, can be rendered hydrophobic.
  • the at least one first material preferably a metal compound as ore
  • the at least one second substance preferably a further metal compound which is not an ore
  • the at least one first substance to be separated is a metal compound selected from the group of compounds of the subgroup metals, for example, Cu, Mo, Ag, Au, Zn, W, Pt, Pd, Rh, etc., and Sn, Pb, As or Bi, the sulfidic ores, the oxidic and / or carbonate ores, for example azurite [Cu 3 (CO 3 ) 2 (OH) 2 ], or malachite [Cu 2 [(OH) 2
  • the sulfidic ores for example, Cu, Mo, Ag, Au, Zn, W, Pt, Pd, Rh, etc.
  • the sulfidic ores, the oxidic and / or carbonate ores for example azurite [Cu 3 (CO 3 ) 2 (OH) 2 ], or
  • the at least one second substance is a hydrophilic metal compound, particularly 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
  • sulfide ores which can be used according to the invention are selected from the group of copper ores consisting of covellite CuS, molybdenum (IV) sulfide, chalcopyrite (copper gravel) CuFeS 2 , bornite Cu 5 FeS 4 , chalcocite Cu 2 S, pentlandite (Ni , Fe) 1-x S, zinc blende and wurtzite, each ZnS, galena PbS and mixtures thereof.
  • Preferred noble metals present in elementary form are, for example, Ag, Au, Pt, Pd or Rh.
  • 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.
  • tailings differ from conventional ores in mines in that the concentration of ores or precious metals in the tailings is significantly lower than in the original ores.
  • the tailings may be present as fine-grained residues in the form of sludges, for example, the particles have diameters of 20 to 50 microns. But there may also be larger particles.
  • Tails unlike ores obtained in mines, may also contain impurities in the form of organic compounds and / or salts, and may optionally have a pH that differs from the neutral pH of the original ores, i. H. in the acidic or basic range.
  • the mixture comprising 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 150 ⁇ 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. Thus, 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 150 microns.
  • the blends to be treated by the process according to the invention contain at least one first substance in an amount of 0.001 to 1.0% by weight, based on the total mixture, and at least one second substance, preferably at least one first substance in an amount of 0.001 to 0.5 wt .-%, based on the total mixture, and at least one second material, more preferably at least one first material in an amount of 0.001 to 0.3 wt .-%, based on the total mixture, and at least a second substance.
  • the amount of at least one second substance preferably corresponds to the difference to 100 wt .-%.
  • sulfidic minerals which are present in the mixtures which can be used according to the invention are those mentioned above.
  • sulfides of metals other than copper may also be present in the mixtures, for example sulfides of iron, lead, zinc or molybdenum, ie FeS / FeS 2 , PbS, ZnS or MoS 2 .
  • oxidic compounds can be used in the ore mixtures to be treated according to the invention 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 )]], baryta (BaSO 4 ), monacite ((La-Lu) PO 4 ).
  • metals and semimetals for example silicates or borates or other salts of metals and semimetals, for example phosphates, sulfates or oxides / hydroxides / carbonates and further salts, for example azurite [Cu 3 (CO 3 ) 2 (OH) 2 ], malachite [ Cu 2 [(OH) 2 (CO 3 )]], baryta (BaSO 4 ), mona
  • At least one first material which is separated by the method according to the invention are noble metals, such as Au, Ag, Pt, Pd, Rh, Ru, etc., which are either solid or bound in the mineral, also associated with others Metals, may be present.
  • a typically used ore mixture which can be separated by the process according to the invention, contains 0.1 to 0.3% by weight, for example 0.2% by weight, of copper sulfide, for example Cu 2 S and / or Bornite Cu 5 FeS 4 , optionally feldspar and / or chromium, iron, titanium and magnesium oxides and balance to 100 wt .-% silica (SiO 2 ).
  • copper sulfide for example Cu 2 S and / or Bornite Cu 5 FeS 4
  • optionally feldspar and / or chromium, iron, titanium and magnesium oxides balance to 100 wt .-% silica (SiO 2 ).
  • 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, optionally 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 is a linear or branched C 4 -C 12 -alkyl, very particularly preferably a linear C 8 -alkyl.
  • Heteroatoms optionally present according to the invention are selected from Si, N, O, P, S and halogens such as F, Cl, Br and I.
  • 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 the modification of metal oxides used.
  • particularly preferred surface-active substances are mono-, di- and trithiols or xanthates, for example potassium octyl xanthate.
  • 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 a cation selected from hydrogen, sodium or potassium.
  • Very particularly preferred surface-active substances are 1-octanethiol, potassium butylxanthate, potassium octylxanthate, octylphosphonic acid or (octylcarbethoxy) thiocarbonylethoxyamine.
  • the at least one hydrophobizing agent is used in step (A) of the process according to the invention in an amount which is sufficient to hydrophobicize as much as possible of the total present in the mixture to be treated at least one substance. Therefore, the amount of hydrophobing agent is dependent on the concentration of the at least one first substance in the mixture to be treated. The amount is further possibly also dependent on the conditioning of the mixture to be treated. If the hydrophobing agent is added, for example in a mill, the amount can be chosen lower. One skilled in the art knows how to determine the amount of hydrophobing agent.
  • the amount of hydrophobing agent in step (A) of the inventive method 0.0001 to 0.2 wt .-%, preferably 0.001 to 0.15 wt .-%, each based on the mixture of mixture to be treated and water repellents.
  • 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, i. in the absence of a dispersant.
  • the mixture to be treated and the at least one 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 a ball mill.
  • step (A) is carried out in 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 dispersion medium in the process according to the invention is water, for example at a neutral pH, in particular at pH 6 to 8.
  • a suspension is preferably provided which has a solids content of, for example, 10 to 50% by weight, preferably 20 to 45% by weight, particularly preferably 35 to 45% by weight. It is also possible according to the invention that the suspension obtained in step (A) has a higher solids content of, for example, 50 to 70% by weight, and this solids content is only reduced in step (B) by dilution to the stated values.
  • 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.
  • step (A) is carried out under the action of a sufficiently high shear energy so that the present ore and the hydrophobizing agent come into contact sufficiently. Therefore, the shear energy which is preferably to be introduced in step (A) of the method according to the invention, for example, depending on the concentration of the valuable substance, the concentration of the hydrophobizing agent and / or the solids content of the dispersion to be treated.
  • the shear energy introduced in step (A) must preferably be so high that in the later process an effective hydrophobic flocculation between hydrophobic magnetic particles and hydrophobized ore is possible. This is done according to the invention preferably by the use of a suitable mill, for example a ball mill.
  • the optional 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 which has been modified on the surface with at least one surface-active substance and at least a second substance.
  • step (B) of the process of the present invention is carried out, ie, at least one suitable dispersant is added to the mixture obtained in step (A) to obtain a dispersion.
  • a suspension is provided which has a solids content of, for example, 10 to 50% by weight, preferably 20 to 45% by weight, particularly preferably 35 to 45% by weight.
  • 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 present invention also relates in particular to the process according to the invention, wherein the dispersion obtained in step (A) and / or (B) has a solids content of 10 to 50% by weight, particularly preferably 20 to 45% by weight, particularly preferably 35 to 45 wt .-%, having.
  • step (B) is not carried out.
  • step (B) it is also possible in this embodiment to perform step (B), i. add further dispersant to obtain a dispersion having a lower solids content.
  • Suitable dispersants are all dispersants which have already been mentioned with respect to step (A).
  • the dispersant in step (B) is water.
  • step (B) either the bulk mixture of step (A) is converted to a dispersion or the already dispersed mixture of step (A) is converted to a lower solids dispersion by the addition of dispersing agent.
  • 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 surface-active substance bonds is, and attach at least one magnetic particle.
  • 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.
  • B is a linear or branched C 6 -C 18 -alkyl, preferably linear C 8 -C 12 -alkyl, very particularly preferably a linear C 8 - or 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 -
  • Very particularly preferred hydrophobicizing substances of the general formula (III) are dodecyltrichlorosilane, octylphosphonic acid, lauric acid, oleic acid, stearic acid or mixtures thereof.
  • step (A) or (B) with at least one hydrophobic magnetic particle in 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 and then added to the dispersion of step (A) or (B).
  • 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. The same dispersing agent as in step (B) can be used in step (C).
  • 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 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 dispersant or dispersant mixture are combined in a suitable reactor, for example a glass reactor, and devices known to those skilled in the art stirred, for example in a glass tank with a mechanically operated paddle, for example at a temperature of 1 to 80 ° C, preferably at ambient 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.
  • the hydrophobized magnetic particle is 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) of the process according to the invention can be carried out in all devices known to the person skilled in the art, for example in a mill, preferably in a ball mill.
  • step (C) is carried out in the same apparatus, preferably a mill, in which step (A) and optionally step (B) are carried out.
  • 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 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 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.
  • 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.
  • the optional step (E) of the method 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 step (E) according to the invention can be carried out if the at least one first substance is to be obtained separately.
  • the cleavage in step (E) is not destructive, that is to say that the individual components present in the dispersion are not changed chemically.
  • 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 (C) of the process according to the invention is carried out by treatment of 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.
  • organic solvents examples include methanol, ethanol, propanol, for example n-propanol or iso-propanol, aromatic solvents, for example benzene, toluene, xylenes, ethers, for example diethyl ether, methyl t-butyl ether, ketones, for example acetone, and Mixtures thereof.
  • 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.
  • H 2 O 2 can be used as the oxidizing agent, for example as a 30% strength by weight aqueous solution (perhydrol).
  • 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, diesel, Solvesso® or Shellsol®. 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 can be separated from the dispersion containing this at least one magnetic particle and the at least one first material 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.
  • the resulting mixture is diluted with water so that the mixture has a solids content of 40% by weight.
  • the magnetic components are separated from the non-magnetic components with a magnet by holding a Co / Sm magnet to the vessel outer wall.
  • Tailings of an original mine are used, the copper content being determined to be 0.2% by weight.
  • the resulting mixture is diluted with water so that the mixture has a solids content of 40% by weight.
  • the magnetic components are separated from the non-magnetic components with a magnet by holding a Co / Sm magnet to the vessel outer wall.
  • Tailings from an original mine are used, the copper content being determined to be 0.1% by weight.
  • the resulting mixture is diluted with water so that the mixture has a solids content of 40% by weight.
  • the magnetic components are separated from the non-magnetic components with a magnet by holding a Co / Sm magnet to the vessel outer wall.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Hard Magnetic Materials (AREA)

Claims (9)

  1. Procédé de séparation d'au moins une première substance d'un mélange contenant cette ou ces premières substances en une quantité de 0,001 à 1,0 % en poids, par rapport à la totalité du mélange, et d'au moins une seconde substance, comprenant les étapes suivantes :
    (A) la mise en contact du mélange contenant au moins une première substance et au moins une seconde substance avec au moins une substance tensioactive en présence d'au moins un dispersant, la substance tensioactive se liant à la ou les premières substances,
    (B) éventuellement l'ajout d'au moins un dispersant au mélange obtenu à l'étape (A), afin d'obtenir une dispersion,
    (C) le traitement de la dispersion de l'étape (A) ou (B) avec au moins une particule magnétique hydrophobe, de manière à ce que la ou les premières substances, auxquelles la ou les substances tensioactives sont reliées, et la ou les particules magnétiques se relient,
    (D) la séparation du produit de liaison de l'étape (C) du mélange par application d'un champ magnétique,
    (E) éventuellement le clivage du produit de liaison séparé à l'étape (D) pour obtenir séparément la ou les premières substances et la ou les particules magnétiques,
    la ou les premières substances étant un composé métallique choisi dans le groupe constitué par les composés des métaux des groupes de transition, les minerais sulfuriques, les minerais oxydiques et/ou contenant des carbonates ou les métaux nobles sous forme élémentaire, et la ou les secondes substances étant de préférence un composé métallique hydrophile.
  2. Procédé selon la revendication 1, caractérisé en ce que la substance tensioactive est une substance de formule générale (I)

            A-Z     (I)

    dans laquelle
    A est choisi parmi alkyle en C3-C30 linéaire ou ramifié, hétéroalkyle en C3-C30, aryle en C6-C30 éventuellement substitué, hétéroalkyle en C6-C30 éventuellement substitué, arylalkyle en C6-C30 et
    Z est un groupe avec lequel le composé de formule générale (I) se relie avec la ou les substances hydrophobes.
  3. Procédé selon la revendication 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 éventuellement des cations choisis dans le groupe constitué par hydrogène, NR4 +, les R représentant indépendamment les uns des autres hydrogène et/ou alkyle en C1-C8, les métaux alcalins ou alcalino-terreux.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la quantité de substance tensioactive à l'étape (A) est de 0,0001 à 0,2 % en poids, par rapport au mélange du mélange à traiter et de la substance tensioactive.
  5. Procédé selon la revendication 1, caractérisé en ce que la ou les secondes substances sont choisies dans le groupe constitué par les composés métalliques oxydiques et hydroxydiques.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la ou les particules magnétiques sont choisies 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)

    avec
    M 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 seconde substance est broyé avant ou pendant l'étape (A) en particules d'une taille de 100 nm à 150 µm.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que la dispersion obtenue à l'étape (A) ou (B) présente une teneur en solides de 10 à 50 % en poids.
EP09764861.2A 2008-12-11 2009-12-09 Enrichissement de minerais de valeur à partir de résidu minier (tailings) Not-in-force EP2376230B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP09764861.2A EP2376230B1 (fr) 2008-12-11 2009-12-09 Enrichissement de minerais de valeur à partir de résidu minier (tailings)
PL09764861T PL2376230T3 (pl) 2008-12-11 2009-12-09 Wzbogacanie rud wartościowych z odpadów kopalnianych (tailings)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08171310 2008-12-11
EP09764861.2A EP2376230B1 (fr) 2008-12-11 2009-12-09 Enrichissement de minerais de valeur à partir de résidu minier (tailings)
PCT/EP2009/066693 WO2010066770A1 (fr) 2008-12-11 2009-12-09 Enrichissement de minerais de valeur à partir de résidu minier (tailings)

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EP2376230A1 EP2376230A1 (fr) 2011-10-19
EP2376230B1 true EP2376230B1 (fr) 2014-07-30

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US (1) US8377312B2 (fr)
EP (1) EP2376230B1 (fr)
JP (1) JP5637997B2 (fr)
KR (1) KR20110095934A (fr)
CN (1) CN102271817B (fr)
AR (1) AR074588A1 (fr)
AU (1) AU2009324379A1 (fr)
BR (1) BRPI0922451A2 (fr)
CA (1) CA2746550A1 (fr)
CL (1) CL2011001419A1 (fr)
MX (1) MX2011006195A (fr)
PE (1) PE20120524A1 (fr)
PL (1) PL2376230T3 (fr)
RU (1) RU2515933C2 (fr)
WO (1) WO2010066770A1 (fr)
ZA (1) ZA201104995B (fr)

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US8377312B2 (en) 2013-02-19
WO2010066770A1 (fr) 2010-06-17
AU2009324379A1 (en) 2011-07-28
CN102271817A (zh) 2011-12-07
RU2011128049A (ru) 2013-01-20
JP2012511414A (ja) 2012-05-24
PL2376230T3 (pl) 2015-01-30
CN102271817B (zh) 2014-10-01
RU2515933C2 (ru) 2014-05-20
PE20120524A1 (es) 2012-04-28
CL2011001419A1 (es) 2011-09-30
BRPI0922451A2 (pt) 2015-12-15
ZA201104995B (en) 2012-10-31
KR20110095934A (ko) 2011-08-25
MX2011006195A (es) 2011-07-01
EP2376230A1 (fr) 2011-10-19
CA2746550A1 (fr) 2010-06-17
AR074588A1 (es) 2011-01-26
US20110240527A1 (en) 2011-10-06
JP5637997B2 (ja) 2014-12-10

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