EP2376230B1 - Enrichment of valuable ores from mine waste (tailings) - Google Patents
Enrichment of valuable ores from mine waste (tailings) Download PDFInfo
- 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
- European Patent Office
- Prior art keywords
- mixture
- process according
- magnetic
- substance
- group
- Prior art date
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- 238000000034 method Methods 0.000 claims description 86
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- 239000000126 substance Substances 0.000 claims description 62
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- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- BNCXNUWGWUZTCN-UHFFFAOYSA-N trichloro(dodecyl)silane Chemical compound CCCCCCCCCCCC[Si](Cl)(Cl)Cl BNCXNUWGWUZTCN-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/005—Pretreatment specially adapted for magnetic separation
- B03C1/015—Pretreatment specially adapted for magnetic separation by chemical treatment imparting magnetic properties to the material to be separated, e.g. roasting, reduction, oxidation
-
- 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.
Description
Die vorliegende Erfindung betrifft ein Verfahren zum Abtrennen wenigstens eines ersten Stoffes aus einer Mischung enthaltend diesen wenigstens einen ersten Stoff in einer Menge von 0,001 bis 1,0 Gew.-%, bezogen auf die gesamte Mischung, und wenigstens einen zweiten Stoff, wobei der erste Stoff zunächst zu seiner Hydrophobierung mit einer oberflächenaktiven Substanz in Kontakt gebracht wird, diese Mischung weiter in Kontakt mit mindestens einem Magnetpartikel gebracht wird, so dass sich der Magnetpartikel und der hydrophobisierte erste Stoff anlagern und dieses Agglomerat von dem wenigstens einen zweiten Stoff durch die Anwendung eines Magnetfeldes abgetrennt wird, und anschließend der wenigstens eine erste Stoff bevorzugt quantitativ von dem Magnetpartikel getrennt wird, wobei bevorzugt der Magnetpartikel wieder in den Prozess zurückgeführt werden kann.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.
Insbesondere betrifft die vorliegende Erfindung ein Verfahren zur Anreicherung von Werterzen aus Minenabfällen, so genannten Tailings. In particular, the present invention relates to a method for the enrichment of ores from mine waste, so-called tailings.
Verfahren zum Abtrennen von Werterzen aus Mischungen sind aus dem Stand der Technik bereits bekannt.Methods for separating ores from mixtures are already known from the prior art.
Im Stand der Technik werden keine Verfahren offenbart, mit denen es möglich ist, aus so genannten "Tailings", d. h. aus Minenabfällen, die nach erfolgter Gewinnung der Werterze durch konventionelle Verfahren wie Flotation oder andere magnetische Verfahren, nur noch einen geringen Anteil an Werterzen aufweisen, diese geringen Mengen an Werterzen abzutrennen. Ein Grund hierfür ist, dass bei der Mahlung des Erzes ein nicht zu vernachlässigender Anteil an sehr feinen Partikeln mit Durchmessern unterhalb 10 µm entsteht, und diese sehr feinen Partikel nur schwer zu flotieren sind.The prior art does not disclose any methods by which it is possible to derive from so-called "tailings", i. H. From mining waste, which after the extraction of the ore by conventional methods such as flotation or other magnetic processes, only a small proportion of ores have to separate these small amounts of ores. One reason for this is that during the grinding of the ore a not insignificant proportion of very fine particles with diameters below 10 μm is formed, and these very fine particles are difficult to float.
Aufgabe der vorliegenden Erfindung ist es, ein Verfahren bereitzustellen, durch das wenigstens ein erster Stoff aus Mischungen enthaltend wenigstens einen ersten Stoff und wenigstens einen zweiten Stoff magnetisch effizient abgetrennt werden kann, insbesondere, wenn dieser erster Stoff in der Mischung in besonders geringer Konzentration vorliegt. Insbesondere ist es eine Aufgabe der vorliegenden Erfindung ein Verfahren bereit zu stellen, mit dem in Minenabfällen in niedriger Konzentration vorliegende Werterze gewonnen werden können. Des Weiteren ist es eine Aufgabe der vorliegenden Erfindung, den abzutrennenden ersten Stoff so zu behandeln, dass das Anlagerungsprodukt zwischen magnetischem Partikel und erstem Stoff genügend stabil ist, um eine hohe Ausbeute an erstem Stoff bei der Abtrennung zu gewährleisten.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. In particular, it is an object of the present invention to provide a method by means of which ore ores present in mining waste in low concentration can be obtained. Furthermore, it is an object of the present invention to treat the first material to be separated in such a way that the addition product between the magnetic particle and the first material is sufficiently stable in order to ensure a high yield of first material during the separation.
Diese Aufgaben werden gelöst durch ein Verfahren zum Abtrennen wenigstens eines ersten Stoffes aus einer Mischung enthaltend diesen wenigstens einen ersten Stoff in einer Menge von 0,001 bis 1,0 Gew.-%, bezogen auf die gesamte Mischung, und wenigstens einen zweiten Stoff, umfassend wenigstens die folgenden Schritte:
- (A) Inkontaktbringen der Mischung enthaltend wenigstens einen ersten Stoff und wenigstens einen zweiten Stoff mit wenigstens einer oberflächenaktiven Substanz, gegebenenfalls in Gegenwart wenigstens eines Dispersionsmittels, wobei die oberflächenaktive Substanz an den wenigstens einen ersten Stoff anbindet,
- (B) gegebenenfalls Zugabe wenigstens eines Dispersionsmittels zu der in Schritt (A) erhaltenen Mischung, um eine Dispersion zu erhalten,
- (C) Behandeln der Dispersion aus Schritt (A) oder (B) mit wenigstens einem hydrophoben Magnetpartikel, so dass sich der wenigstens eine erste Stoff, an den die wenigstens eine oberflächenaktive Substanz angebunden ist, und der wenigstens eine Magnetpartikel anlagern,
- (D) Abtrennen des Anlagerungsproduktes aus Schritt (C) von der Mischung durch Anlegen eines magnetischen Feldes,
- (E) gegebenenfalls Spalten des abgetrennten Anlagerungsproduktes aus Schritt (D), um den wenigstens einen ersten Stoff und den wenigstens einen Magnetpartikel separat zu erhalten, wobei der wenigstens eine erste Stoff eine Metallverbindung ausgewählt aus der Gruppe der Verbindungen der Nebengruppenmetalle, der sulfidischen Erze, der oxidischen und/oder carbonathaltigen Erze oder der Edelmetalle in elementarer Form ist und der wenigstens eine zweite Stoff bevorzugt eine hydrophile Metallverbindung ist.
- (A) 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 to the at least one first substance,
- (B) optionally adding at least one dispersing agent to the mixture obtained in step (A) to obtain a dispersion,
- (C) treating the dispersion from step (A) or (B) with at least one hydrophobic magnetic particle so that the at least one first substance to which the at least one surface-active substance is attached and the at least one magnetic particle attach,
- (D) separating the adduct from step (C) from the mixture by applying a magnetic field,
- (E) optionally cleaving the separated adduct of step (D) to separately obtain the at least one first and at least one magnetic particles, the at least one first being a metal compound selected from the group of the compounds of the subgroup metals, the sulfidic ores, the oxidic and / or carbonate-containing ores or the noble metals are in elemental form and the at least one second material is preferably a hydrophilic metal compound.
Das erfindungsgemäße Verfahren dient dazu, aus Mischungen, die wenigstens einen ersten Stoff in einer geringen Konzentration und wenigstens einen zweiten Stoff enthalten, den wenigstens einen ersten Stoff abzutrennen.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.
Die mit dem erfindungsgemäßen Verfahren zu behandelnden Mischungen, die wenigstens einen ersten Stoff in geringer Konzentration neben wenigstens einem zweiten Stoff enthalten, sind beispielsweise so genannte "Tailings", d. h. Minenabfälle, die nach Abtrennen des Hauptanteils an Werterzen durch konventionelle, dem Fachmann bekannte Verfahren, übrig bleiben, und deren Gehalt an Werterzen für konventionelle Verfahren, beispielsweise Flotationsverfahren, zu gering ist. Des Weiteren können die übrig gebliebenen Werterz-Partikel aufgrund ihrer zu geringen Durchmesser, beispielsweise kleiner 10 µm, nicht durch konventionelle Verfahren abgetrennt werden.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.
Es ist auch möglich, aber nicht bevorzugt, dass durch das erfindungsgemäße Verfahren Mischungen behandelt werden, die mit der erfindungsgemäßen niedrigen Konzentration an Werterzen natürlich vorkommen.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.
Im Rahmen der vorliegenden Erfindung bedeutet "hydrophob", dass das entsprechende Teilchen nachträglich durch Behandlung mit der wenigstens einen oberflächenaktiven Substanz hydrophobiert sein kann. Es ist auch möglich, dass ein an sich hydrophobes Teilchen durch Behandlung mit der wenigstens einen oberflächenaktiven Substanz zusätzlich hydrophobiert wird.In the context of the present 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.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird eine Mischung enthaltend den wenigstens einen ersten Stoff und den wenigstens einen zweiten Stoff behandelt, wobei sich die Oberflächeneigenschaften der genannten Stoffe so unterscheiden, dass der wenigstens eine erste Stoff, bevorzugt eine Metallverbindung als Werterz, selektiv in Gegenwart des wenigstens einen zweiten Stoffes, bevorzugt eine weitere Metallverbindung, die kein Werterz ist, hydrophobiert werden kann. Besonders bevorzugte erste und zweite Stoffe werden im Folgenden genannt.In a preferred embodiment of the method according to the invention, 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. Particularly preferred first and second substances are mentioned below.
Somit ist der abzutrennende wenigstens eine erste Stoff eine Metallverbindung ausgewählt aus der Gruppe der Verbindungen der Nebengruppenmetalle, beispielsweise Cu, Mo, Ag, Au, Zn, W, Pt, Pd, Rh, etc., und Sn, Pb, As oder Bi, der sulfidischen Erze, der oxidischen und/oder carbonathaltigen Erze, beispielsweise Azurit [Cu3(CO3)2(OH)2], oder Malachit [Cu2[(OH)2|CO3]]), oder der Edelmetalle in elementarer Form, an die sich bevorzugt selektiv eine oberflächenaktive Verbindung unter Erzeugung von hydrophoben Oberflächeneigenschaften anlagern kann.Thus, 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 | CO 3 ]]), or the noble metals in elemental A form to which preferably a surface-active compound can selectively attach to produce hydrophobic surface properties.
Der wenigstens eine zweite Stoff ist eine hydrophile Metallverbindung, besonders bevorzugt ausgewählt aus der Gruppe bestehend aus oxidischen und hydroxidischen Metallverbindungen, beispielsweise Siliziumdioxid SiO2, Silikate, Alumosilikate, beispielsweise Feldspate, beispielsweise Albit Na(Si3Al)O8, Glimmer, beispielsweise Muskovit KAl2[(OH,F)2AlSi3O10], Granate (Mg, Ca, FeII)3(Al, FeIII)2(SiO4)3, Al2O3, FeO(OH), FeCO3, Fe2O3, Fe3O4 und weitere verwandte Mineralien und Mischungen davon.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.
Beispiele für erfindungsgemäß einsetzbare sulfidische Erze sind z.B. ausgewählt aus der Gruppe der Kupfererze bestehend aus Covellit CuS, Molybdän(IV)-sulfid, Chalkopyrit (Kupferkies) CuFeS2, Bornit Cu5FeS4, Chalkozyt (Kupferglanz) Cu2S, Pentlandit (Ni, Fe)1-xS, Zinkblende und Wurtzit, jeweils ZnS, Galenit PbS und Mischungen davon. Bevorzugt in elementarer Form vorliegende Edelmetalle sind beispielsweise Ag, Au, Pt, Pd oder Rh.Examples of 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.
Geeignete erfindungsgemäß einsetzbare oxidische Metallverbindungen sind bevorzugt ausgewählt aus der Gruppe bestehend aus Siliziumdioxid SiO2, Silikate, Alumosilikate, beispielsweise Feldspate, beispielsweise Albit Na(Si3Al)O8, Glimmer, beispielsweise Muskovit KAl2[(OH,F)2AlSi3O10], Granate (Mg, Ca, FeII)3(Al, FeIII)2(SiO4)3 und weitere verwandte Mineralien und Mischungen davon.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.
In dem erfindungsgemäßen Verfahren werden demnach bevorzugt Erzmischungen eingesetzt, welche durch Behandlung von Minenvorkommen mit konventionellen Verfahren zur Abtrennung der Werterze gewonnen werden. Konventionelle Verfahren sind dem Fachmann bekannt, beispielsweise konventionelle Flotation, insbesondere Spezialverfahren wie Ultra- oder Carrierflotation, oder Leachverfahren wie Dump-Leaching, Heap-Leaching oder Tank-Leaching. Diese als Tailings bezeichneten Minenabfälle unterscheiden sich von herkömmlichen in Minen erhaltenen Erze dadurch, dass die Konzentration der Werterze bzw. der Edelmetalle in den Tailings deutlich geringer als in den ursprünglichen Erzen ist. Des Weiteren können die Tailings als feinkörnige Rückstände in Form von Schlämmen vorliegen, beispielsweise weisen die Partikel Durchmesser von 20 bis 50 µm auf. Es können aber auch größere Partikel vorliegen. Tailings können auch im Gegensatz zu in Minen erhaltenen Erzen Verunreinigungen in Form von organischen Verbindungen und/oder Salzen enthalten, und können gegebenenfalls einen pH-Wert aufweisen, der von dem neutralen pH-Wert der Originalerze abweicht, d. h. im sauren oder im basischen Bereich liegt.Accordingly, ore mixtures which are obtained by treating mine deposits with conventional methods for separating the ores are preferably used in the process according to the invention. Conventional methods are known to the person skilled in the art, for example conventional flotation, in particular special methods such as ultra or carrier flotation, or leaching methods such as dump leaching, heap leaching or tank leaching. These tailings, referred to as 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. Furthermore, 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.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens liegt die Mischung enthaltend wenigstens einen ersten Stoff und wenigstens einen zweiten Stoff in Schritt (A) in Form von Partikeln mit einer Größe 100 nm bis 150 µm vor, siehe beispielsweise
Im Allgemeinen enthalten die durch das erfindungsgemäße Verfahren zu behandelnden Mischungen wenigstens einen ersten Stoff in einer Menge von 0,001 bis 1,0 Gew.- %, bezogen auf die gesamte Mischung, und wenigstens einen zweiten Stoff, bevorzugt wenigstens einen ersten Stoff in einer Menge von 0,001 bis 0,5 Gew.-%, bezogen auf die gesamte Mischung, und wenigstens einen zweiten Stoff, besonders bevorzugt wenigstens einen ersten Stoff in einer Menge von 0,001 bis 0,3 Gew.-%, bezogen auf die gesamte Mischung, und wenigstens einen zweiten Stoff. Die Menge des wenigstens einen zweiten Stoffes entspricht dabei bevorzugt der Differenz zu 100 Gew.-%.In general, 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 .-%.
Beispiele für sulfidische Mineralien, die in den erfindungsgemäß einsetzbaren Mischungen vorliegen, sind die oben genannten. Zusätzlich können in den Mischungen auch Sulfide anderer Metalle als Kupfer vorliegen, beispielsweise Sulfide von Eisen, Blei, Zink oder Molybdän, d.h. FeS/FeS2, PbS, ZnS oder MoS2. Des Weiteren können in den erfindungsgemäß zu behandelnden Erzmischungen oxidische Verbindungen von Metallen und Halbmetallen, beispielsweise Silikate oder Borate oder andere Salze von Metallen und Halbmetallen, beispielsweise Phosphate, Sulfate oder Oxide/Hydroxide/Carbonate und weitere Salze vorliegen, beispielsweise Azurit [Cu3(CO3)2(OH)2], Malachit [Cu2[(OH)2(CO3)]], Baryt (BaSO4), Monacit ((La-Lu)PO4). Weitere Beispiele für den wenigstens einen ersten Stoff, der durch das erfindungsgemäße Verfahren abgetrennt wird, sind Edelmetalle, wie beispielsweise Au, Ag, Pt, Pd, Rh, Ru etc., die entweder gediegen oder in gebundenem Zustand im Mineral, auch vergesellschaftet mit anderen Metallen, vorliegen können.Examples of sulfidic minerals which are present in the mixtures which can be used according to the invention are those mentioned above. In addition, 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 . Furthermore, 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 ). Further examples of the 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.
Eine typischerweise eingesetzte Erzmischung, die mit dem erfindungsgemäßen Verfahren getrennt werden kann, enthält 0,1 bis 0,3 Gew.-%, beispielsweise 0,2 Gew.-% Kupfersulfid, beispielsweise Cu2S und/oder Bornit Cu5FeS4, gegebenenfalls Feldspat und/oder Chrom-, Eisen-, Titan- und Magnesiumoxide und Rest zu 100 Gew.-% Siliziumdioxid (SiO2).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 ).
Die einzelnen Schritte des erfindungsgemäßen Verfahrens werden im Folgenden detailliert beschrieben:The individual steps of the method according to the invention are described in detail below:
Schritt (A) des erfindungsgemäßen Verfahrens umfasst das Inkontaktbringen der Mischung enthaltend wenigstens einen ersten Stoff und wenigstens einen zweiten Stoff mit wenigstens einer oberflächenaktiven Substanz, gegebenenfalls in Gegenwart wenigstens eines Dispersionsmittels, wobei die oberflächenaktive Substanz selektiv an den wenigstens einen ersten Stoff anbindet,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,
Geeignete und bevorzugte erste und zweite Stoffe sind oben genannt.Suitable and preferred first and second substances are mentioned above.
Im Rahmen der vorliegenden Erfindung bedeutet "oberflächenaktive Substanz" eine Substanz, die in der Lage ist, die Oberfläche des abzutrennenden Teilchens in Anwesenheit der anderen Teilchen, die nicht abgetrennt werden sollen, so zu ändern, dass eine Anlagerung eines hydrophoben Teilchens durch hydrophobe Wechselwirkungen zu Stande kommt. Erfindungsgemäß einsetzbare oberflächenaktive Substanzen lagern sich an den mindestens einen ersten Stoff an und bewirken dadurch eine geeignete Hydrophobizität des ersten Stoffes.In the context of the present invention, "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.
Bevorzugt wird in dem erfindungsgemäßen Verfahren eine oberflächenaktive Substanz der allgemeinen Formel (I)
A-Z (I)
eingesetzt, die an den wenigstens einen ersten Stoff anbindet, worin
- A
- ausgewählt aus linearem oder verzweigtem C3-C30-Alkyl, C3-C30-Heteroalkyl, gegebenenfalls substituiertes C6-C30-Aryl, gegebenenfalls substituiertes C6-C30-Heteroalkyl, C6-C30-Arylalkyl ist und
- Z
- eine Gruppe ist, mit der die Verbindung der allgemeinen Formel (I) an den wenigstens einen hydrophoben Stoff anbindet.
AZ (I)
used, which binds to the at least one first material, wherein
- A
- selected from linear or branched C 3 -C 30 alkyl, C 3 -C 30 heteroalkyl, optionally substituted C 6 -C 30 aryl, optionally substituted C 6 -C 30 heteroalkyl, C 6 -C 30 -arylalkyl and
- Z
- is a group with which binds the compound of general formula (I) to the at least one hydrophobic substance.
In einer besonders bevorzugten Ausführungsform ist A ein lineares oder verzweigtes C4-C12-Alkyl, ganz besonders bevorzugt ein lineares C8-Alkyl. Erfindungsgemäß gegebenenfalls vorhandene Heteroatome sind ausgewählt aus Si, N, O, P, S und Halogenen wie F, Cl, Br und I.In a particularly preferred embodiment, 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.
In einer weiteren besonders bevorzugten Ausführungsform ist Z ausgewählt aus der Gruppe bestehend aus anionischen Gruppen -(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- mit X ausgewählt aus der Gruppe bestehend aus O, S, NH, CH2 und n = 0, 1 oder 2, mit gegebenenfalls Kationen ausgewählt aus der Gruppe bestehend aus Wasserstoff, NR4 + mit R gleich unabhängig voneinander Wasserstoff und/oder C1-C8-Alkyl, Alkali- oder Erdalkalimetallen. Die genannten Anionen und die entsprechenden Kationen bilden erfindungsgemäß neutral geladene Verbindungen der allgemeinen Formel (I).In a further particularly preferred embodiment Z 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, - (X) n -S - with X is selected from the group consisting of O, S, NH, CH 2 and n = 0, 1 or 2, with optionally cations selected from the group consisting of hydrogen, NR 4 + where R is independently hydrogen and / or C 1 - C 8 alkyl, alkali or alkaline earth metals. The anions mentioned and the corresponding cations form neutral charged compounds of the general formula (I) according to the invention.
Für Edelmetalle, beispielsweise Au, Pd, Rh etc., sind besonders bevorzugte oberflächenaktive Substanzen Mono-, Di- und Trithiole oder 8-Hydroxychinoline, beispielsweise beschrieben in
Für Metalloxide, beispielsweise FeO(OH), Fe3O4, ZnO etc., Carbonate, beispielsweise Azurit [Cu(CO3)2(OH)2], Malachit [Cu2[(OH)2CO3]], sind besonders bevorzugte oberflächenaktive Substanzen Octylphosphonsäure (OPS), (EtO)3Si-A, (MeO)3Si-A, mit den oben genannten Bedeutungen für A. In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens werden als oberflächenaktive Substanzen keine Hydroxamate zur Modifizierung von Metalloxiden eingesetzt.For 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. In a preferred embodiment of the process according to the invention, the surface-active substances used are not hydroxamates for the modification of metal oxides used.
Für Metallsulfide, beispielsweise Cu2S, MoS2, etc., sind besonders bevorzugte oberflächenaktive Substanzen Mono-, Di- und Trithiole oder Xanthogenate, beispielsweise Kaliumoctylxanthat.For metal sulfides, for example Cu 2 S, MoS 2 , etc., particularly preferred surface-active substances are mono-, di- and trithiols or xanthates, for example potassium octyl xanthate.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens bedeutet Z -(X)n-CS2 -, -(X)n-PO2 - oder -(X)n-S- mit X gleich O und n gleich 0 oder 1 und einem Kation ausgewählt aus Wasserstoff, Natrium oder Kalium. Ganz besonders bevorzugte oberflächenaktive Substanzen sind 1-Octanthiol, Kaliumbutylxanthat, Kaliumoctylxanthat, Octylphosphonsäure oder (Octylcarbethoxy)-thiocarbonylethoxyamin.In a preferred embodiment of the process according to the invention, 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.
Kaliumoctylxanthat (IV) und (Octylcarbethoxy)-thiocarbonylethoxyamin (V) sind im Folgenden abgebildet:
Das wenigstens eine Hydrophobierungsmittel wird in Schritt (A) des erfindungsgemäßen Verfahrens in einer Menge eingesetzt, die ausreicht, um möglichst den gesamten in der zu behandelnden Mischung vorliegenden wenigstens einen Stoff zu hydrophobieren. Daher ist die Menge an Hydrophobierungsmittel abhängig von der Konzentration des wenigstens einen ersten Stoffes in der zu behandelnden Mischung. Die Menge ist des Weiteren gegebenenfalls auch von der Konditionierung der zu behandelnden Mischung abhängig. Wird das Hydrophobierungsmittel beispielsweise in einer Mühle zugegeben, kann die Menge geringer gewählt werden. Ein Fachmann weiß, wie die Menge an Hydrophobierungsmittel zu bestimmen ist.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.
In einer bevorzugten Ausführungsform beträgt die Menge an Hydrophobierungsmittel In Schritt (A) des erfindungsgemäßen Verfahrens 0,0001 bis 0,2 Gew.-%, bevorzugt 0,001 bis 0,15 Gew.-%, jeweils bezogen auf die Mischung aus zu behandelnder Mischung und Hydrophobierungsmittel.In a preferred embodiment, 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.
Das Inkontaktbringen in Schritt (A) des erfindungsgemäßen Verfahrens kann durch alle dem Fachmann bekannte Verfahren geschehen. Schritt (A) kann in Substanz oder in Dispersion, bevorzugt in Suspension, besonders bevorzugt in wässriger Suspension, durchgeführt werden.The contacting in 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.
In einer Ausführungsform des erfindungsgemäßen Verfahrens wird Schritt (A) in Substanz, d.h. in Abwesenheit eines Dispersionsmittels, durchgeführt.In one embodiment of the method according to the invention, step (A) is carried out in bulk, i. in the absence of a dispersant.
Beispielsweise werden die zu behandelnde Mischung und die wenigstens eine oberflächenaktive Substanz ohne weiteres Dispersionsmittel in den entsprechenden Mengen zusammen gegeben und vermischt. Geeignete Mischungsapparaturen sind dem Fachmann bekannt, beispielsweise Mühlen, wie eine Kugelmühle.For example, 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.
In einer bevorzugten Ausführungsform wird Schritt (A) in Dispersion, bevorzugt in Suspension, durchgeführt. Als Dispersionsmittel sind alle Dispersionsmittel geeignet, in denen die Mischung aus Schritt (A) nicht vollständig löslich ist. Geeignete Dispersionsmittel zur Herstellung der Aufschlämmung oder Dispersion gemäß Schritt (B) des erfindungsgemäßen Verfahrens sind ausgewählt aus der Gruppe bestehend aus Wasser, wasserlöslichen organischen Verbindungen, beispielsweise Alkoholen mit 1 bis 4 Kohlenstoffatomen, und Mischungen davon.In a preferred embodiment, step (A) is carried out in dispersion, preferably in suspension. As 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.
In einer besonders bevorzugten Ausführungsform ist das Dispersionsmittel in dem erfindungsgemäßen Verfahren Wasser, beispielsweise bei einem neutralen pH-Wert, insbesondere bei pH 6 bis 8.In a particularly preferred embodiment, 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.
Bevorzugt wird in Schritt (A) eine Suspension bereitgestellt, die einen Feststoffgehalt von beispielsweise 10 bis 50 Gew.-%, bevorzugt 20 bis 45 Gew.-%, besonders bevorzugt 35 bis 45 Gew.-%, aufweist. Es ist erfindungsgemäß auch möglich, dass die in Schritt (A) erhaltene Suspension einen höheren Feststoffgehalt von beispielsweise 50 bis 70 Gew.-% aufweist, und dieser Feststoffgehalt erst in Schritt (B) durch Verdünnen auf die genannten Werte gesenkt wird.In step (A), 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.
Schritt (A) des erfindungsgemäßen Verfahrens wird im Allgemeinen bei einer Temperatur von 1 bis 80 °C, bevorzugt bei 20 bis 40 °C, besonders bevorzugt bei Umgebungstemperatur durchgeführt.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.
Für das erfindungsgemäße Verfahren ist es bevorzugt, dass Schritt (A) unter Einwirkung einer genügend hohen Scherenergie durchgeführt wird, damit das vorliegende Werterz und das Hydrophobierungsmittel in ausreichendem Maß in Kontakt treten. Daher ist die Scherenergie, die bevorzugt in Schritt (A) des erfindungsgemäßen Verfahrens eingebracht werden soll, beispielsweise abhängig von der Konzentration des Wertstoffes, der Konzentration des Hydrophobierungsmittels und/oder dem Feststoffgehalt der zu behandelnden Dispersion. Die in Schritt (A) eingebrachte Scherenergie muss bevorzugt so hoch sein, dass im späteren Verfahren eine effektive hydrophobe Flokulation zwischen hydrophoben magnetischen Partikeln und hydrophobisiertem Werterz möglich ist. Dies geschieht erfindungsgemäß bevorzugt durch die Verwendung einer geeigneten Mühle, beispielsweise einer Kugelmühle.For the process according to the invention it is preferred that 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.
Der optionale Schritt (B) des erfindungsgemäßen Verfahrens umfasst die Zugabe wenigstens eines Dispersionsmittels zu der in Schritt (A) erhaltenen Mischung, um eine Dispersion zu erhalten.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.
Die in Schritt (A) erhaltene Mischung enthält in einer Ausführungsform, falls Schritt (A) in Substanz durchgeführt wird, wenigstens einen ersten Stoff, der an der Oberfläche mit wenigstens einer oberflächenaktiven Substanz modifiziert worden ist und wenigstens einen zweiten Stoff. Wird Schritt (A) in Substanz durchgeführt, wird Schritt (B) des erfindungsgemäßen Verfahrens durchgeführt, d.h. wenigstens ein geeignetes Dispersionsmittel wird zu der in Schritt (A) erhaltenen Mischung zugegeben, um eine Dispersion zu erhalten. Dabei wird bevorzugt in Schritt (B) eine Suspension bereitgestellt, die einen Feststoffgehalt von beispielsweise 10 bis 50 Gew.-%, bevorzugt 20 bis 45 Gew.-%, besonders bevorzugt 35 bis 45 Gew.-%, aufweist.In one embodiment, 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. When step (A) is carried out in bulk, 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. In this case, preferably in step (B), 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.
Im Allgemeinen kann die Menge an Dispersionsmittel, zugegeben in Schritt (A) und/oder Schritt (B) erfindungsgemäß so gewählt werden, dass eine Dispersion erhalten wird, welche gut rührbar und/oder förderbar ist.In general, 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.
Die vorliegende Erfindung betrifft insbesondere auch das erfindungsgemäße Verfahren, wobei die in Schritt (A) und/oder (B) erhaltene Dispersion einen Feststoffgehalt von 10 bis 50 Gew.-%, besonders bevorzugt 20 bis 45 Gew.-%, besonders bevorzugt 35 bis 45 Gew.-%, aufweist.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.
In der Ausführungsform, in der Schritt (A) des erfindungsgemäßen Verfahrens in Dispersion durchgeführt wird, wird Schritt (B) nicht durchgeführt. Es ist jedoch auch bei dieser Ausführungsform möglich, Schritt (B) durchzuführen, d.h. weiteres Dispersionsmittel zuzugeben, um eine Dispersion mit einem niedrigeren Feststoffgehalt zu erhalten.In the embodiment in which step (A) of the process according to the invention is carried out in dispersion, step (B) is not carried out. However, it is also possible in this embodiment to perform step (B), i. add further dispersant to obtain a dispersion having a lower solids content.
Als geeignete Dispersionsmittel sind alle Dispersionsmittel geeignet, die bereits bezüglich Schritt (A) genannt worden sind. In einer besonders bevorzugten Ausführungsform ist das Dispersionsmittel in Schritt (B) Wasser.Suitable dispersants are all dispersants which have already been mentioned with respect to step (A). In a particularly preferred embodiment, the dispersant in step (B) is water.
In Schritt (B) wird somit entweder die in Substanz vorliegende Mischung aus Schritt (A) in eine Dispersion überführt, oder die bereits in Dispersion vorliegende Mischung aus Schritt (A) wird durch Zugabe von Dispersionsmittel in eine Dispersion mit niedrigerem Feststoffgehalt überführt.Thus, in 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.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird Schritt (B) nicht durchgeführt, sondern Schritt (A) wird in wässriger Dispersion durchgeführt, so dass in Schritt (A) direkt eine Mischung in wässriger Dispersion erhalten wird, die die richtige Konzentration aufweist, um in Schritt (C) des erfindungsgemäßen Verfahrens eingesetzt zu werden.In a preferred embodiment of the process according to the invention, 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.
Die Zugabe von Dispersionsmittel in Schritt (B) des erfindungsgemäßen Verfahrens kann erfindungsgemäß nach allen dem Fachmann bekannten Verfahren erfolgen.The addition of dispersant in 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.
Schritt (C) des erfindungsgemäßen Verfahrens umfasst das Behandeln der Dispersion aus Schritt (A) oder (B) mit wenigstens einem hydrophoben Magnetpartikel, so dass sich der wenigstens eine in Schritt (A) hydrophobierte erste Stoff, an den die wenigstens eine oberflächenaktive Substanz angebunden ist, und der wenigstens eine Magnetpartikel anlagern.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.
In Schritt (C) des erfindungsgemäßen Verfahrens können alle dem Fachmann bekannten magnetischen Substanzen und Stoffe eingesetzt werden. In einer bevorzugten Ausführungsform ist der wenigstens eine Magnetpartikel ausgewählt aus der Gruppe bestehend aus magnetischen Metallen, beispielsweise Eisen, Cobalt, Nickel und Mischungen davon, ferromagnetischen Legierungen von magnetischen Metallen, beispielsweise NdFeB, SmCo und Mischungen davon, magnetischen Eisenoxiden, beispielsweise Magnetit, Maghemit, kubischen Ferriten der allgemeinen Formel (II)
M2+ xFe2+ 1-xFe3+ 2O4 (II)
mit
- M
- ausgewählt aus Co, Ni, Mn, Zn und Mischungen davon und
- x
- ≤ 1,
M 2+ x Fe 2+ 1-x Fe 3+ 2 O 4 (II)
With
- M
- selected from Co, Ni, Mn, Zn and mixtures thereof and
- x
- ≤ 1,
In einer besonders bevorzugten Ausführungsform der vorliegenden Anmeldung ist der wenigstens eine magnetische Partikel Magnetit Fe3O4 oder Kobaltferrit Co2+ xFe2+ 1-xFe3+ 2O4 mit x ≤ 1.In a particularly preferred embodiment of the present application, 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.
In einer weiteren bevorzugten Ausführungsform ist der wenigstens eine magnetische Partikel an der Oberfläche mit wenigstens einer hydrophoben Verbindung hydrophobiert. Bevorzugt ist die hydrophobe Verbindung ausgewählt aus Verbindungen der allgemeinen Formel (III)
B-Y (III),
worin
- B
- ausgewählt ist aus linearem oder verzweigtem C3-C30-Alkyl, C3-C30-Heteroalkyl, gegebenenfalls substituiertes C6-C30-Aryl, gegebenenfalls substituiertes C6-C30-Heteroalkyl, C6-C30-Arylalkyl und
- Y
- eine Gruppe ist, mit der die Verbindung der allgemeinen Formel (III) an den wenigstens einen magnetischen Partikel anbindet.
BY (III),
wherein
- B
- is selected from linear or branched C 3 -C 30 alkyl, C 3 -C 30 heteroalkyl, optionally substituted C 6 -C 30 aryl, optionally substituted C 6 -C 30 heteroalkyl, C 6 -C 30 arylalkyl and
- Y
- is a group with which the compound of the general formula (III) binds to the at least one magnetic particle.
In einer besonders bevorzugten Ausführungsform ist B ein lineares oder verzweigtes C6-C18-Alkyl, bevorzugt lineares C8-C12-Alkyl, ganz besonders bevorzugt ein lineares C8- oder C12-Alkyl. Erfindungsgemäß gegebenenfalls vorhandene Heteroatome sind ausgewählt aus N, O, P, S und Halogenen wie F, Cl, Br und I.In a particularly preferred embodiment, 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.
In einer weiteren besonders bevorzugten Ausführungsform ist Y ausgewählt aus der Gruppe bestehend aus -(X)n-SiHal3, -(X)n-SiHHal2, -(X)n-SiH2Hal mit Hal gleich F, Cl, Br, I, und anionischen Gruppen wie -(X)n-SiO3 3-, -(X)n-CO2 -, -(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-CO2 -, -(X)n-CS2 -, -(X)n-COS-, -(X)n-C(S)NHOH, -(X)n-S- mit X = O, S, NH, CH2 und n = 0, 1 oder 2, und gegebenenfalls Kationen ausgewählt aus der Gruppe bestehen aus Wasserstoff, NR4 + mit R gleich unabhängig voneinander Wasserstoff und/oder C1-C8-Alkyl, Alkali-, Erdalkalimetallen oder Zink, des Weiteren -(X)n-Si(OZ)3 mit n = 0, 1 oder 2 und Z = Ladung, Wasserstoff oder kurzkettiger Alkylrest.In a further particularly preferred embodiment, 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 -COS - , - (X) n -C (S) NHOH, - (X) n -S - with X = O, S, NH, CH 2 and n = 0, 1 or 2, and optionally cations selected from the group consisting of hydrogen, NR 4 + with R equal independently of one another hydrogen and / or C 1 -C 8 alkyl , Alkali metals, alkaline earth metals or zinc, furthermore - (X) n-Si (OZ) 3 with n = 0, 1 or 2 and Z = charge, hydrogen or short-chain alkyl radical.
Ganz besonders bevorzugte hydrophobierende Substanzen der allgemeinen Formel (III) sind Dodecyltrichlorsilan, Octylphosphonsäure, Laurinsäure, Ölsäure, Stearinsäure oder Mischungen davon.Very particularly preferred hydrophobicizing substances of the general formula (III) are dodecyltrichlorosilane, octylphosphonic acid, lauric acid, oleic acid, stearic acid or mixtures thereof.
Das Behandeln der Dispersion aus Schritt (A) oder (B) mit wenigstens einem hydrophoben Magnetpartikel in Schritt (C) des erfindungsgemäßen Verfahrens kann nach allen dem Fachmann bekannten Verfahren erfolgen.The treatment of the dispersion from 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.
In einer Ausführungsform des erfindungsgemäßen Verfahrens wird der wenigstens eine magnetische Partikel in einem geeigneten Dispersionsmittel dispergiert und dann zu der Dispersion aus Schritt (A) oder (B) gegeben. Als Dispersionsmittel sind alle Dispersionsmittel geeignet, in denen der wenigstens eine Magnetpartikel nicht vollständig löslich ist. Geeignete Dispersionsmittel zur Dispergierung gemäß Schritt (C) des erfindungsgemäßen Verfahrens sind ausgewählt aus der Gruppe bestehend aus Wasser, wasserlöslichen organischen Verbindungen und Mischungen davon, besonders bevorzugt Wasser. Es kann in Schritt (C) das gleiche Dispersionsmittel wie in Schritt (B) eingesetzt werden. Im Allgemeinen kann die Menge an Dispersionsmittel zum Vordispergieren der Magnetpartikel erfindungsgemäß so gewählt werden, dass eine Aufschlämmung oder Dispersion erhalten wird, welche gut rührbar und/oder förderbar ist. Die Dispersion der Magnetpartikel kann erfindungsgemäß nach allen dem Fachmann bekannten Verfahren hergestellt werden. In einer bevorzugten Ausführungsform werden die zu dispergierenden Magnetpartikel und die entsprechende Menge Dispersionsmittel bzw. Dispersionsmittelgemisch in einem geeigneten Reaktor, beispielsweise einem Glasreaktor, zusammengegeben und mit dem Fachmann bekannten Vorrichtungen gerührt, beispielsweise in einer Glaswanne mit einem mechanisch betriebenen Flügelrührer, beispielsweise bei einer Temperatur von 1 bis 80 °C, bevorzugt bei Umgebungstemperatur.In one embodiment of the process of the invention, 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). In general, 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. According to the invention, the dispersion of the magnetic particles can be prepared by all methods known to the person skilled in the art. In a preferred embodiment, 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.
Das Behandeln der Dispersion aus Schritt (B) mit wenigstens einem hydrophoben Magnetpartikel geschieht im Allgemeinen so, dass beide Komponenten durch dem Fachmann bekannte Methoden zusammengegeben werden. In einer bevorzugten Ausführungsform wird der hydrophobierte magnetische Partikel in fester Form zu einer Dispersion der zu behandelnden Mischung gegeben. In einer weiteren bevorzugten Ausführungsform liegen beide Komponenten in dispergierter Form vor.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. In a preferred embodiment, the hydrophobized magnetic particle is added in solid form to a dispersion of the mixture to be treated. In a further preferred embodiment, both components are present in dispersed form.
Schritt (C) wird im Allgemeinen bei einer Temperatur von 1 bis 80 °C, bevorzugt 10 bis 30 °C durchgeführt. Schritt (C) des erfindungsgemäßen Verfahrens kann in allen dem Fachmann bekannten Vorrichtungen erfolgen, beispielsweise in einer Mühle, bevorzugt in einer Kugelmühle. In einer besonders bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird Schritt (C) in der gleichen Vorrichtung, bevorzugt einer Mühle durchgeführt, in der Schritt (A) und gegebenenfalls Schritt (B) durchgeführt werden.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. In a particularly preferred embodiment of the process according to the invention, step (C) is carried out in the same apparatus, preferably a mill, in which step (A) and optionally step (B) are carried out.
In Schritt (C) lagert sich der wenigstens eine magnetische Partikel an den hydrophoben Stoff der zu behandelnden Mischung an. Die zwischen den beiden Komponenten bestehende Bindung basiert auf hydrophoben Wechselwirkungen. Zwischen dem wenigstens einen magnetischen Partikel und dem hydrophilen Anteil der Mischung findet im Allgemeinen keine bindende Wechselwirkung statt, so dass zwischen diesen Komponenten keine Anlagerung stattfindet. Nach Schritt (C) liegen somit in der Mischung Anlagerungsprodukte des wenigstens eine hydrophoben Stoffes und des wenigstens einen magnetischen Partikels neben dem wenigstens einen hydrophilen Stoff vor.In 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. After 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.
Schritt (D) des erfindungsgemäßen Verfahrens umfasst das Abtrennen des Anlagerungsproduktes aus Schritt (C) von der Mischung durch Anlegen eines magnetischen Feldes.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.
Schritt (D) kann in einer bevorzugten Ausführungsform durchgeführt werden, indem ein Dauermagnet in den Reaktor eingebracht wird, in dem sich die Mischung aus Schritt (C) befindet. In einer bevorzugten Ausführungsform befindet sich zwischen Dauermagnet und zu behandelnder Mischung eine Trennwand aus nicht magnetischem Material, beispielsweise die Glaswand des Reaktors. In einer weiteren bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird in Schritt (D) ein elektrisch schaltbarer Magnet eingesetzt, der nur dann magnetisch ist, wenn ein elektrischer Strom fließt. Geeignete Vorrichtungen sind dem Fachmann bekannt.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. 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. In a further preferred embodiment of the method according to the invention, 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.
Schritt (D) des erfindungsgemäßen Verfahrens kann bei jeder geeigneten Temperatur durchgeführt werden, beispielsweise 10 bis 60 °C.Step (D) of the process according to the invention may be carried out at any suitable temperature, for example 10 to 60 ° C.
Während Schritt (D) wird die Mischung bevorzugt permanent mit einem geeigneten Rührer gerührt.During step (D), the mixture is preferably stirred continuously with a suitable stirrer.
In Schritt (D) kann das Anlagerungsprodukt aus Schritt (C) gegebenenfalls durch alle dem Fachmann bekannten Verfahren abgetrennt werden, beispielsweise durch Ablassen der Flüssigkeit mit dem hydrophilen Anteil der Suspension aus dem Bodenventil aus dem für Schritt (D) benutzten Reaktor oder Abpumpen der nicht durch den mindestens einen Magneten festgehaltenen Anteile der Suspension durch einen Schlauch.In 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.
Der optionale Schritt (E) des erfindungsgemäßen Verfahrens umfasst das Spalten des abgetrennten Anlagerungsproduktes aus Schritt (D), um den wenigstens einen ersten Stoff und den wenigstens einen Magnetpartikel separat zu erhalten. Der erfindungsgemäße Schritt (E) kann durchgeführt werden, wenn der wenigstens eine, erste Stoff separat erhalten werden soll. In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens erfolgt das Spalten in Schritt (E) nicht zerstörerisch, d.h., dass die in der Dispersion vorliegenden Einzelkomponenten chemisch nicht verändert werden. Beispielsweise erfolgt die erfindungsgemäße Spaltung nicht durch Oxidation des Hydrophobierungsmittels, beispielsweise unter Erhalt der Oxidationsprodukte oder von Abbauprodukten des Hydrophobierungsmittels.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. In a preferred embodiment of the process according to the invention, the cleavage in step (E) is not destructive, that is to say that the individual components present in the dispersion are not changed chemically. For example, 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.
Das Spalten kann nach allen dem Fachmann bekannten Verfahren erfolgen, die dazu geeignet sind, das Anlagerungsprodukt derart zu spalten, dass der wenigstens eine magnetische Partikel in wieder einsetzbarer Form zurück gewonnen werden kann. In einer bevorzugten Ausführungsform wird der abgespaltene Magnetpartikel wieder in Schritt (C) eingesetzt.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. In a preferred embodiment, the cleaved magnetic particle is used again in step (C).
In einer bevorzugten Ausführungsform erfolgt das Spalten in Schritt (C) des erfindungsgemäßen Verfahrens durch Behandlung des Anlagerungsproduktes mit einer Substanz ausgewählt aus der Gruppe bestehend aus organischen Lösungsmitteln, basischen Verbindungen, sauren Verbindungen, Oxidationsmitteln, Reduktionsmitteln, oberflächenaktiven Verbindungen und Mischungen davon.In a preferred embodiment, 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.
Beispiele für geeignete organische Lösungsmittel sind Methanol, Ethanol, Propanol, beispielsweise n-Propanol oder iso-Propanol, aromatische Lösungsmittel, beispielsweise Benzol, Toluol, Xylole, Ether, beispielsweise Diethylether, Methyl-t-butyl-ether, Ketone, beispielsweise Aceton, und Mischungen davon. Beispiele für erfindungsgemäß einsetzbare basische Verbindungen sind wässrige Lösungen basischer Verbindungen, beispielsweise wässrige Lösungen von Alkali- und/oder Erdalkalihydroxiden, beispielsweise KOH, NaOH, wässrige Ammoniaklösungen, wässrige Lösungen organischer Amine der allgemeinen Formel R2 3N, wobei R2 unabhängig voneinander ausgewählt ist aus der Gruppe bestehend aus C1-C8-Alkyl, gegebenenfalls substituiert mit weiteren funktionellen Gruppen. In einer bevorzugten Ausführungsform erfolgt Schritt (D) durch Zugabe von wässriger NaOH-Lösung bis zu einem pH-Wert von 13, beispielsweise für die Abtrennung von mit OPS modifiziertem Cu2S. Die sauren Verbindungen können mineralische Säuren sein, beispielsweise HCl, H2SO4, HNO3 oder Mischungen davon, organische Säuren, beispielsweise Carbonsäuren. Als Oxidationsmittel kann beispielsweise H2O2 eingesetzt werden, beispielsweise als 30 gew.-%ige wässrige Lösung (Perhydrol). Für die Abtrennung von mit Thiolen modifiziertem Cu2S wird bevorzugt H2O2 oder Na2S2O4 eingesetzt.Examples of 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, and Mixtures thereof. Examples of basic compounds which can be used according to the invention are aqueous solutions of basic compounds, for example, aqueous solutions of alkali metal and / or alkaline earth metal hydroxides, for example KOH, NaOH, aqueous ammonia solutions, aqueous solutions of organic amines of the general formula R 2 3 N, where R 2 is independently selected from the group consisting of C 1 -C 8 alkyl optionally substituted with further functional groups. In a preferred embodiment, 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. For example, H 2 O 2 can be used as the oxidizing agent, for example as a 30% strength by weight 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.
Beispiele für erfindungsgemäß einsetzbare oberflächenaktive Verbindungen sind nichtionische, anionische, kationische und/oder zwitterionische Tenside.Examples of surface-active compounds which can be used according to the invention are nonionic, anionic, cationic and / or zwitterionic surfactants.
In einer bevorzugten Ausführungsform wird das Anlagerungsprodukt aus hydrophoben Stoff und magnetischem Teilchen mit einem organischen Lösungsmittel, besonders bevorzugt mit Aceton, Diesel, Solvesso® oder Shellsol®, gespalten. Dieser Vorgang kann auch mechanisch unterstützt werden. In einer bevorzugten Ausführungsform wird Ultraschall zur Unterstützung des Spaltungsvorgangs eingesetzt.In a preferred embodiment, 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.
Im Allgemeinen wird das organische Lösungsmittel in einer Menge verwendet, die ausreicht, um möglichst das gesamte Anlagerungsprodukt zu spalten. In einer bevorzugten Ausführungsform werden 20 bis 100 ml des organischen Lösungsmittels pro Gramm zu spaltendem Anlagerungsprodukt aus hydrophobem Stoff und magnetischem Partikel verwendet.In general, 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.
Erfindungsgemäß liegt nach der Spaltung der wenigstens eine erste Stoff und der wenigstens eine Magnetpartikel als Dispersion in dem genannten Spaltungsreagenz, bevorzugt einem organischen Lösungsmittel, vor.According to the invention, after cleavage, 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.
Der wenigstens eine Magnetpartikel kann aus der Dispersion enthaltend diesen wenigstens einen Magnetpartikel und den wenigstens einen ersten Stoff durch einen permanenten oder schaltbaren Magneten von der Lösung abgetrennt werden. Details dieses Abtrennens sind analog zu Schritt (D) des erfindungsgemäßen Verfahrens.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.
Bevorzugt wird der abzutrennende erste Stoff, bevorzugt die abzutrennende Metallverbindung, von dem organischen Lösungsmittel durch Abdestillieren des organischen Lösungsmittels getrennt. Der so erhältliche erste Stoff kann durch weitere, dem Fachmann bekannte Verfahren gereinigt werden. Das Lösungsmittel kann, gegebenenfalls nach Aufreinigung, wieder in das erfindungsgemäße Verfahren zurückgeführt werden.Preferably, 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.
Es werden Originaltailings einer Mine verwendet, wobei der Kupfergehalt mit 0,2 Gew.-% bestimmt wird.Original tailings of a mine are used, the copper content being determined to be 0.2% by weight.
100 g getrocknetes Material werden mit 160 mL (535 g) ZrO2-Kugeln (Durchmesser = 1,7 - 2,3 mm), 0,13 g (Octylcarbetoxy)-thiocarbonyethoxy-amin (H17C8OC=ONHC=SOC8H17), 62 mL Wasser und 1 mL Benzin in einen ZrO2-Behälter eingewogen und 30 Min. bei 200 U/min. konditioniert. Anschließend werden 2,0 g hydrophobes Magnetit (mit Octylphosphonsäure modifiziertes Fe3O4, Durchmesser = 4 µm) zugegeben und nochmals 30 min. bei 200 U/min. gemahlen.100 g of dried material are mixed with 160 mL (535 g) ZrO 2 spheres (diameter = 1.7-2.3 mm), 0.13 g (octylcarbetoxy) -thiocarbonyethoxy-amine (H 17 C 8 OC = ONHC = SOC 8 H 17 ), 62 mL of water and 1 mL of benzine are weighed into a ZrO 2 container and incubated for 30 min. At 200 rpm. conditioned. Subsequently, 2.0 g of hydrophobic magnetite (with Octylphosphonsäure modified Fe 3 O 4 , diameter = 4 microns) was added and again for 30 min. at 200 rpm. ground.
Die so entstandene Mischung wird mit Wasser verdünnt, so dass das Gemisch einen Feststoffgehalt von 40 Gew.-% aufweist. Anschließend werden die magnetischen Bestandteile von den unmagnetischen Bestandteilen mit einem Magneten getrennt, indem ein Co/Sm-Magnet an die Gefäß-Außenwand gehalten wird.The resulting mixture is diluted with water so that the mixture has a solids content of 40% by weight. Subsequently, the magnetic components are separated from the non-magnetic components with a magnet by holding a Co / Sm magnet to the vessel outer wall.
Von den 100 g eingesetzten Material sowie den 2,0 g eingesetzten Magnetit erhält man nach Trocknung 2,7 g magnetisches Material, welches einen Kupfergehalt von 5,2 Gew.-% aufweist. Dies entspricht 0,14 g (70%) des in den behandelten Tailings vorhandenen Kupfers.Of the 100 g of material used and the 2.0 g of magnetite used, 2.7 g of magnetic material are obtained after drying, which has a copper content of 5.2% by weight. This corresponds to 0.14 g (70%) of the copper present in the treated tailings.
Es werden Tailings einer Originalmine verwendet, wobei der Kupfergehalt mit 0,2 Gew.-% bestimmt wird.Tailings of an original mine are used, the copper content being determined to be 0.2% by weight.
100 g getrocknetes Material werden mit 160 mL (535 g) ZrO2-Kugeln (Durchmesser = 1,7 - 2,3 mm), 0.13 g Kaliumoctylxanthat, 62 mL Wasser und 1 mL Benzin in einen ZrO2-Behälter eingewogen und 30 Min. bei 200 U/min. konditioniert. Anschließend werden 2,0 g hydrophobes Magnetit (mit Octylphosphonsäure modifiziertes Fe3O4, Durchmesser = 4 µm) zugegeben und nochmals 30 min. bei 200 U/min. gemahlen.100 g dried material are weighed into a ZrO 2 container with 160 mL (535 g) ZrO 2 spheres (diameter = 1.7-2.3 mm), 0.13 g potassium octylxanthate, 62 mL water and 1 mL gasoline and left for 30 min at 200 rpm. conditioned. Subsequently, 2.0 g of hydrophobic magnetite (with Octylphosphonsäure modified Fe 3 O 4 , diameter = 4 microns) was added and again for 30 min. at 200 rpm. ground.
Die so entstandene Mischung wird mit Wasser verdünnt, so dass das Gemisch einen Feststoffgehalt von 40 Gew.-% aufweist. Anschließend werden die magnetischen Bestandteile von den unmagnetischen Bestandteilen mit einem Magneten getrennt, indem ein Co/Sm-Magnet an die Gefäß-Außenwand gehalten wird.The resulting mixture is diluted with water so that the mixture has a solids content of 40% by weight. Subsequently, the magnetic components are separated from the non-magnetic components with a magnet by holding a Co / Sm magnet to the vessel outer wall.
Von den 100 g eingesetzten Material sowie den 2 g eingesetzten Magnetit erhält man nach Trocknung 2,41 g magnetisches Material, welches einen Kupfergehalt von 4,5 % aufweist. Dies entspricht 0,108 g (54%) des in den behandelten Tailings vorhandenen Kupfers.Of the 100 g of material used and the 2 g of magnetite used, after drying, 2.41 g of magnetic material are obtained, which has a copper content of 4.5%. having. This corresponds to 0.108 g (54%) of the copper present in the treated tailings.
Es werden Tailings einer Originalmine verwendet, wobei der Kupfergehalt mit 0,1 Gew.-% bestimmt wird.Tailings from an original mine are used, the copper content being determined to be 0.1% by weight.
Es werden 100 g getrocknetes Material, 100 g ZrO2-Kugel (Durchmesser = 1,7 - 2,3 mm), 2 g Kaliumoctylxanthat und 20 g Wasser in ein ZrO2-Gefäß eingewogen und 30 min. bei 200 U/min. konditioniert. Anschließend werden 2 g Magnetit (mit Octylphosphonsäure modifiziertes Fe3O4, Durchmesser = 4 µm) und 0,2 g Shellsol zugegeben und weitere 5 min. bei 150 U/min. gemahlen.100 g of dried material, 100 g of ZrO 2 sphere (diameter = 1.7-2.3 mm), 2 g of potassium octylxanthate and 20 g of water are weighed into a ZrO 2 vessel and incubated for 30 min. at 200 rpm. conditioned. Subsequently, 2 g of magnetite (with Octylphosphonsäure modified Fe 3 O 4 , diameter = 4 microns) and 0.2 g Shellsol added and another 5 min. at 150 rpm. ground.
Die so entstandene Mischung wird mit Wasser verdünnt, so dass das Gemisch einen Feststoffgehalt von 40 Gew.-% aufweist. Anschließend werden die magnetischen Bestandteile von den unmagnetischen Bestandteilen mit einem Magneten getrennt, indem ein Co/Sm-Magnet an die Gefäß-Außenwand gehalten wird.The resulting mixture is diluted with water so that the mixture has a solids content of 40% by weight. Subsequently, the magnetic components are separated from the non-magnetic components with a magnet by holding a Co / Sm magnet to the vessel outer wall.
Von den 100 g eingesetzten Material sowie den 2 g eingesetzten Magnetit erhält man nach Trocknung 2,67 g magnetisches Material, welches einen Kupfergehalt von 3,1 % aufweist. Dies entspricht 0,083 g (83%) des in den behandelten Tailings vorliegenden Kupfers.Of the 100 g of material used and the 2 g magnetite used is obtained after drying 2.67 g of magnetic material, which has a copper content of 3.1%. This corresponds to 0.083 g (83%) of the copper present in the treated tailings.
Claims (9)
- A process for separating at least one first material from a mixture comprising this at least one first material in an amount of from 0.001 to 1.0% by weight, based on the total mixture, and at least one second material, which comprises the following steps:(A) contacting of the mixture comprising at least one first material and at least one second material with at least one surface-active substance in the presence of at least one dispersion medium, with the surface-active substance binding to the at least one first material,(B) optionally, addition of at least one dispersion medium to the mixture obtained in step (A) in order to obtain a dispersion,(C) treatment of the dispersion from step (A) or (B) with at least one hydrophobic magnetic particle so that the at least one first material to which the at least one surface-active substance is bound and the at least one magnetic particle agglomerate,(D) separation of the agglomerate from step (C) from the mixture by application of a magnetic field,(E) optionally, dissociation of the agglomerate separated off in step (D) in order to obtain the at least one first material and the at least one magnetic particle separately,with the at least one first material being a metal compound selected from the group consisting of compounds of the transition metals, sulfidic ores, oxidic and/or carbonate-comprising ores and noble metals in elemental form and the at least one second material preferably being a hydrophilic metal compound.
- The process according to claim 1, wherein the surface-active substance is a substance of the general formula (I)
A-Z (I)
whereA is selected from among linear or branched C3-C30-alkyl, C3-C30-heteroalkyl, optionally substituted C6-C30-aryl, optionally substituted C6-C30-heteroalkyl, C6-C30-arylalkyl andZ is a group by means of which the compound of the general formula (I) binds to the at least one hydrophobic material. - The process according to claim 2, wherein Z is selected from the group consisting of anionic groups - (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 where X is selected from the group consisting of 0, S, NH, CH2 and n = 0, 1 or 2, optionally with cations selected from the group consisting of hydrogen, NR4 + where the radicals R are each, independently of one another, hydrogen or C1-C8-alkyl, an alkali metal or alkaline earth metal.
- The process according to any of claims 1 to 3, wherein the amount of surface-active substance in step (A) is from 0.0001 to 0.2% by weight, based on the mixture of a mixture to be treated and surface-active substance.
- The process according to claim 1, wherein the at least one second material is selected from the group consisting of oxidic and hydroxidic metal compounds.
- The process according to any of claims 1 to 5, wherein the at least one magnetic particle is selected from the group consisting of magnetic metals and mixtures thereof, ferromagnetic alloys of magnetic metals and mixtures thereof, magnetic iron oxides, cubic ferrites of the general formula (II)
M2+ xFe2+ 1-xFe3+ 2O4 (II)
whereM is selected from among Co, Ni, Mn, Zn and mixtures thereof andx ≤ 1,hexagonal ferrites and mixtures thereof. - The process according to any of claims 1 to 6, wherein the dispersion medium is water.
- The process according to any of claims 1 to 7, wherein the mixture comprising at least one first material and at least one second material is milled to particles having a size of from 100 nm to 150 µm before or during step (A).
- The process according to any of claims 1 to 8, wherein the dispersion obtained in step (A) or (B) has a solids content of from 10 to 50% by weight.
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| PL09764861T PL2376230T3 (en) | 2008-12-11 | 2009-12-09 | Enrichment of valuable ores from mine waste (tailings) |
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| PCT/EP2009/066693 WO2010066770A1 (en) | 2008-12-11 | 2009-12-09 | Enrichment of valuable ores from mine waste (tailings) |
| EP09764861.2A EP2376230B1 (en) | 2008-12-11 | 2009-12-09 | Enrichment of valuable ores from mine waste (tailings) |
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| PE20110485A1 (en) | 2008-07-18 | 2011-07-09 | Siemens Ag | SELECTIVE SEPARATION OF SUBSTANCES WITH MODIFIED MAGNETIC PARTICLES |
| EP2313200B1 (en) | 2008-07-18 | 2012-06-27 | Basf Se | Inorganic particles comprising an organic coating that can be hydrophilically/hydrophobically temperature controlled |
| EP2321373A1 (en) | 2008-09-04 | 2011-05-18 | Basf Se | Modified particles and dispersions comprising said particles |
| WO2010060698A2 (en) | 2008-11-03 | 2010-06-03 | Basf Se | Pigment compositions |
| EP2401084B1 (en) | 2009-02-24 | 2019-05-22 | Basf Se | Cu-mo separation |
| EA022857B1 (en) | 2009-03-04 | 2016-03-31 | Басф Се | Magnetic separation of nonferrous metal ores by means of multi-stage conditioning |
| PE20120731A1 (en) | 2009-03-04 | 2012-06-15 | Basf Se | MAGNETIC HYDROPHOBIC AGGLOMERATES |
| US20110229384A1 (en) | 2010-03-18 | 2011-09-22 | Basf Se | Concentrate quality in the enrichment of ug-2 platinum ore |
| US20110272623A1 (en) | 2010-05-06 | 2011-11-10 | Siemens Ag | Formulation of hydrophobized magnetite |
| US8865000B2 (en) | 2010-06-11 | 2014-10-21 | Basf Se | Utilization of the naturally occurring magnetic constituents of ores |
| US9376457B2 (en) | 2010-09-03 | 2016-06-28 | Basf Se | Hydrophobic, functionalized particles |
-
2009
- 2009-12-09 AU AU2009324379A patent/AU2009324379A1/en not_active Abandoned
- 2009-12-09 MX MX2011006195A patent/MX2011006195A/en active IP Right Grant
- 2009-12-09 CN CN200980154100.7A patent/CN102271817B/en not_active Expired - Fee Related
- 2009-12-09 EP EP09764861.2A patent/EP2376230B1/en not_active Not-in-force
- 2009-12-09 US US13/139,091 patent/US8377312B2/en not_active Expired - Fee Related
- 2009-12-09 BR BRPI0922451A patent/BRPI0922451A2/en not_active IP Right Cessation
- 2009-12-09 WO PCT/EP2009/066693 patent/WO2010066770A1/en active Application Filing
- 2009-12-09 PE PE2011001204A patent/PE20120524A1/en not_active Application Discontinuation
- 2009-12-09 JP JP2011540066A patent/JP5637997B2/en not_active Expired - Fee Related
- 2009-12-09 PL PL09764861T patent/PL2376230T3/en unknown
- 2009-12-09 KR KR1020117015920A patent/KR20110095934A/en not_active Application Discontinuation
- 2009-12-09 CA CA2746550A patent/CA2746550A1/en not_active Abandoned
- 2009-12-09 RU RU2011128049/03A patent/RU2515933C2/en not_active IP Right Cessation
- 2009-12-10 AR ARP090104799A patent/AR074588A1/en active IP Right Grant
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2011
- 2011-06-10 CL CL2011001419A patent/CL2011001419A1/en unknown
- 2011-07-07 ZA ZA2011/04995A patent/ZA201104995B/en unknown
Also Published As
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|---|---|
| RU2515933C2 (en) | 2014-05-20 |
| AR074588A1 (en) | 2011-01-26 |
| EP2376230A1 (en) | 2011-10-19 |
| JP5637997B2 (en) | 2014-12-10 |
| JP2012511414A (en) | 2012-05-24 |
| PL2376230T3 (en) | 2015-01-30 |
| WO2010066770A1 (en) | 2010-06-17 |
| CN102271817A (en) | 2011-12-07 |
| US8377312B2 (en) | 2013-02-19 |
| MX2011006195A (en) | 2011-07-01 |
| PE20120524A1 (en) | 2012-04-28 |
| CA2746550A1 (en) | 2010-06-17 |
| CL2011001419A1 (en) | 2011-09-30 |
| CN102271817B (en) | 2014-10-01 |
| AU2009324379A1 (en) | 2011-07-28 |
| KR20110095934A (en) | 2011-08-25 |
| US20110240527A1 (en) | 2011-10-06 |
| BRPI0922451A2 (en) | 2015-12-15 |
| RU2011128049A (en) | 2013-01-20 |
| ZA201104995B (en) | 2012-10-31 |
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