EP2579987B1 - Nutzung der natürlich vorkommenden magnetischen bestandteile von erzen - Google Patents

Nutzung der natürlich vorkommenden magnetischen bestandteile von erzen Download PDF

Info

Publication number
EP2579987B1
EP2579987B1 EP11724259.4A EP11724259A EP2579987B1 EP 2579987 B1 EP2579987 B1 EP 2579987B1 EP 11724259 A EP11724259 A EP 11724259A EP 2579987 B1 EP2579987 B1 EP 2579987B1
Authority
EP
European Patent Office
Prior art keywords
magnetic particles
substance
process according
mixture
magnetic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP11724259.4A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2579987A1 (de
Inventor
Alexej Michailovski
Imme Domke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=44342917&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2579987(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by BASF SE filed Critical BASF SE
Priority to PL11724259T priority Critical patent/PL2579987T3/pl
Priority to EP11724259.4A priority patent/EP2579987B1/de
Publication of EP2579987A1 publication Critical patent/EP2579987A1/de
Application granted granted Critical
Publication of EP2579987B1 publication Critical patent/EP2579987B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B03C1/005—Pretreatment specially adapted for magnetic separation
    • B03C1/015—Pretreatment specially adapted for magnetic separation by chemical treatment imparting magnetic properties to the material to be separated, e.g. roasting, reduction, oxidation
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C2201/00—Details of magnetic or electrostatic separation
    • B03C2201/18—Magnetic separation whereby the particles are suspended in a liquid

Definitions

  • the present invention relates to a method for separating at least one first substance, which is a hydrophobic metal compound or carbon, from a mixture comprising these at least one first substance, at least one second substance, which is a hydrophilic metal compound, and magnetic particles, comprising the following steps (A) at least partially separating the magnetic particles by applying a magnetic field gradient, optionally in the presence of at least one dispersing agent, in order to obtain a mixture comprising at least a first substance and at least a second substance and a reduced amount of magnetic particles, the step ( A) separated magnetic particles are used in step (B), and the magnetic particles separated in step (A) are hydrophobized on the surface with at least one surface-active substance before use in step (B), (B) contacting the mixture e Containing at least a first substance and at least a second substance from step (A) with the magnetic particles obtained in step (A) and optionally further magnetic particles which are hydrophobicized on the surface with at least one surface-active substance, so that the at least one first Attach substance
  • the present invention relates to a method for enriching ores in the presence of gait.
  • Methods for separating value ores from mixtures containing these are already known from the prior art.
  • WO 02/0066168 A1 relates to a process for the separation of valuable ores from mixtures containing these, in which suspensions or slurries of these mixtures are treated with particles which are magnetic and / or floatable in aqueous solutions. After adding the magnetic and / or buoyant particles, a magnetic field is applied so that the agglomerates are separated from the mixture.
  • the degree of binding of the magnetic particles to the ore and the strength of the bond is not sufficient to carry out the process with a sufficiently high yield and effectiveness.
  • US 4,657,666 discloses a process for the enrichment of value ores, wherein the gait present in the gangue is reacted with magnetic particles, whereby agglomerates are formed due to the hydrophobic interactions.
  • the magnetic particles are made hydrophobic on the surface by treatment with hydrophobic compounds, so that there is a connection to the ore.
  • 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 ethyl xanthate before the magnetic particle is added. In this method, a separation of valuable ore and magnetic particles takes place by destroying the surface-activating substance which has been applied to the valuable ore in the form of the surface-activating solution. Furthermore, only C 4 hydrophobizing agents are used for the ore in this process.
  • US 4,834,898 discloses a method for separating non-magnetic materials by contacting them with magnetic reagents which are coated with two layers of surface-active substances. US 4,834,898 further discloses that the surface charge of the non-magnetic particles to be separated can be affected by various types and concentrations of electrolyte reagents. For example, the surface charge is changed by adding multivalent anions, for example tripolyphosphate ions.
  • WO 2007/008322 A1 discloses a magnetic particle, which is hydrophobic on the surface, for the separation of impurities from mineral substances by magnetic separation processes. According to WO 2007/008322 A1 a dispersant selected from sodium silicate, sodium polyacrylate or sodium hexametaphosphate can be added to the solution or dispersion.
  • WO 2009/030669 A2 discloses a method for separating valuable ores from mixtures of these with the gait through magnetic particles, the valuable ore first being hydrophobicized with a suitable substance, so that the hydrophobicized valuable ore and the magnetic particles can accumulate and be separated off.
  • WHERE 2009/065802 A2 discloses a similar method for separating ore from gait by magnetic particles, the attachment of magnetic particles and ore based on different surface charges. Both methods can still be improved in terms of their efficiency.
  • hydrophobic means that the corresponding particle is inherently hydrophobic, or can subsequently be rendered hydrophobic by treatment with the at least one surface-active substance. It is also possible for an intrinsically hydrophobic particle to be additionally rendered hydrophobic by treatment with the at least one surface-active substance.
  • hydrophobic means that the surface of a corresponding “hydrophobic substance” or a “hydrophobized substance” has a contact angle of> 90 ° with water against air.
  • hydrophilic means that the surface of a corresponding “hydrophilic substance” has a contact angle of ⁇ 90 ° with water against air.
  • the at least one hydrophobic metal compound is selected from the group of the sulfidic ores, the oxidic and / or carbonate-containing ores, for example azurite [Cu 3 (CO 3 ) 2 (OH) 2 ], cuprite [Cu 2 O] or malachite [Cu 2 [(OH) 2
  • sulfidic ores which can be used according to the invention are e.g. B. selected from the group of copper ores consisting of covellite CuS, molybdenum (IV) sulfide, chalcopyrite (copper pebbles) CuFeS 2 , bornite Cu 5 FeS 4 , chalcocyte (copper luster) Cu 2 S, zinc blende ZnS, galena PbS, pentlandite (Ni , Fe) x S with x approximately equal to 0.9, and mixtures thereof.
  • B selected from the group of copper ores consisting of covellite CuS, molybdenum (IV) sulfide, chalcopyrite (copper pebbles) CuFeS 2 , bornite Cu 5 FeS 4 , chalcocyte (copper luster) Cu 2 S, zinc blende ZnS, galena PbS, pentlandite (Ni , Fe) x S with x approximately equal to 0.9, and mixture
  • the at least one second substance is preferably selected from the group consisting of oxidic and hydroxide metal compounds, for example silicon dioxide SiO 2 , silicates, aluminosilicates, for example feldspar, 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 O3, 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 feldspar, for example albite Na (Si 3 Al) O 8 , mica, for example muscovite KAl 2 [(OH , F) 2 AlSi 3 O 10 ], garnets
  • untreated ore mixtures which are obtained from mine deposits are preferably used in the process according to the invention.
  • the first substances to be separated are made hydrophobic on the surface.
  • the average size of the magnetic particles present in the mixture to be treated according to the invention is generally from 100 nm to 100 ⁇ m.
  • the magnetic particles are generally in an amount of 0.05 to 10% by weight, preferably 0.1 to 5% by weight, particularly preferably 0.2 to 2% by weight, in each case based on the entire mixture.
  • the mixture comprising at least one first substance, at least one second substance and magnetic particles in step (A) is in the form of particles with an average size of 100 nm to 100 ⁇ m, see for example US 5,051,199 .
  • this particle size is obtained by grinding. Suitable processes and devices are known to the person skilled in the art, for example wet milling in a ball mill.
  • a preferred embodiment of the method according to the invention is characterized in that the mixture containing at least a first substance, at least a second substance and magnetic particles is ground to particles with an average size of 100 nm to 100 ⁇ m before or during step (A).
  • Preferred mixtures have a content of at least one first substance, in particular sulfidic minerals, of at least 0.4% by weight, particularly preferably at least 1% by weight, in each case based on the mixture as a whole.
  • the at least one second substance in particular oxidic minerals, is preferably present in the mixture to be treated according to the invention in an amount such that the sum of magnetic particles, at least one first substance, at least one second substance and optionally further minerals results in 100% by weight .
  • 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 can 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 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 other salts, for example azurite [Cu 3 (CO 3 ) 2 (OH) 2 ], malachite [Cu 2 [ (OH) 2 (CO 3 )]], barite (BaSO 4 ), monacite ((La-Lu) PO 4 ).
  • noble metals for example Au, Pt, Pd, Rh etc., preferably in the solid state.
  • a typically used ore mixture which can be separated by the inventive method has the following composition: about 30 wt .-% SiO 2, about 30 wt .-% Na (Si 3 Al) O 8, 2 wt .-% FeCuS 2 , approx. 0.01% by weight MoS 2 , approx. 1% by weight Fe 3 O 4 , balance chromium, iron, titanium and magnesium oxides.
  • Step (A) of the method according to the invention comprises at least partially separating the magnetic particles by applying a magnetic field gradient, optionally in the presence of at least one dispersing agent, in order to obtain a mixture comprising at least one first substance and at least one second substance and a reduced amount of magnetic particles , wherein those separated in step (A) magnetic particles are used in step (B), and the magnetic particles separated in step (A) are hydrophobicized on the surface with at least one surface-active substance before use in step (B).
  • the magnetic particles can generally be separated off by all magnetic separation processes known to the person skilled in the art.
  • step (A) of the process according to the invention is carried out without the addition of a dispersing agent, i. H. carried out in the absence of a dispersant.
  • Step (A) of the process according to the invention is carried out in a second, preferred embodiment in dispersion, i.e. H. carried out in the presence of at least one dispersant, d. H. the at least one first substance, the at least one second substance and the mixture containing the magnetic particles is present in at least one dispersant.
  • step (A) of the method according to the invention preferably first comprises the preparation of a dispersion. Methods for producing a dispersion are known to the person skilled in the art.
  • dispersants in which the mixture to be treated according to the invention is not completely soluble are generally suitable as dispersants.
  • Suitable dispersants are selected, for example, from the group consisting of water, water-soluble organic compounds, for example alcohols having 1 to 4 carbon atoms, and mixtures thereof.
  • the dispersant is water.
  • the amount of dispersant can be selected so that a dispersion is obtained which is easy to stir and / or convey.
  • the amount of mixture to be treated is 10 to 50% by weight, particularly preferably 25 to 40% by weight, based on the total slurry or dispersion.
  • Suitable devices for magnetic separation preferably on an industrial scale, are known to the person skilled in the art.
  • Step (A) of the method according to the invention can be carried out in all suitable devices known to the person skilled in the art, for example in a wet drum separator, high-gradient magnetic separator or related devices.
  • Step (A) of the process according to the invention can be carried out at any suitable temperature, for example 10 to 60 ° C.
  • the magnetic particles which are present in the minerals to be treated preferably are at least partially separated off in order to obtain a mixture comprising at least one first substance and at least one second substance and a reduced amount of magnetic particles.
  • the magnetic particles in step (A) are generally separated off at least 50%, preferably at least 60%, particularly preferably at least 70%, very particularly preferably completely. It is preferred according to the invention to remove as large a proportion of the magnetic particles as possible in step (A) of the method according to the invention in order to obtain the described advantages according to the invention to the greatest extent possible.
  • the separated magnetic particles can generally be separated from the remaining dispersion by all methods known to the person skilled in the art.
  • step (A) of the process according to the invention on the one hand a mixture containing at least a first and a second substance in a dispersing agent, and on the other hand magnetic particles, separately from one another, are obtained.
  • the magnetic particles obtained in step (A) of the process according to the invention in particular the ferromagnetic minerals, can be used as raw material according to the invention and can be supplied to workup processes known to the person skilled in the art, for example smelting processes.
  • the magnetic particles obtained in step (A) are optionally subjected to further steps before use in step (B), for example grinding the particles to an average size of 100 nm to 20 ⁇ m, preferably by wet grinding.
  • the crushing is wet, preferably aqueous, in a ball mill, such as. B. in a rotary or agitator ball mill.
  • Inert bodies with a diameter of 1 to 50 mm, consisting of metal or preferably of ceramic materials, can serve as grinding media.
  • the magnetic particles separated in step (A) are hydrophobized on the surface with at least one surface-active substance before use in step (B) or, depending on the embodiment of step (B), are functionalized accordingly.
  • the hydrophobization is preferably carried out by contacting the comminuted magnetic particles, which are separated off in step (A), with a suitable hydrophobizing agent, e.g. B. long-chain fatty acids, phosphonic acids, phosphoric acid mono- or diesters, or their salts, alternatively generated with mono- or dialkylsilanols, for example in situ by hydrolysis of corresponding alkyl alkoxysilanes, mono- or dialkylsiloxanes.
  • a suitable hydrophobizing agent e.g. B. long-chain fatty acids, phosphonic acids, phosphoric acid mono- or diesters, or their salts, alternatively generated with mono- or dialkylsilanols, for example in situ by hydrolysis of corresponding alkyl alkoxysilanes, mono- or dialkylsiloxanes.
  • the hydrophobization can be carried out in an aqueous or organic, preferably aqueous, medium.
  • a drying and / or calcination step for example at a temperature below 200 ° C., of the hydrophobized magnetic particle is carried out before the reuse in step (B).
  • a method is preferred which dispenses with this drying step.
  • An advantage of the method according to the invention, in particular step (A) according to the invention, is that magnetic particles which have a disruptive effect on the overall method are removed from the mixture before the at least one first substance is actually separated off.
  • the separation according to the invention in step (A) removes the naturally occurring magnetic particles which are inactive in step (B) of the method according to the invention, as a result of which the space-time yield of the entire method can be increased.
  • the amount of magnetic particles to be used can additionally be reduced.
  • Step (B) of the method according to the invention comprises contacting the mixture comprising at least a first substance and at least a second substance from step (A) with magnetic particles which are hydrophobicized on the surface with at least one surface-active substance, so that the at least one first Attach material and the magnetic particles, the attachment taking place by attractive forces between the at least one first material and the magnetic particles.
  • step (B) of the process according to the invention it is generally possible to use all magnetic particles known to the person skilled in the art which meet the requirements of the process according to the invention, for example dispersibility in the dispersant used and ability to form sufficiently stable agglomerates with the at least one first substance.
  • the magnetic particles should have a sufficiently high saturation magnetizability, for example 25-300 emu / g, and a low remanence, so that the agglomerate can be separated from the dispersion in sufficient amount in step (C) of the process according to the invention.
  • step (B) magnetite Fe 3 O 4 is very particularly preferably used as the magnetic particle.
  • the size of the magnetic particles used according to the invention is preferably 10 nm to 1 ⁇ m.
  • step (A) The magnetic particles separated in step (A) are used in step (B). It is furthermore possible that in this preferred embodiment further magnetic particles of the same or a different type are added to the magnetic particles obtained in step (A) before they are used in step (B).
  • B is a linear or branched C 6 -C 18 alkyl, preferably linear C 8 -C 12 alkyl, very particularly preferably a linear C 12 alkyl.
  • Heteroatoms optionally present 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 with Hal 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 -PS 3 2- , - (X) n -PS 2 - , - (X) n -POS - , - (X) n -PO 2 - , - (X) n -CO 2 - , - (X) n -CS 2 - , - (X) n -COS
  • n 2 in the formulas mentioned, there are two identical or different, preferably identical, groups B bound to a group Y.
  • Very particularly preferred hydrophobizing substances of the general formula (II) are alkyltrichlorosilanes (alkyl group with 6-12 carbon atoms), alkyltrimethoxysilanes (alkyl group with 6-12 carbon atoms), mono- and dialkyl esters of phosphoric acid (alkyl group with 6-15 carbon atoms), long-chain saturated and unsaturated fatty acids such as B. lauric acid, oleic acid, stearic acid or mixtures thereof.
  • the at least one first substance to be separated and the magnetic particles accumulate in step (B) of the method according to the invention.
  • step (B) can generally be carried out by all attractive forces known to the person skilled in the art between the at least one first substance and the magnetic particles. According to the invention, essentially only the at least one first substance and the magnetic particles accumulate in step (B) of the method according to the invention, whereas the at least one second substance and the magnetic particles essentially do not accumulate.
  • the mixture comprising at least one first substance and at least one second substance is ground before or during step (B) to give particles with a size of 100 nm to 100 ⁇ m.
  • the at least one first substance and the magnetic particles are deposited due to hydrophobic interactions, different surface charges and / or compounds present in the mixture which selectively couple the at least one first substance and the magnetic particles , on.
  • step (B) is carried out by first bringing the at least one first substance contained in the mixture into contact with a surface-active substance in order to make it hydrophobic, this mixture is further brought into contact with magnetic particles, so that the magnetic particles and the at least one first substance that is hydrophobicized on the surface attach.
  • surface-active substance means a substance which is able to remove the surface of the particle to be separated, i. H. of the at least one first substance, in the presence of the other particles which are not to be separated, so that an attachment of a hydrophobic particle is brought about by hydrophobic interactions.
  • Surface-active substances which can be used according to the invention selectively attach to the at least one first substance and thereby bring about a suitable hydrophobicity of the first substance.
  • “selective addition” means that the distribution coefficient of the surface-active substance between the surface of the at least one first substance and the surface of the at least one second substance is generally> 1, preferably> 100, particularly preferably> 10000, that is, the surface-active substance preferably attaches to the surface of the at least one first substance and not to the surface of the at least one second substance.
  • A is a linear or branched C 4 -C 12 alkyl, very particularly preferably a linear C 4 or C 8 alkyl.
  • Heteroatoms optionally present according to the invention are selected from N, O, P, S and halogens such as F, Cl, Br and I.
  • A is preferably a linear or branched, preferably linear, C 6 -C 20 -alkyl.
  • A is preferably a branched C 6 -C 14 -alkyl, the at least one substituent, preferably having 1 to 6 carbon atoms, preferably in the 2-position, being present, for example 2-ethylhexyl and / or 2-propylheptyl.
  • n 2 in the formulas mentioned, there are two identical or different, preferably identical, groups A bonded to a group Z.
  • A is independently a linear or branched, preferably linear, C 6 -C 20 alkyl, for example n Octyl, or a branched C 6 -C 14 alkyl, the branching preferably being in the 2-position, for example 2-ethylhexyl and / or 2-propylheptyl.
  • the counterions in these compounds are preferably cations selected from the group consisting of hydrogen, NR 4 + with R, independently of one another, hydrogen and / or C 1 -C 8 -alkyl, alkali or alkaline earth metals, in particular sodium or potassium.
  • Very particularly preferred compounds of the general formula (III) are n-octyl xanthates, di-n-octyl dithiophosphates, 2-ethylhexyl and 2-propylheptyl xanthates and dithiophosphates, for example sodium or potassium n-octyl xanthate, sodium or potassium di-n-octyldithiophosphate, or mixtures of these compounds.
  • particularly preferred surface-active substances are mono-, di- and trithiols or 8-hydroxyquinolines, for example described in EP 1 200 408 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 meanings given above for A or long-chain saturated or unsaturated fatty acids such as.
  • OPS octylphosphonic acid
  • EtO EtO 3 Si-A
  • MeO 3 Si-A
  • no hydroxamates are used as surface-active substances for modifying metal oxides.
  • particularly preferred surface-active substances are mono-, di- and trithiols or xanthates.
  • Z is - (X) n -CS 2 - , - (X) n -PO 2 - or - (X) n -S - with X equal to O and n equal to 0 or 1 and one Cation selected from hydrogen, sodium or potassium.
  • Very particularly preferred surface-active substances are 1-octanethiol, potassium n-octylxanthate, potassium butylxanthate, octylphosphonic acid or carboxythionocarbamates
  • the at least one surface-active substance is generally used in an amount sufficient to achieve the desired effect. In a preferred embodiment, the at least one surface-active substance is used in an amount of 5 to 1000 g per ton of mixture to be treated.
  • magnetic particles are mentioned above.
  • magnetic particles are particularly preferably used which are hydrophobized on the surface with at least one surface-active substance.
  • Particularly preferred surface-active substances are the above-mentioned compounds of the general formula (II).
  • step (B) of the process according to the invention the mixture to be treated from step (A) is first mixed with at least one hydrocarbon in an amount of from 0.01 to 0.4% by weight, based on the sum of treating mixture and at least one hydrocarbon in contact, and this mixture is further brought into contact with magnetic particles.
  • Embodiment B2 is particularly advantageous if, in addition to the at least one first and at least one second substance, at least one third substance is also present in the mixture.
  • the at least one third substance is preferably selected from the group that has already been mentioned for the at least one second substance, the at least one second and the at least one third substance being different.
  • hydrocarbon means an organic chemical compound which is essentially composed of carbon, hydrogen and optionally oxygen. If the hydrocarbons which can be used according to the invention also contain oxygen in addition to carbon and hydrogen, this is present, for example, in the form of ester, carboxylic acid and / or ether groups. In step (B) according to embodiment B2 of the process according to the invention, both an essentially uniform hydrocarbon and a mixture of hydrocarbons can be used.
  • Hydrocarbons or mixtures which can be used according to the invention generally have a low viscosity under the conditions of the process according to the invention, so that they are liquid and easily mobile under the process conditions according to the invention. It is preferred to use hydrocarbons or mixtures which have a viscosity of 0.1 to 100 cP, preferably 0.5 to 5 cP, in each case at 20 ° C.
  • Hydrocarbons or mixtures which can be used according to the invention generally have a flash point of 20 20 ° C., preferably ⁇ 40 ° C.
  • the present invention therefore also relates to the method according to the invention, the at least one hydrocarbon having a flash point of 20 20 ° C., particularly preferably 40 40 ° C.
  • the at least one hydrocarbon is selected from the group consisting of mineral oils, vegetable oils, biodiesel, BtL fuels (biomass-to-liquid), products of coal liquefaction, products of the GtL process (gas to liquid) Natural gas) and mixtures thereof.
  • Mineral oils are, for example, crude oil derivatives and / or oils produced by distillation from lignite, hard coal, peat, wood, petroleum and possibly also other mineral raw materials.
  • Mineral oils generally consist of hydrocarbon mixtures of paraffinic, i.e. H. saturated chain hydrocarbons, naphthenic, d. H. saturated annular hydrocarbons, and aromatic hydrocarbons.
  • a particularly preferred crude oil derivative is diesel or gas oil.
  • Diesel generally has a composition known to those skilled in the art. Essentially, diesel is based on mineral oil, i.e. H. Diesel is a fraction in the separation of mineral oil by distillation. The main components of diesel are mainly alkanes, cycloalkanes and aromatic hydrocarbons with about 9 to 22 carbon atoms per molecule and a boiling range from 170 ° C to 390 ° C.
  • Vegetable oils are generally among the fats and fatty oils that are obtained from oil plants. Vegetable oils consist of triglycerides, for example. Vegetable oils suitable according to the invention are selected, for example, from the group consisting of sunflower oil, rapeseed oil, safflower oil, soybean oil, corn oil, peanut oil, olive oil, herring oil, cottonseed oil, palm oil and mixtures thereof.
  • Biodiesel generally has a composition known to those skilled in the art. Biodiesel essentially contains methyl esters of saturated C 16 -C 18 and unsaturated C 18 fatty acids, in particular rapeseed oil methyl esters
  • Coal liquefaction products can be obtained, for example, by the Fischer-Tropsch or Sasol process.
  • the BtL and GtL processes are known to the person skilled in the art.
  • diesel, kerosene and / or light gas oil is used as the hydrocarbon.
  • diesel from the brands Solvesso® and / or Shellsol® can be used advantageously.
  • step (B) according to embodiment B2 of the process according to the invention, at least one hydrophobizing agent can optionally also be added.
  • Suitable hydrophobicizing agents are the above-mentioned compounds of the general formula (III).
  • step (B) of the process according to the invention the mixture to be treated from step (A) is first brought into contact with at least one hydrophobizing agent, so that an adduct is formed from the at least one hydrophobizing agent and the at least one first substance.
  • This adduct is then brought into contact with magnetic particles functionalized on the surface with at least one polymeric compound which has an LCST ( Lower Critical Solution Temperature ) at a temperature at which the polymeric compound has a hydrophobic character, so that the adduct and the functionalized magnetic particles agglomerate.
  • LCST Lower Critical Solution Temperature
  • the at least one hydrophobizing agent is generally used in an amount sufficient to achieve the desired effect.
  • the at least one hydrophobizing agent in an amount from 0.01 to 5% by weight, based on the at least one first substance present in the mixture.
  • step (B) comprises contacting the adduct of at least one first substance and hydrophobicizing agent with magnetic particles that are surface-functionalized with at least one polymeric compound that has a transition temperature LCST ( Lower Critical Solution Temperature ).
  • LCST Lower Critical Solution Temperature
  • the magnetic particles are functionalized on the surface with at least one polymeric compound.
  • the polymeric compounds used according to the invention are distinguished by the fact that they have a transition temperature LCST ( Lower Critical Solution Temperature ). Below this LCST, the polymeric compound has a hydrophilic character, since the polymer chain has a hydration shell, for example due to the addition of water molecules. Above the LCST, the polymeric compound has a hydrophobic character, since the polymer chain is no longer surrounded by a hydration shell, for example. Depending on the polymeric compound, the reverse case is also possible, namely that the polymeric compound has a hydrophobic character below the LCST and has a hydrophilic character above the LCST.
  • LCST Lower Critical Solution Temperature
  • polymeric compound If such a polymeric compound is heated from below the LCST to a temperature above the LCST, the polymeric compound switches from hydrophilic to hydrophobic at the LCST, or vice versa.
  • the polymers which can be used according to the invention thus have a hydrophilic or hydrophobic character, depending on the temperature.
  • the change in the polymeric compound from hydrophobic to hydrophilic or vice versa corresponds to a phase transition which generally takes place in a closed system in a narrow temperature range of, for example, 0.5 ° C.
  • the phase transition can extend over a broader range of, for example, 15 ° C., for example by changing the concentration of the components present, for example polymers and / or foreign substances, varying the pH and / or the pressure.
  • the temperature range in which the transition takes place generally increases with increasing chain length.
  • the properties described for the polymeric compounds which can be used according to the invention are essentially also present in the case of the particles, in particular magnetic particles, modified with these polymeric compounds.
  • the polymeric compound is hydrophobic above the LCST and hydrophilic below the LCST.
  • polymer means a, preferably organic, compound with a molecular weight of at least 500 g / mol, preferably 500 to 10,000 g / mol, particularly preferably 1000 to 7000 g / mol.
  • the at least one polymeric compound is selected from the group consisting of polyvinyl ethers, for example polyvinyl methyl ether, poly-N-alkyl-acrylamides, for example poly-NC 1 -C 6 -alkyl acrylamides, in particular poly N-isopropylacrylamide, or N-alkyl-acrylamide-acrylamide copolymers, poly-N-vinyl-caprolactams, copolymers based on alkylene oxides, for example copolymers of ethylene oxide, propylene oxide and / or butylene oxide, preferably polymeric compounds, obtainable by alkoxylation of C 1 -C 12 alcohols with 1 to 130 units of ethylene oxide, propylene oxide and / or butylene oxide, and mixtures thereof.
  • polyvinyl ethers for example polyvinyl methyl ether
  • poly-N-alkyl-acrylamides for example poly-NC 1 -C 6 -alkyl acrylamides, in particular poly N-
  • Suitable polymeric compounds and processes for their preparation are, for example, in Li et al., International Journal of Pharmacology (2006), 2 (5), 513-519 , and Crespy et al., Polymer International (2007), 56 (12), 1461-1468 , called. These polymeric compounds are hydrophilic below the LCST and hydrophobic above the LCST.
  • the polymeric compounds mentioned which have an LCST are bonded to the corresponding magnetic particles by means of functional groups.
  • These functional groups can be present per se in the polymeric compounds mentioned, or the functional groups can be introduced into the polymeric compounds by processes known to the person skilled in the art, i. H. the polymeric compounds are functionalized.
  • Suitable functional groups are those which ensure a sufficiently strong bond between magnetic particles and polymeric compound, for example selected from the group consisting of thiol group -SH, carboxylic acid group -CO 2 H, optionally at least partially esterified phosphonic acid group -PO 3 R ' 2 with R' is hydrogen or C 1 -C 6 -alkyl (Va), optionally at least partially esterified phosphoric acid group -O-PO 3 R “ 2 with R” is hydrogen or C 1 -C 6 -alkyl (Vb), hydroxamate group (Vc), xanthate group (Vd) and mixtures thereof, particularly preferably selected from the group consisting of thiol group -SH, carboxylic acid group -CO 2 H, optionally at least partially esterified phosphonic acid group -PO 3 R ' 2 with R' equal to hydrogen or C 1 -C 6 alkyl (Va), optionally at least partially esterified phosphoric acid group -O-PO 3 R " 2 with R
  • F denotes a functional group which binds selectively to the at least one magnetic particle.
  • the choice of this functional group depends on the at least one magnetic particle to which the functional group is to bind.
  • a bond which is stable to dissociation should preferably be formed between the at least one magnetic particle and the at least one polymeric compound of the general formula (VI).
  • F is selected from the group consisting of carboxylic acid group -CO 2 H, optionally at least partially esterified phosphonic acid group -PO 3 R ' 2 with R' equal to hydrogen or C 1 -C 6 alkyl (Va), optionally at least partially esterified Phosphoric acid group -O-PO 3 R " 2 where R" is hydrogen or C 1 -C 6 alkyl (Vb), hydroxamate group (Vc), xanthate group (Vd) and mixtures thereof, particularly preferably an optionally at least partially esterified phosphonic acid group (Va) or an optionally at least partially esterified phosphoric acid group (Vb).
  • the functional groups Va to Vd are preferably bound to the polymer via free electron pairs.
  • B denotes an alkyl radical having 1 to 6 carbon atoms, for example methyl, ethyl, propyl, butyl, for example n-butyl, pentyl, hexyl.
  • the polymeric compounds of the general formula (VI) have an LCST which generally depends in each case on the amount of the individual alkylene oxides, ie. H. Ethylene oxide, propylene oxide and / or butylene oxide, is dependent in the polymer.
  • a polymeric compound that is composed exclusively of propylene oxide has, for example, an LCST of ⁇ -10 ° C.
  • a polymeric compound that is made up exclusively of ethylene oxide has, for example, an LCST of> 120 ° C.
  • the LCST of the polymeric compound used in the process according to the invention is -10 to 100 ° C., particularly preferably 5 to 45 ° C., very particularly preferably 20 to 40 ° C.
  • the LCST of a polymeric compound is in a temperature range of approx. 5 to 15 ° C. The width of this range is generally dependent on the uniformity, ie the monodispersity, of the polymeric compound used. The higher the monodispersity, the narrower the range of the LCST.
  • the functionalization of the magnetic particles with the at least one polymeric compound can be carried out by all methods known to the person skilled in the art.
  • the magnetic particles are functionalized with the at least one polymeric compound by first producing the magnetic particles themselves using known processes. These magnetic particles are then modified by contacting a solution of the functionalized polymeric compound, in particular compounds of the general formula (VI), in water or in an organic solvent, for example low molecular weight alcohols or ketones, and the product obtained is used to remove excess polymer Washed compound with an appropriate solvent.
  • a solution of the functionalized polymeric compound in particular compounds of the general formula (VI)
  • an organic solvent for example low molecular weight alcohols or ketones
  • the contacting in embodiment B3 of step (B) is preferably carried out at a temperature at which the polymeric compound used has a hydrophobic character, so that the switchable functionalized magnetic particles and the hydrophobized at least one first substance agglomerate.
  • this temperature can be above or below the LCST, preferably the temperature is above the LCST.
  • the contacting in embodiment B3 of step (B) is preferably carried out at a temperature which is greater than the LCST of the polymeric compound and less than the boiling point of the suspending agent used, particularly preferably at a temperature which is 1 to 20 ° C. above the LCST lies.
  • the contacting according to embodiment B3 is carried out at a temperature of 6 to 65 ° C., particularly preferably 21 to 60 ° C.
  • the contacting is carried out in embodiment B3 at a temperature which is above the melting temperature of the suspending agent used and below the LCST of the polymeric compound.
  • the contacting in embodiment B3 is preferably carried out at a temperature which is 1 to 20 ° C. below the LCST.
  • the contacting in embodiment B3 is therefore preferably carried out at a temperature of -15 to 44 ° C., particularly preferably 0 to 39 ° C.
  • step (B) of the process according to the invention is carried out by producing a dispersion of the mixture comprising at least a first substance and at least a second substance and the magnetic particles in a suitable dispersant, and adjusting the pH of the dispersion obtained to Value at which the at least one first substance and the magnetic particles carry opposite surface charges so that they agglomerate.
  • All magnetic particles known to the person skilled in the art which meet the requirements of embodiment B4 of step (B) of the process according to the invention can be used as magnetic particles, for example dispersibility in the dispersant used and ability to agglomerate with the at least one first substance.
  • the magnetic particles should have a defined coating with surface charges at a defined pH. These surface charges can be quantified with the so-called ⁇ potential.
  • the above-mentioned magnetic particles are preferably used.
  • the dispersion prepared according to embodiment B4 from step (B) contains at least one buffer system.
  • Suitable buffer systems for setting a specific pH are known to the person skilled in the art and are commercially available.
  • the addition of a buffer system to the suspension serves to set a suitable pH that is relatively stable.
  • the dispersion produced according to embodiment B4 of step (B) of the process according to the invention preferably has a pH of 2 to 13.
  • the pH of the dispersion produced depends on the isoelectric points of the substances to be separated. The limits of the pH range are also determined by the stability of the magnetic particles used, for example Fe 3 O 4 is not stable below pH 2.88.
  • the pH of the dispersion obtained is adjusted to a value at which the at least one first substance and the magnetic particles carry opposite surface charges, so that they agglomerate.
  • the agglomeration of the at least one first substance and the magnetic particles is based on their different surface charge in aqueous suspension as a function of the pH.
  • the surface charge of a particle in equilibrium with the surrounding liquid phase is determined by the zeta potential ⁇ . This varies depending on the pH of the solution or suspension.
  • the surface charge of the particle changes sign, i.e. the zeta potential ⁇ to be measured is exactly at the isoelectric point. If the zeta potential ⁇ on the y axis is plotted against the pH value on the x axis in a coordinate system, the resulting curve at the isoelectric point intersects the x axis.
  • Particles with different surface charges agglomerate with each other, while charged particles repel each other.
  • the dispersion prepared according to embodiment B4 of step (B) there are at least a first substance, at least a second substance and magnetic particles with the isoelectric points IEP (1), IEP (2) and IEP (M), where IEP (1) ⁇ IEP (M) ⁇ IEP (2) applies.
  • IEP (1) ⁇ pH ⁇ IEP (M) i.e. the pH of the suspension lies between the isoelectric points of the at least one first substance and the magnetic particles, the at least one first substance and the magnetic particles have opposite surface charges, while the at least one second substance and the magnetic particles have the same surface charge , so that the at least one first substance and the magnetic particles agglomerate.
  • the isoelectric point of the substances present in the mixture comprising at least a first substance, at least a second substance and magnetic particles, can be determined via the ⁇ potential of the individual substances in aqueous solution.
  • the measured ⁇ potential varies with the device type used, the measurement method and the evaluation method.
  • Important parameters to be specified are temperature, pH value, concentration of the salt background solution, conductivity and measuring voltage, so that the parameters mentioned must be known for comparable measurements.
  • the pH is therefore preferably set to a value which lies between the isoelectric point of the at least one first substance and the isoelectric point of the magnetic particles.
  • the pH can be adjusted by all methods known to the person skilled in the art, for example adding at least one basic or at least one acidic compound to the dispersion obtained. Whether a basic or an acidic compound has to be added depends on the pH value of the dispersion produced. If the pH of this dispersion is less than the range between the isoelectric point of the at least one first substance and the isoelectric point of the magnetic particles, at least one base is added to increase the pH. If the pH of this dispersion is greater than the range between the isoelectric point of the at least one first substance and the isoelectric point of the magnetic particles, at least one acid is added to lower the pH.
  • Suitable basic compounds are selected from the group consisting of organic or inorganic bases, for example ammonia, sodium hydroxide solution NaOH, potassium hydroxide solution KOH, amines, for example triethylamine, soluble alkali metal carbonates and mixtures thereof.
  • Suitable acidic compounds are selected from the group consisting of organic or inorganic acids, for example mineral acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, organic acids such as formic acid, acetic acid, propionic acid, methanesulfonic acid and mixtures thereof.
  • mineral acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid
  • organic acids such as formic acid, acetic acid, propionic acid, methanesulfonic acid and mixtures thereof.
  • the pH value for separating Cu 2 S from SiO 2 is preferably adjusted to pH 3.
  • the pH is preferably set to> 2.
  • F 1 and F 2 each represent functional groups which bind selectively to the magnetic particles (F 1 ) or to the at least one first substance (F 2 ).
  • “selective” means that the corresponding functional group F 1 or F 2 is 50 to 95%, preferably 70 to 98%, particularly preferably 80 to 98%, based on F 1 , of the magnetic particles or , based on F 2 , bind to the at least one first substance, in each case in the presence of the at least one second substance, in each case based on all bonds between functional groups and components present in the mixture.
  • F 1 denotes a functional group which binds selectively to the magnetic particles in the presence of silicates, particularly preferably selected from phosphonic acid group -OP (OH) 2 or carboxylic acid group-COOH.
  • Very particularly preferred functional groups F 2 of the general formula (VIII) are selected from the group of the compounds of the formulas (VIIIa), (VIIIb), (VIIIc), (VIIId) and (VIII):
  • A denotes structural unit selected from CRH 2 group with R selected from hydrogen or linear or branched carbon radical having 1 to 30 carbon atoms, aromatic or heteroaromatic unit, Cyclic or heterocyclic unit, unsaturated, branched or unbranched carbon chain with 2 to 30 carbon atoms, hetero atom or combinations of the aforementioned structural units, preferably CH 2 group, it being also possible according to the invention that in the basic structure formed by - (A) n - the bifunctional compounds -CC double and / or triple bonds are present.
  • Heteroatoms are, for example, O, S, N, and / or P.
  • Suitable aromatic or heteroaromatic units are selected, for example, from substituted or unsubstituted aromatic or heteroaromatic units having 6 to 20 carbon and optionally heteroatoms, for example phenyl, benzyl and / or naphthyl.
  • the aromatic units can be linked into the chain via the 1,2, 1,3 and / or 1,4 positions.
  • x and y describe the number of functional groups F 1 or F 2 present in the molecule.
  • X and y are preferably independently of one another 1, 2 or 3, particularly preferably 1 or 2, very particularly preferably 1.
  • a very particularly preferred compound of the general formula (VII) is (2-mercapto-phenyl) phosphonic acid
  • the functional group F 1 in the compound of the general formula (VII) binds to the at least one magnetic particle and the functional group F 2 in the compound of the general formula (VII) to the at least one first substance.
  • the dispersion contains agglomerates of magnetic particles and the at least one first substance, the at least one second substance and optionally at least a third substance in front. According to the invention, this dispersion is preferably transferred directly to step (D).
  • Step (C) of the process according to the invention comprises separating the addition product from the mixture from step (B) by applying a magnetic field gradient.
  • Suitable devices for magnetic separation in step (C), preferably on an industrial scale, are known to the person skilled in the art.
  • Step (C) of the method according to the invention can be carried out in all suitable devices known to the person skilled in the art, for example in a wet drum separator, high-gradient magnetic separator or related devices.
  • Step (C) of the process according to the invention can be carried out at any suitable temperature, for example 10 to 60 ° C.
  • step (C) the addition product from step (B) can, if appropriate, be separated off by all processes known to the person skilled in the art.
  • Step (D) of the method according to the invention comprises cleaving the separated addition product from step (C) in order to obtain the at least one first substance and the magnetic particles separately.
  • step (D) of the process according to the invention depends on the method by which the agglomerates were formed in step (B).
  • the splitting can be carried out by methods which are suitable for splitting the adduct in such a way that the magnetic particles can be recovered in a reusable form.
  • the magnetic particles particularly preferably together with magnetic particles separated in step (A), are used again in step (B).
  • the splitting in step (E) of the process according to the invention is carried out by treating the adduct with a substance selected from the group consisting of organic solvents, basic compounds, acidic compounds, oxidizing agents, reducing agents, surface-active compounds and mixtures thereof.
  • suitable organic solvents are methanol, ethanol, propanol, for example n-propanol or iso-propanol, aromatic solvents, for example benzene, toluene, xylenes, ethers, for example diethyl ether, methyl t-butyl ether, ketones, for example acetone, aromatic or aliphatic hydrocarbons, for example saturated hydrocarbons with, for example, 8 to 16 carbon atoms, for example dodecane and / or Shellsol®, diesel fuels and mixtures thereof.
  • the main components of diesel fuel are mainly alkanes, cycloalkanes and aromatic hydrocarbons with about 9 to 22 carbon atoms per molecule and a boiling range between 170 ° C and 390 ° C.
  • step (E) is carried out by adding aqueous NaOH solution up to a pH of 13, for example for the removal of Cu 2 S modified with OPS.
  • the acidic compounds can 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 for example, can be used as the oxidizing agent, for example as a 30% by weight aqueous solution (perhydrol).
  • H 2 O 2 or Na 2 S 2 O 4 is preferably used for the removal of Cu 2 S modified with thiols.
  • Examples of surface-active compounds which can be used according to the invention are nonionic, anionic, cationic and / or zwitterionic surfactants.
  • the adduct of hydrophobic substance and magnetic particles is cleaved with an organic solvent, particularly preferably with acetone and / or diesel. This process can also be supported mechanically. In a preferred embodiment, ultrasound is used to support the cleavage process.
  • the organic solvent is used in an amount sufficient to cleave as much as possible the entire adduct. In a preferred embodiment, 20 to 100 ml of the organic solvent are used per gram of adduct of hydrophobic material and magnetic particles to be cleaved.
  • step (E) of the process according to the invention in which agglomerate formation takes place by means of polymeric compounds which have an LCST ( Lower Critical Solution Temperature ), the separation of the agglomerates in step (E) can be carried out by setting a temperature is, in which the polymeric compounds has no hydrophobic character, so that the agglomerates are split.
  • LCST Lower Critical Solution Temperature
  • step (B) of the process according to the invention in which the formation of agglomerates takes place by adjusting the pH of the dispersion obtained to a value at which the at least one first substance and the magnetic particles carry opposite surface charges, the separation of the Agglomerates occur by setting a pH value at which the at least one first substance and the magnetic particles have the same surface charges, so that the agglomerates are split.
  • the at least one first substance and the magnetic particles are present as a dispersion either in said cleavage reagent, preferably an organic solvent, and / or in water.
  • the method according to the invention additionally has the following step (E): (E) separating the magnetic particles from the mixture from step (D) to obtain the at least one first substance.
  • the magnetic particles can be separated from the solution comprising these magnetic particles and the at least one first substance by means of a permanent or switchable magnet.
  • the separation in the optional step (E) is carried out analogously to step (C) of the method according to the invention.
  • Individual process parameters, for example solids content, flow rate, can be changed accordingly in step (E).
  • the desired at least one first substance is present in a dispersion optionally containing a cleavage reagent and / or water.
  • the first substance to be separated preferably the metal compound to be separated, is preferably separated from the cleavage reagent, for example an organic solvent, for example by distillation.
  • the first substance obtainable in this way can be purified by further processes known to the person skilled in the art.
  • the solvent can, if appropriate after purification, be returned to the process according to the invention.
  • the water can likewise be removed by processes known to the person skilled in the art, for example distillation, filtration, decanting and / or centrifuging.
  • step (A), (B), (C) (D) and / or optionally (E) according to the invention further dispersing agent can optionally be added to the present dispersion.
  • further dispersing agents can be added in order to obtain dispersions with lower solids contents in the individual steps.
  • Suitable dispersants to be added are all dispersants which have already been mentioned with regard to step (A), in particular water.
  • dispersing agents can be carried out by all processes known to the person skilled in the art.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Magnetic Resonance Imaging Apparatus (AREA)
EP11724259.4A 2010-06-11 2011-06-10 Nutzung der natürlich vorkommenden magnetischen bestandteile von erzen Active EP2579987B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL11724259T PL2579987T3 (pl) 2010-06-11 2011-06-10 Zastosowanie naturalnie występujących składników magnetycznych z rud
EP11724259.4A EP2579987B1 (de) 2010-06-11 2011-06-10 Nutzung der natürlich vorkommenden magnetischen bestandteile von erzen

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10165690 2010-06-11
PCT/EP2011/059736 WO2011154540A1 (de) 2010-06-11 2011-06-10 Nutzung der natürlich vorkommenden magnetischen bestandteile von erzen
EP11724259.4A EP2579987B1 (de) 2010-06-11 2011-06-10 Nutzung der natürlich vorkommenden magnetischen bestandteile von erzen

Publications (2)

Publication Number Publication Date
EP2579987A1 EP2579987A1 (de) 2013-04-17
EP2579987B1 true EP2579987B1 (de) 2020-03-18

Family

ID=44342917

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11724259.4A Active EP2579987B1 (de) 2010-06-11 2011-06-10 Nutzung der natürlich vorkommenden magnetischen bestandteile von erzen

Country Status (6)

Country Link
EP (1) EP2579987B1 (es)
AU (1) AU2011263640B2 (es)
CL (1) CL2012003499A1 (es)
PE (1) PE20131009A1 (es)
PL (1) PL2579987T3 (es)
WO (1) WO2011154540A1 (es)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI3223952T3 (fi) 2014-11-27 2024-03-27 Basf Se Energiansyöttö agglomeraation aikana magneettierottelua varten
CN108440641B (zh) * 2018-02-07 2021-11-19 复旦大学 一种特异性分离富集磷酸化肽和糖基化肽的方法
PE20210804A1 (es) 2018-08-13 2021-04-23 Basf Se Combinacion de separacion de portador magnetico y una separacion adicional para el procesamiento de minerales

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009065802A2 (de) * 2007-11-19 2009-05-28 Basf Se Magnetische trennung von substanzen basierend auf ihren unterschiedlichen oberflächenladungen

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB205122A (en) * 1922-04-12 1923-10-12 Alfred Arthur Lockwood Improved process for treating tin ores and concentrates
US3672579A (en) * 1970-08-10 1972-06-27 Univ Minnesota Process for beneficiating magnetite iron ore
US3926789A (en) * 1973-07-05 1975-12-16 Maryland Patent Dev Co Inc Magnetic separation of particular mixtures
US4289528A (en) * 1978-07-03 1981-09-15 Hazen Research, Inc. Process for beneficiating sulfide ores
AU548500B2 (en) 1981-10-26 1985-12-12 Denehurst Limited Magnetic flotation
GB8314138D0 (en) * 1983-05-21 1983-06-29 British Petroleum Co Plc Benefication of carbonaceous fuels
US4810368A (en) * 1985-04-10 1989-03-07 Electro Minerals (Canada) Inc. Automatic method for separating and cleaning silicon carbide furnace materials
GB8726857D0 (en) 1987-11-17 1987-12-23 Fospur Ltd Froth floatation of mineral fines
US4834898A (en) 1988-03-14 1989-05-30 Board Of Control Of Michigan Technological University Reagents for magnetizing nonmagnetic materials
US5161694A (en) * 1990-04-24 1992-11-10 Virginia Tech Intellectual Properties, Inc. Method for separating fine particles by selective hydrophobic coagulation
FR2733702B1 (fr) * 1995-05-04 1997-10-17 Sofresid Procede de separation magnetique du carbure de fer
DE19936472A1 (de) 1999-08-03 2001-02-15 Stn Atlas Elektronik Gmbh Haftvermittler
CZ20021608A3 (cs) * 1999-11-17 2003-06-18 Roche Diagnostics Gmbh Magnetické skleněné částice, metody jejich přípravy a použití
AUPR319001A0 (en) 2001-02-19 2001-03-15 Ausmelt Limited Improvements in or relating to flotation
US20030170686A1 (en) * 2001-12-07 2003-09-11 Rene Hoet Method and apparatus for washing magnetically responsive particles
US8033398B2 (en) 2005-07-06 2011-10-11 Cytec Technology Corp. Process and magnetic reagent for the removal of impurities from minerals
MX2010002462A (es) * 2007-09-03 2010-03-26 Basf Se Procesamiento de menas abundantes utilizando particulas magneticas.
PL2313200T3 (pl) * 2008-07-18 2012-11-30 Basf Se Cząstki nieorganiczne z powłoką organiczną o właściwościach hydrofilowych/hydrofobowych, które mogą ulegać zmianie pod wpływem temperatury

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009065802A2 (de) * 2007-11-19 2009-05-28 Basf Se Magnetische trennung von substanzen basierend auf ihren unterschiedlichen oberflächenladungen

Also Published As

Publication number Publication date
PE20131009A1 (es) 2013-09-19
AU2011263640A1 (en) 2013-01-10
AU2011263640B2 (en) 2014-02-20
EP2579987A1 (de) 2013-04-17
WO2011154540A1 (de) 2011-12-15
PL2579987T3 (pl) 2020-08-24
CL2012003499A1 (es) 2013-02-15

Similar Documents

Publication Publication Date Title
EP2498913B1 (de) Verfahren zur effizienzsteigerung beim erztrennungsprozess mittels hydrophober magnetischer partikel durch gezielten eintrag mechanischer energie
EP2401084B1 (de) Cu-mo-trennung
EP2190584B1 (de) Aufbereitung von werterzen durch magnetpartikel
EP2376230B1 (de) Anreicherung von werterzen aus minenabfall (tailings)
EP2313200B1 (de) Anorganische partikel mit einer durch temperatur hydrophil/hydrophob schaltbaren organischen beschichtung
EP2403649B1 (de) Magnetische hydrophobe agglomerate
EP2403648B1 (de) Magnetische trennung von buntmetallerzen durch mehrstufige konditionierung
EP2212027B1 (de) Magnetische trennung von substanzen basierend auf ihren unterschiedlichen oberflächenladungen
US8865000B2 (en) Utilization of the naturally occurring magnetic constituents of ores
EP2171106B1 (de) Verfahren zur erzanreicherung mittels hydrophober, fester oberflächen
EP2313201B1 (de) Selektive stofftrennung mit modifizierten magnetpartikeln
EP2519356B1 (en) Modified high intensity magnetic separation (hims) process
EP3092048B1 (en) Process for reducing the volume flow comprising magnetic agglomerates by elutriation
EP2579987B1 (de) Nutzung der natürlich vorkommenden magnetischen bestandteile von erzen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20130111

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

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

Owner name: BASF SE

Owner name: SIEMENS AKTIENGESELLSCHAFT

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20190319

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20191016

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASF SE

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502011016552

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1245295

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200415

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: FI

Ref legal event code: FGE

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

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

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200618

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20200318

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

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200618

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200619

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

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

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

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

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200812

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200718

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502011016552

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

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

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

26N No opposition filed

Effective date: 20201221

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20200618

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

Ref country code: LU

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

Effective date: 20200610

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20200630

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

Ref country code: CH

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

Effective date: 20200630

Ref country code: LI

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

Effective date: 20200630

Ref country code: IE

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

Effective date: 20200610

Ref country code: FR

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

Effective date: 20200630

Ref country code: GB

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

Effective date: 20200618

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

Ref country code: BE

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

Effective date: 20200630

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1245295

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200610

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

Ref country code: AT

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

Effective date: 20200610

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

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

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

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200318

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

Ref country code: SE

Payment date: 20220622

Year of fee payment: 12

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

Ref country code: PL

Payment date: 20220517

Year of fee payment: 12

Ref country code: FI

Payment date: 20220621

Year of fee payment: 12

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

Ref country code: DE

Payment date: 20220628

Year of fee payment: 12

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502011016552

Country of ref document: DE

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

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

Ref country code: FI

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

Effective date: 20230610

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

Ref country code: DE

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

Effective date: 20240103

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

Ref country code: SE

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

Effective date: 20230611