WO2009080648A1 - Anwendung magnetischer, ionischer flüssigkeiten als extraktionsmittel - Google Patents
Anwendung magnetischer, ionischer flüssigkeiten als extraktionsmittel Download PDFInfo
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- WO2009080648A1 WO2009080648A1 PCT/EP2008/067731 EP2008067731W WO2009080648A1 WO 2009080648 A1 WO2009080648 A1 WO 2009080648A1 EP 2008067731 W EP2008067731 W EP 2008067731W WO 2009080648 A1 WO2009080648 A1 WO 2009080648A1
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- pentyl
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/44—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids
- H01F1/447—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids characterised by magnetoviscosity, e.g. magnetorheological, magnetothixotropic, magnetodilatant liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0419—Solvent extraction of solutions which are liquid in combination with an electric or magnetic field or with vibrations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/005—Pretreatment specially adapted for magnetic separation
- B03C1/015—Pretreatment specially adapted for magnetic separation by chemical treatment imparting magnetic properties to the material to be separated, e.g. roasting, reduction, oxidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
- B03C1/025—High gradient magnetic separators
- B03C1/031—Component parts; Auxiliary operations
- B03C1/033—Component parts; Auxiliary operations characterised by the magnetic circuit
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0492—Applications, solvents used
Definitions
- the invention relates to a method which uses ionic liquids, in particular magnetic ionic liquids, for extraction, in particular for liquid-liquid, liquid-solid or liquid-gaseous extraction, the separation of the phases taking place in a magnetic field.
- ionic liquids in particular magnetic ionic liquids
- Ionic liquids are - in the sense of recognized literature (eg Wasserscheid, Peter, Welton, Tom (Eds.), "Ionic Liquids in Synthesis", published by Wiley-VCH 2003, ISBN 3-527-30515-7, Rogers, Robin D. ; Seddon, Kenneth R. (Eds.); “Ionic Liquids - Industrial Applications to Green Chemistry", ACS Symposium Series 818, 2002; ISBN 0841237891 ”) - liquid organic salts or salt mixtures consisting of organic cations and organic or inorganic anions Melting points of less than 100 ° C.
- inorganic salts can be additionally dissolved, as well as molecular auxiliaries
- molecular auxiliaries we see the limit of the melting point of ionic liquids, which is arbitrarily set at 100 ° C. in a broader sense, and thus also exclude such molten salts which have a melting point above 100 ° C. but below 200 ° C. Otherwise, they do not differ in their properties.
- Ionic liquids have very interesting properties, such as a very low to almost non-measurable vapor pressure, a very large liquidus range, good electrical conductivity and unusual solvation properties. These properties predestine them for use in various areas of technical applications.
- solvents in organic and inorganic synthesis in general, in transition metal catalysis, biocatalysis, phase transfer catalysis, in multiphase reactions, in photochemistry, in the Polymer synthesis and nanotechnology
- extractants in liquid-liquid and liquid-gaseous extraction in general, the desulfurization of crude oil, the removal of heavy metals from wastewater, liquid membrane extraction
- electrolytes in batteries, fuel cells, capacitors , Solar cells, sensors, electrochromics, electroplating, electrochemical metalworking, electrochemical synthesis in general, electroorganic synthesis, nanotechnology
- lubricants as thermofluids, as gels, as reagents for organic synthesis, in the "Green Chemistry” (Substitute for Volatile Organic Compounds), as
- Kapillarzonenelektrophorese as liquid crystals, etc. (incomplete list) are used.
- One object of the invention may be to find liquid extraction media which can be separated independently of the action of gravitational force and / or centrifugal force and independent of the density difference of the two phases and which may also be widely used in their chemical and physical properties given separation problem are customizable.
- the ionic liquid may have a melting point of below 200 0 C.
- the ionic liquid has a melting point of below 100 0 C and more preferably below 20 0 C.
- a method of extracting a component from an extraction stock comprising generating an extract of the component and an extraction medium by contacting the extraction material with the extraction medium having an ionic liquid, and further separating the extract by means of a magnetic field.
- an apparatus for extracting a component from an extraction stock comprising an extraction medium for extracting a component from an extraction material, the extraction medium comprising an ionic liquid, and a magnetic field generating unit for separating an extract ,
- the ionic liquid may be a paramagnetic liquid.
- an extraction medium for extracting a component from an extraction stock, wherein the extraction medium comprises a paramagnetic ionic liquid.
- Embodiments of using an extraction medium will be described below. However, the features of the embodiments also apply to the method of extraction, the device for extracting and the extractant.
- the ionic liquid is a paramagnetic ionic liquid.
- a paramagnetic ionic liquid may, in particular, be understood as meaning an ionic liquid which additionally has the property of giving a force when an external, inhomogeneous magnetic field is applied learn, which draws this into the magnetic field, so that it has a magnetic susceptibility> 1.
- the optimization of the properties for the respective extractive application may be carried out within wide limits by a variation of the structure of anion and cation or a variation of their combination, which by the way is more commonly called "designer solvents" by the ionic liquids. (see, for example, Freemantle, M., Chem. Eng., News, 78, 2000, 37).
- the extraction is a liquid / liquid or liquid / solid or liquid / gaseous extraction.
- the paramagnetic ionic liquid has an anion comprising a transition metal compound.
- the paramagnetic ionic liquid has a cation comprising a transition metal and / or a transition metal compound.
- transition metals It. IUPAC Rule 1.21 in particular the elements of atomic numbers 21-30, 39-48, 57-80, 89-103, 104 to hypothetical 112 are understood.
- the paramagnetic ionic liquid corresponds to one of the general formulas [A] + [M + v X v + i] - , ([A] + ) 2 [M + v X v + 2 ] 2 " , or ([A ] + ) 3 [M + v X v + 3 ] 3 " , where [A] + is a quaternary ammonium cation [R 1 R 1 R 2 R 3 N] + , a phosphonium cation [R 1 R 1 R 2 R 3 P] + , a sulfonium cation [R 1 R 1 R 2 S] + or a heteroaromatic cation, where M + v is a transition metal atom with the oxidation number + v and where X is an ion or a ligand with the charge number -1 is.
- R 1 , R 1 , R 2 and R 3 may hereby be radicals which are described in more detail below
- the paramagnetic ionic Liquid a solution of a paramagnetic inorganic and / or organic salt in a non-paramagnetic ionic liquid. That is, the paramagnetic ionic liquid may be generated by dissolving or mixing a paramagnetic inorganic or paramagnetic organic salt in a non-paramagnetic ionic liquid per se.
- the non-paramagnetic ionic liquid corresponds to the general formula ([A] + ) a [B] a ⁇ , where [A] + is a quaternary ammonium cation [R 1 R 1 R 2 R 3 N] + , a phosphonium cation [R 17 R 1 R 2 R 3 P] + , a sulfonium cation [R 17 R 1 R 2 S] + or a heteroaromatic cation.
- R 1 ' , R 1 , R 2 and R 3 may hereby be radicals which are described in more detail below.
- the paramagnetic salt has a melting point of below 200 0 C.
- the paramagnetic salt may have a melting point of below 100 0 C and preferably below 20 0 C.
- the paramagnetic ionic liquid comprises a solution of a paramagnetic inorganic and / or paramagnetic organic salt in an ionic liquid and the paramagnetic ionic liquid has a melting point of below 200 ° C.
- the paramagnetic liquid may have a melting point of below 100 0 C and preferably below 20 0 C. That is, the paramagnetic ionic liquid which is then used as the extraction medium may be generated by dissolving or mixing a paramagnetic inorganic or paramagnetic organic salt in a non-paramagnetic ionic liquid or in an already paramagnetic liquid itself.
- Paramagnetic salts in particular, may be salts (and their solutions in molecular solvents) that are transformed into an inhomogeneous external
- ferrofluids are not true liquids, but suspensions of up to nano finely ground ferrite particles, ie. Ferrite particles (solids), which are ground down to a few microns to a few nanometers, in various solvents. They show strong reaction to external magnetic fields.
- paramagnetic ionic liquids are used as extraction media for liquid / liquid or liquid / solid or liquid / gaseous extraction and separated in a magnetic field.
- R 1 , R 1 ' , R 2 , R 3 are each independently hydrogen, optionally sub.
- the heteroaromatic of the formula is usually a 5- or 6-membered heteroaromatic, which has at least one nitrogen atom and optionally an oxygen or sulfur atom, and which is unsubstituted or substituted and / or anneliert, preferably the heteroaromatic of the formula IIb is selected from Group:
- R is hydrogen, Ci-C 30 alkyl, C 3 -C 2 -cycloalkyl, C 2 -C 30 -alkenyl, C 3 -C 2 -
- Haloalkyl cyclopentyl, cyclohexyl, phenyl, toIyI or benzyl;
- R 1 , R 1 , R 2 , R 3 are each independently hydrogen, optionally sub. Alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl or heteroaryl; or two of R 1 , R 1 ' , R 2 , R 3 together with the heteroatom to which they are attached form a ring, which is saturated or unsaturated, unsubstituted or substituted, and this chain is represented by one or more heteroatoms selected from the group O, S, NH or N-Ci-C 4 alkyl may be interrupted;
- R 4 , R 5 , R 6 , R 7 , R 8 independently of one another are hydrogen, halogen, nitro, cyano, OR C , SR C , NR c R d , COR C , COOR C , CO-NR c R d , Ci- C 3 o-alkyl, C 3 -C 2 -cycloalkyl, C 2 -C 30 -alkenyl, C 3 -C 2 -cycloalkenyl, aryl or heteroaryl, where the 6 last-mentioned radicals can carry one or more halogen radicals and / or 1 to 3 radicals selected from the group Ci-
- R c , R d are independently hydrogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl, cyclopentyl, cyclohexyl, phenyl, ToIyI or benzyl;
- Hydrogen, halogen or Ci-Ce-alkyl in particular hydrogen or
- Fluoride chloride, bromide, iodide; hexafluorophosphate; hexafluoroarsenate; hexafluoroantimonate; Trifluoroarsenat; Nitrite; Nitrate; Sulfate; Bisulfate; carbonate; hydrogen carbonate; alkyl carbonate;
- organic sulfonate of the general formula (Vb) [R m -SC> 3] - , wherein R m is a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which is an or contain multiple heteroatoms and / or may be substituted by one or more functional groups or halogen;
- organic sulfate of the general formula (Vc) [R m -OS ⁇ 3] - wherein R m is a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which is an or contain multiple heteroatoms and / or may be substituted by one or more functional groups or halogen;
- Carboxylate of the general formula (Vd) [R n -COO] - wherein R n is hydrogen or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which is one or more Heteroatoms and / or may be substituted by one or more functional groups or halogen;
- R 0 to R u are independently hydrogen or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic , aromatic or araliphatic radical having 1 to 30 carbon atoms, which may contain one or more heteroatoms and / or may be substituted by one or more functional groups or halogen.
- R m is a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which contain one or more heteroatoms and / or by one or more functional groups or halogen may be substituted
- R n is hydrogen or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms containing one or more heteroatoms and / or may be substituted by one or more functional groups or halogen;
- Called carbonate An example of a triply negatively charged anion is called phosphate.
- Radicals having 1 to 30 carbon atoms are the radicals R 1 to R 1 in the tetrasubstituted borate (Va), the radical R m in the organic sulfonate (Vb) and sulfate (Vc), the radical R n in the carboxylate (Vd) and the radicals R 0 to R u in the imides (Vf), (Vg) and (Vh) are independently of each other preferably
- Cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl, methoxy, ethoxy, formyl, acetyl or CnF 2 (na) + (ib) H 2 a + b with n ⁇ 30, 0 ⁇ a ⁇ n and b 0 or 1 (for example CF 3 , C 2 F 5 , CH 2 CH 2 -C (n- 2 ) F 2 (n - 2 ) + i, C 6 Fi 3 , C 8 Fi 7 , C I QF 2I , Ci 2 F 25 ); C 3 - to Ci 2 cycloalkyl, and whose aryl, heteroaryl, cycloalkyl, halo, hydroxy, amino, carboxy, formyl, -O-, -CO- or -CO-O-substituted derivatives, such as cyclopentyl, 2-methyl-1-cyclopentyl, 3-methyl-1-
- R 1 is identical in this preferred to R 1, which preferably represents fluorine , Trifluoromethyl, pentafluoroethyl, phenyl, 3,5-bis (trifluoromethyl) phenyl.
- Particularly preferred tetrasubstituted borates (Va) are tetrafluoroborate, tetraphenylborate and tetra [3,5-bis (trifluoromethyl) phenyl] borate.
- Particularly preferred organic sulfonates are trifluoromethanesulfonate (triflate), methanesulfonate, nonadecafluorononanesulfonate (nonaflate) and p-toluenesulfonate;
- Particularly preferred organic sulfates (Vc) are methyl sulfate, ethyl sulfate, n-propyl sulfate, i-propyl sulfate, butyl sulfate,
- the radical R n is preferably hydrogen, trifluoromethyl
- carboxylates are formate, acetate, propionate, butyrate, valerate, benzoate, mandelate, trichloroacetate, dichloroacetate, chloroacetate, trifluoroacetate, difluoroacetate, fluoroacetate.
- z is preferably 0.
- R 0 to R u are independently preferred for hydrogen, trifluoromethyl, pentafluoroethyl, phenyl, trichloromethyl, dichloromethyl, chloromethyl, Trifluoromethyl, difluoromethyl, fluoromethyl or unbranched or branched Ci- to C 2 -alkyl, such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-l-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-
- Particularly preferred imides (Vf), (Vg) and (Vh) are [F 3 C-SO 2 -N-SO 2 - CF 3] "[F 3 C-SO 2 -N-CO-CF 3]", [F 3 C-CO-N-CO-CF 3 ] " and those in which the radicals R 0 to R u independently of one another represent hydrogen, methyl, ethyl, propyl, butyl, phenyl, trichloromethyl, dichloromethyl, chloromethyl, trifluoromethyl, Difluoromethyl or fluoromethyl stand.
- hexafluorophosphate hexafluoroarsenate
- hexafluoroantimonate hexafluoroantimonate
- Trifluoroarsenat Nitrite; Nitrate; Sulfate; Bisulfate; carbonate; hydrogen carbonate; alkyl carbonate; aryl carbonate; Phosphate;
- organic sulfonate of the general formula (Vb) [R m -S ⁇ 3 ] - , wherein R m is a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which is one or more Heteroatoms and / or may be substituted by one or more functional groups or halogen;
- Carboxylate of the general formula (Vd) [R n -COO] - wherein R n is hydrogen or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which is one or more Contain heteroatoms and / or by a or more functional groups or halogen may be substituted;
- Carbon atoms which may contain one or more heteroatoms and / or may be substituted by one or more functional groups or halogen;
- radicals R to R 1 in tetrasubstituted borate (Va), the radical R m in the organic sulfonate (Vb) and sulfate (Vc), the radical R n in the carboxylate (Vd) and the radicals R 0 to R u in the imides (Vf), (Vg) and (Vh) are independently of each other preferably
- Ci Ci to C 3 o-alkyl and their aryl, heteroaryl, cycloalkyl, halogen, hydroxy, amino, carboxy, formyl, -O-, -CO-, -CO-O- or -CO -N ⁇ substituted components such as methyl, ethyl, 1-propyl, 2-
- Ci 2 cycloalkyl and whose aryl, heteroaryl, cycloalkyl, halo, hydroxy, amino, carboxy, formyl, -O-, -CO- or -CO-0-substituted derivatives, such as cyclopentyl, 2-methyl-1-cyclopentyl, 3
- anion [B] 3 is an organic sulfonate (Vb) [R m - SO 3]" or sulfate (Vc) [R m -OSO 3] "as the radical R m is preferably methyl, trifluoromethyl , Pentafluoroethyl, p-tolyl or C 9 F 19.
- Particularly preferred organic sulfonates (Vb) are trifluoromethanesulfonate (triflate), methanesulfonate, nonadecafluorononanesulfonate (nonaflate) and p-toluenesulfonate.
- organic sulfates are methyl sulfate, ethyl sulfate, n-propyl sulfate, i-propyl sulfate, butyl sulfate, pentyl sulfate, hexyl sulfate, heptyl sulfate, octyl sulfate, nonyl sulfate and decyl sulfate and longer-chain n-alkyl sulfates; Benzyl sulfate, alkyl aryl sulfate.
- the radical R n is preferably hydrogen, trifluoromethyl, pentafluoroethyl, phenyl, hydroxyphenylmethyl, trichloromethyl, dichloromethyl , Chloromethyl, trifluoromethyl, difluoromethyl, fluoromethyl or unbranched or branched Ci to Ci 2 alkyl, such as
- Trifluoromethyl, difluoromethyl, fluoromethyl or unbranched or branched Ci- to C 2 -alkyl such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-l-propyl (isobutyl), 2-methyl-2-propyl
- Particularly preferred imides (Vf), (Vg) and (Vh) are [F 3 C-SO 2 -N-SO 2 - CF 3] "[F 3 C-SO 2 -N-CO-CF 3]", [F 3 C-CO-N-CO-CF 3 ] " and those in which the radicals R 0 to R u independently of one another represent hydrogen, methyl, ethyl,
- transition metal salt e.g. in
- R 1 , R 1 ' , R 2 , R 3 are each independently hydrogen, optionally sub.
- NH or N-Ci-C 4 -alkyl can be interrupted, and
- M + V is a transition metal atom with the oxidation number + v and X is an ion or a ligand with the charge number -1.
- the heteroaromatic of the formula is usually a 5- or 6-membered heteroaromatic which has at least one nitrogen atom and optionally an oxygen or sulfur atom, and which is unsubstituted or substituted and / or fused, preferably the heteroaromatic is selected from the group:
- R is hydrogen, Ci-C 30 alkyl, C 3 -C 2 cycloalkyl, C 2 -C 3 -alkenyl, C 3 -C 2 - cycloalkenyl, C 2 -C 30 alkynyl, aryl or heteroaryl, where the 7 last-mentioned radicals may carry one or more halogen radicals and / or 1 to 3 radicals selected from the group Ci-Ce-alkyl, aryl, heteroaryl, C 3 -C 7 cycloalkyl, halogen, OR C , SR C , NR c R d , COR C , COOR C , CO-NR c R d , wherein R c and R d is hydrogen, Ci-C 6 alkyl, Ci-C 6 - haloalkyl, cyclopentyl, cyclohexyl, phenyl, ToIyI or benzyl;
- R 1 , R 1 , R 2 , R 3 are each independently hydrogen, optionally sub. Alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl or heteroaryl; or two of R 1 , R 1 , R 2 , R 3 together with the heteroatom to which they are attached form a ring, which is saturated or unsaturated, unsubstituted or substituted, and this chain may be interrupted by one or more heteroatoms selected from the group O, S, NH or N-Ci-C 4 alkyl;
- R 4 , R 5 , R 6 , R 7 , R 8 independently of one another are hydrogen, halogen, nitro, cyano, OR C , SR C , NR c R d , COR C , COOR C , CO-NR c R d , Ci- C 30 -alkyl, C 3 -C 2 - cycloalkyl, C 2 -C 30 -alkenyl, C 3 -C 2 -cycloalkenyl, aryl or heteroaryl, wherein the 6 latter residues can carry one or more halogen residues and / or 1 to 3 Radicals selected from the group Ce-Ce-alkyl, aryl, heteroaryl, C 3 -C 7 -cycloalkyl, halogen, OR C , SR C , NR c R d , COR C , COOR C , CO-NR c R d , wherein R c and R d independently of one another represent hydrogen
- O, S, N, NH or N-Ci-C 4 -alkyl may be interrupted
- R e , R f , R 9 , R h independently of one another represent hydrogen, C 1 -C 6 -alkyl, aryl,
- Heteroaryl, C 3 -C 7 -cycloalkyl, halogen, OR C , SR C , NR c R d , COOR C , CO-NR c R d or COR C is substituted, wherein R c , R d are independently hydrogen, Ci-Ce-alkyl, Ci-Ce-haloalkyl, cyclopentyl, cyclohexyl, phenyl, ToIyI or benzyl;
- Ci-Ce-alkyl preferably hydrogen, halogen or Ci-Ce-alkyl, in particular hydrogen or
- M + v is selected from the elements of the transition metals, preferably selected from the elements Ce, Cs, Cr, Co, Cu, Dy, Er, Eu, Gd, Ho, Ir, Fe, Mn, Mo, Nd, Ni, Pt, Pu, Pr, Re, Rh, Rb, Ru, Sm, Ta, Tb, Tm, Ti, W, U, V, and Y particularly preferably in the oxidation states Ce +2 , Ce +3 , Ce +4 , Cs +1 , Cr +2 , Cr +3 , Cr +6 , Co +2 , Co +3 , Cu +1 , Cu +2 , Dy +3 , Er +2 , Eu +3 , Eu +3 , Gd +2 , Gd +3 , Ho +2 , Ho +3 , Ir +4 , Fe +2 , Fe +3 , Mn +2 , Mn +3 , Mo +2 , Mo +3 , Mo +4 , Mo +5 , Nd +
- Each of the v + 1, v + 2 or v + 3 ions or ligands X is preferably selected independently from one another
- Fluoride chloride, bromide, iodide, thiocyanate, hexafluorophosphate; hexafluoroarsenate; hexafluoroantimonate; Trifluoroarsenat; Nitrite; Nitrate; Sulfate; Bisulfate; carbonate; hydrogen carbonate; alkyl carbonate; aryl carbonate; Phosphate; Hydrogen phosphate; dihydrogen phosphate; tetrasubstituted borate of the general formula (Va) [BR 1 R 1 F ⁇ R 1 ] " , wherein R 1 to R 1 independently of one another for fluorine or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having from 1 to 30 carbon atoms which may contain one or more heteroatoms and / or may be substituted by one or more functional groups or halogen;
- organic sulfonate of the general formula (Vb) [R m -SO 3 ] - , wherein R m is a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 30 carbon atoms, which is one or more Heteroatoms and / or may be substituted by one or more functional groups or halogen;
- Carbon atoms which may contain one or more heteroatoms and / or may be substituted by one or more functional groups or halogen;
- Carbon atoms which may contain one or more heteroatoms and / or may be substituted by one or more functional groups or halogen;
- Radicals having 1 to 30 carbon atoms are the radicals R 1 to R 1 in the tetrasubstituted borate (Va), the radical R m in the organic sulfonate (Vb) and sulfate (Vc), the radical R n in the carboxylate (Vd) and the radicals R 0 to R u in the imides (Vf), (Vg) and (Vh) are independently of each other preferably
- Aryl or heteroaryl having 2 to 30 carbon atoms and their alkyl, aryl, heteroaryl, cycloalkyl, halogen, hydroxy, amino, carboxy, formyl, -O-, -CO- or -CO-O- substituted components such as phenyl, 2-methyl-phenyl (2-ToIyI), 3-methyl-phenyl (3-ToIyI), 4-methyl-phenyl, 2-ethyl-phenyl, 3-ethyl-phenyl, 4-ethyl phenyl,
- X is a tetrasubstituted borate (Va) [BR 1 R ⁇ R 1] ", so, in this preferred all four radicals R 1 to R 1 are identical, which preferably represents fluorine, trifluoromethyl, pentafluoroethyl, phenyl, 3 5-bis (trifluoromethyl) phenyl
- Particularly preferred tetrasubstituted borates (Va) are tetrafluoroborate, tetraphenylborate and tetra [3,5-bis (trifluoromethyl) phenyl] borate.
- X is an organic sulfonate (Vb) [R m -SO 3 ] - or sulfate (Vc) [R m -OSO 3 ] - then the radical R m is preferably methyl, trifluoromethyl, pentafluoroethyl, p-tolyl or CgFi 9 .
- Particularly preferred organic sulfonates are trifluoromethanesulfonate (triflate), methanesulfonate, nonadecafluorononanesulfonate (nonaflate) and p-toluenesulfonate;
- Particularly preferred organic sulfates (Vc) are methyl sulfate, ethyl sulfate, n-propyl sulfate, i-propyl sulfate, butyl sulfate, pentyl sulfate, hexyl sulfate, heptyl sulfate, octyl sulfate, nonyl sulfate and
- Decyl sulfate and longer-chain n-alkyl sulfates Benzyl sulfate, alkyl aryl sulfate.
- R n is preferably hydrogen, trifluoromethyl, pentafluoroethyl, phenyl, hydroxyphenylmethyl, trichloromethyl, dichloromethyl, chloromethyl, Trifluoromethyl, difluoromethyl, fluoromethyl or unbranched or branched Ci- to C 2 -alkyl, such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-l-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl,
- Particularly preferred carboxylates (Vc) are formate, acetate, propionate, butyrate, valerate, benzoate, mandelate, trichloroacetate, dichloroacetate, chloroacetate, trifluoroacetate, difluoroacetate, fluoroacetate.
- PF x (CyF 2 y + i -z H z ) 6-x ⁇
- z is preferably 0.
- radicals R 0 to R u independently of one another are preferably hydrogen, trifluoromethyl, pentafluoroethyl, phenyl, trichloromethyl, dichloromethyl, chloromethyl, trifluoromethyl, difluoromethyl, fluoromethyl or unbranched or branched Ci- to C 2 -alkyl, such as methyl, ethyl, 1-propyl, 2-
- Particularly preferred imides (Vf), (Vg) and (VH) are [F 3 C-SO 2 -N-SO 2 - CF 3] "[F 3 C-SO 2 -N-CO-CF 3]", [F 3 C-CO-N-CO-CF 3 ] " and those in which the Radicals R 0 to R u independently of one another represent hydrogen, methyl, ethyl, propyl, butyl, phenyl, trichloromethyl, dichloromethyl, chloromethyl, trifluoromethyl, difluoromethyl or fluoromethyl.
- Each X may also be independently selected from the following group of complexing ligands:
- acetylacetone acyl; adenine; 2,2'-azobisisobutyronitrile;alanine;allyl;allyloxycarbonyl;Water;aryl;arginine;asparagine;aspartate;BIABN;biotinyl; Dimethoxy-1,1'-biphenyl 2,2 '-bis (diphenyl-phosphino) -6,6';
- 2,2'-Binaphtyldiphenyldiphosphin l, 2-bis [4,5-dihydro-3H-binaphtho [1,2-c: 2 ' , 1 ' -e] phosphepino] benzene; 1,1 '-bis ⁇ 4,5-dihydro-3H-dinaphtho [l, 2-c: 2', 1 '-e] phosphepino ⁇ ferrocene; 4,4 '-di-tert-butyl-4,4', 5,5 '-tetrahydro-3,3' -bis-3H-di-naphtho [2, lc: l ', 2' - e] phosphepine; BINAL; 4,5-dihydro-3H-dinaphtho [2, lc; l ' , 2 ' - e] phosphepin; 2,2'-Binaphty
- Benzylmethylphenylphosphin benzyl; tert-butoxycarbonyl; Bis (2 - ((S) -4-iso-propyl-4,5-dihydrooxazol-2-yl) -phenyl) amine; Bis (2 - ((S) -4-tert-butyl-4,5-dihydrooxazol-2-yl) -phenyl) amine; 1, 2-bis (2,5-diethylphospholano) ethane; Butoxy-carbonyl-4-diphenylphosphino-2-diphenylphosphino-methyl-pyrrolidine; 2,2'-bipyridine; benzoyl;
- dipivaloylmethanate Dess-Martin periodinane; 1,4,7,10-tetraaza-cyclododecane-1,4,7,10-tetraacetate; Diphenylphosphenylethan; Diphenylphosphenylmethan; Diphenylphosphenylpropan; deoxy-ribose;
- Diethylenetriamine pentaacetate Bis (2,5-dimethylphospholano) -benzene; ethylenediaminetetraacetate; ethylenediamine; fluorenylmethoxycarbonyl; 7,7-dimethyl-1, 1, 1, 2,2,3,3-heptafluoroooctane-4,6-dionato; galactose;
- hexamethylphosphoramide hydroxyproline; isoleucine; leucine; lysine;
- sialic acid N-glycolyl-neuraminic acid; 2,3-bis (diphenylphosphino) bicyclo [2.2.1] hept-5-ene; Nitrilo triacetic acid; ornithine; succinate; oxalate; Phenyl o -anisylmethylphosphine; phthalocyanine; phenylalanine;
- proline pyridyl; pybox; Pyroglutamate; pyrazine; ribose; sarcosine; halls;
- triphenylphosphane tryptophan; tyrosine; tetrazole; ubiquitin; uracil;
- the in b. described paramagnetic ionic liquid with transition metal cation substantially the in c. corresponds to described paramagnetic salts, so far as they have a melting point of below 200 0 C, preferably below 100 0 C, more preferably below 20 0 C, otherwise the high melting point only by dissolving as in c. described can be compensated.
- Transition metal compounds may or may not be paramagnetic, however, since the lone electron occupying orbitals of the transition metal atoms are e.g. can be fully occupied with complex ligand electrons, so that the paramagnetism disappears ("low-spin complexes").
- paramagnetic ionic liquids may be provided with further functional groups and / or added with additives to facilitate the Physicochemical properties to adapt to the respective extraction problem.
- the magnetic field can be introduced via a permanent magnet or an electromagnet, and it is also possible to use superconducting electromagnets.
- the phase separation can be spatially precisely defined, the speed of the field being used to regulate the velocity.
- a separation can also be achieved at the same density without the use of filtration.
- the phase separation can be accelerated and also aerosols can be effectively separated.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
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BRPI0821720-3A BRPI0821720A2 (pt) | 2007-12-20 | 2008-12-17 | Aplicação de líquidos iônicos, magnéticos como agente de extração |
RU2010130257/07A RU2558726C2 (ru) | 2007-12-20 | 2008-12-17 | Применение магнитных ионных жидкостей в качестве экстрагирующего средства |
JP2010538701A JP2011506088A (ja) | 2007-12-20 | 2008-12-17 | 抽出剤としての磁性、イオン液体の使用 |
AU2008340098A AU2008340098B2 (en) | 2007-12-20 | 2008-12-17 | Use of magnetic, ionic liquids as an extraction agent |
US12/809,234 US9005450B2 (en) | 2007-12-20 | 2008-12-17 | Use of magnetic, ionic liquids as an extraction agent |
EP08864792.0A EP2235724B1 (de) | 2007-12-20 | 2008-12-17 | Anwendung magnetischer, ionischer flüssigkeiten als extraktionsmittel |
CN200880126048.XA CN101933104B (zh) | 2007-12-20 | 2008-12-17 | 磁性离子液体作为萃取剂的用途 |
CA2712365A CA2712365C (en) | 2007-12-20 | 2008-12-17 | Use of magnetic, ionic liquids as an extraction agent |
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US1546907P | 2007-12-20 | 2007-12-20 | |
US61/015,469 | 2007-12-20 |
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PCT/EP2008/067731 WO2009080648A1 (de) | 2007-12-20 | 2008-12-17 | Anwendung magnetischer, ionischer flüssigkeiten als extraktionsmittel |
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US (1) | US9005450B2 (de) |
EP (1) | EP2235724B1 (de) |
JP (1) | JP2011506088A (de) |
CN (1) | CN101933104B (de) |
AU (1) | AU2008340098B2 (de) |
BR (1) | BRPI0821720A2 (de) |
CA (1) | CA2712365C (de) |
RU (1) | RU2558726C2 (de) |
WO (1) | WO2009080648A1 (de) |
Cited By (2)
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CN102091670A (zh) * | 2010-12-29 | 2011-06-15 | 中国科学院过程工程研究所 | 一种磁性离子液体分离浓缩方法 |
WO2013079514A1 (de) | 2011-11-30 | 2013-06-06 | Universität Rostock | Schwefel-freie übergangsmetall-isocyanat-basierte ionische flüssigkeiten |
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US8888993B2 (en) | 2010-07-30 | 2014-11-18 | Chevron U.S.A. Inc. | Treatment of a hydrocarbon feed |
DE102011080230A1 (de) * | 2011-08-01 | 2013-02-07 | Helmholtz-Zentrum Dresden - Rossendorf E.V. | Extraktion von Edelmetall(ionen) mittels ionischer Flüssigkeiten |
CN102500460B (zh) * | 2011-09-26 | 2014-04-30 | 中国科学院过程工程研究所 | 一种气助超顺磁性萃取方法 |
CN103130718B (zh) * | 2012-10-10 | 2016-05-25 | 江苏大学 | 一种磁性离子液体及其制备方法和用途 |
CN105617711B (zh) * | 2014-10-16 | 2018-04-10 | 中国药科大学 | 一种磁性离子液体结合相关微萃取装置用于复杂样品中微量组分分离方法 |
CN105624439B (zh) * | 2014-10-27 | 2017-11-10 | 有研稀土新材料股份有限公司 | 一种磁流体萃取剂分离低浓度稀土离子的方法 |
US10322417B2 (en) * | 2015-07-01 | 2019-06-18 | Uchicago Argonne, Llc | Magnetically enhanced phase separation for solvent extraction |
CN108642033A (zh) * | 2018-04-17 | 2018-10-12 | 天津科技大学 | 一种温和条件下制备弱磁性铁酶复合物的方法 |
CN110252256B (zh) * | 2019-06-28 | 2021-11-05 | 河北科技大学 | 一种磁性离子液体、其应用和改性活性炭及其制备方法 |
CN110385198B (zh) * | 2019-08-05 | 2020-07-17 | 潍坊奇为新材料科技有限公司 | 一种用于非金属矿的分选装置 |
CN112427139B (zh) * | 2020-10-14 | 2021-09-07 | 清华大学 | 磁性液体分筛装置 |
CN113620820B (zh) * | 2021-08-11 | 2023-12-29 | 辽宁大学 | 一种功能化磁性离子液体及其制备方法和应用 |
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- 2008-12-17 EP EP08864792.0A patent/EP2235724B1/de not_active Not-in-force
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- 2008-12-17 WO PCT/EP2008/067731 patent/WO2009080648A1/de active Application Filing
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CN102091670A (zh) * | 2010-12-29 | 2011-06-15 | 中国科学院过程工程研究所 | 一种磁性离子液体分离浓缩方法 |
WO2013079514A1 (de) | 2011-11-30 | 2013-06-06 | Universität Rostock | Schwefel-freie übergangsmetall-isocyanat-basierte ionische flüssigkeiten |
DE102011055859A1 (de) | 2011-11-30 | 2013-06-06 | Universität Rostock | Schwefel-freie Übergangsmetall-Isocyanat-basierte ionische Flüssigkeiten |
Also Published As
Publication number | Publication date |
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EP2235724B1 (de) | 2014-11-19 |
AU2008340098A1 (en) | 2009-07-02 |
CA2712365A1 (en) | 2009-07-02 |
CN101933104B (zh) | 2016-12-28 |
CA2712365C (en) | 2016-05-24 |
CN101933104A (zh) | 2010-12-29 |
EP2235724A1 (de) | 2010-10-06 |
AU2008340098B2 (en) | 2014-09-04 |
US20110020509A1 (en) | 2011-01-27 |
US9005450B2 (en) | 2015-04-14 |
BRPI0821720A2 (pt) | 2015-06-16 |
JP2011506088A (ja) | 2011-03-03 |
RU2010130257A (ru) | 2012-01-27 |
RU2558726C2 (ru) | 2015-08-10 |
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