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WO2003039719A2 - Procede d'extraction de substances a partir de solutions contenant des liquides ioniques au moyen d'une membrane - Google Patents

Procede d'extraction de substances a partir de solutions contenant des liquides ioniques au moyen d'une membrane Download PDF

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Publication number
WO2003039719A2
WO2003039719A2 PCT/EP2002/012253 EP0212253W WO03039719A2 WO 2003039719 A2 WO2003039719 A2 WO 2003039719A2 EP 0212253 W EP0212253 W EP 0212253W WO 03039719 A2 WO03039719 A2 WO 03039719A2
Authority
WO
WIPO (PCT)
Prior art keywords
aryl
alkyl
membrane
substituted
general formula
Prior art date
Application number
PCT/EP2002/012253
Other languages
German (de)
English (en)
Other versions
WO2003039719A3 (fr
Inventor
Peter Wasserscheid
Udo Kragl
Jan KRÖCKEL
Original Assignee
Solvent Innovation Gmbh
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
Application filed by Solvent Innovation Gmbh filed Critical Solvent Innovation Gmbh
Priority to AU2002363375A priority Critical patent/AU2002363375A1/en
Publication of WO2003039719A2 publication Critical patent/WO2003039719A2/fr
Publication of WO2003039719A3 publication Critical patent/WO2003039719A3/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/147—Microfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/24—Dialysis ; Membrane extraction
    • B01D61/246—Membrane extraction

Definitions

  • the invention relates to methods for separating non-volatile or non-volatile substances from solutions with ionic liquids under
  • Ionic liquids are salts that melt at low temperatures ( ⁇ 100 ° C) and represent a new class of solvents with a non-molecular, ionic character. Even though the first representatives have been known since 1914, ionic liquids have only been intensively investigated as solvents for chemical reactions in the last 15 years. Ionic liquids have no measurable vapor pressure. This is a great advantage from a process engineering point of view, since it enables the separation of a reaction mixture by distillation as an effective method for product separation. The known problems of azeotroping between solvents and products do not occur. Ionic liquids are temperature stable up to over 200 ° C. A suitable choice of cation and anion enables a gradual adjustment of the polarity and thus a coordination of the solubility properties.
  • the process according to the invention is based on the surprising finding that the selectivity of membranes also for the separation of heavy and non-volatile substances from solutions with ionic liquids can be used.
  • the solution of the high-boiling or non-volatile substance in the ionic liquid possibly after adding a suitable auxiliary solvent such as. B. water or a lower alcohol such. B. isopropanol - filtered through a suitable membrane.
  • a suitable auxiliary solvent such as. B. water or a lower alcohol such. B. isopropanol - filtered through a suitable membrane.
  • a suitable auxiliary solvent such as. B. water or a lower alcohol such. B. isopropanol - filtered through a suitable membrane.
  • the membrane is separated without the substance to be separated having to be converted into the gas phase.
  • the isolated nonvolatile or nonvolatile substance can be isolated, if appropriate from the auxiliary solvent used by distillation.
  • the pure ionic liquid obtained can be used again in chemical reactions or extraction applications.
  • the method is also suitable for removing ionic liquids from unspecified impurities which either originate from the manufacturing process or arise during use.
  • the membranes used consist either of organic polymers, which can be of natural or artificial origin (e.g. cellulose, polyamide) or inorganic materials (e.g. titanium dioxide).
  • the selectivity is based either on a pure difference in the size of the components to be separated, on different charge of the components or on different solubility of the components in the Membrane material.
  • the component here denotes the ionic liquid, the compound to be separated off and any auxiliary solvent which may be present. As a rule, there will be a combination of the separation mechanisms, especially with the nanofiltration used here.
  • the membranes can be designed as a flat membrane, membrane stack, winding module or hollow fiber membrane.
  • Liquid are dissolved, the proportion of ionic liquid can be between 0.001 and 99.999 vol.%;
  • the ionic liquids are compounds of the general formula
  • n 1 or 2 and the anion [Y] n "is selected from the group consisting of tetrafluoroborate ([BF 4 ] " ), tetrachloroborate ([BCU] " ),
  • Hexafluoroarsenate [AsF 6 ] " ), tetrachloroaluminate ([AICUD, Trichlorozincate [(ZnCI 3 ] “ ), dichlorocuprate, sulfate ([S0 4 ] 2” ), carbonate ([C0 3 ] 2 " ), fluorosulfonate, [R ' -COO] “ , [R'-S0] “ , [ R ' ⁇ S0 4 ] " or [(R'- S0 2 ) 2 ] " , and R' is a linear or branched 1 to 12 carbon atom containing aliphatic or alicyclic alkyl or a C 5 -C 8 aryl, C 5 -C 8 aryl -C 6 alkyl or -C 6 alkyl C 5 -
  • Cis-aryl radical which may be substituted by halogen atoms, the cation [A] + is selected from quaternary ammonium cations of the general formula
  • imidazole core can be substituted with at least one group which is selected from -CC 6 -alkyl, -C-C 6 -alkoxy-, Ci-Ce-aminoalkyl-, C 5 -C ⁇ 2 -aryl- or C 5 -C 2 aryl -C 5 alkyl groups,
  • pyridine core can be substituted with at least one group which is selected from -CC 6 alkyl, Ci-C ⁇ -alkoxy, Ci-Ce-aminoalkyl, C 5 -C 2 aryl or C5 -C ⁇ 2 -aryl -C ⁇ -C 6 - alkyl groups,
  • pyrazole nucleus can be substituted with at least one group selected from C 6 -C 6 alkyl, C 1 -C 6 alkoxy,
  • Ci-Ce-aminoalkyl C 5 -C 2 -aryl or C 5 -C 2 -aryl -CC-C 6 - alkyl groups, and triazolium cations of the general formula
  • the triazole core can be substituted with at least one group which is selected from -CC 6 alkyl, -C-C 6 alkoxy, Ci-Ce aminoalkyl, C 5 -C 2 aryl or C 5 -Ci2-Aryl -CC 6 - alkyl groups, and the radicals R 1 , R 2 , R 3 are selected independently of one another from the group consisting of
  • Heteroatom selected from N, O and S, with at least one
  • Group selected from -C 6 alkyl groups and / or halogen atoms can be substituted
  • Aryl radical which can optionally be substituted with at least one C 6 -C 6 -alkyl group and / or a halogen atom.
  • the alkyl, aryl, arylalkyl and alkylaryl sulfonate groups can be substituted by halogen atoms, in particular fluorine, chlorine or bromine.
  • halogen atoms in particular fluorine, chlorine or bromine.
  • the non-halogenated representatives are the methanesulfonate, benzenesulfonate and the toluenesulfonate group, and all others in the prior art
  • the alkyl, aryl, arylalkyl and alkylaryl carboxylate groups can be substituted by halogen atoms, in particular fluorine, chlorine or bromine.
  • halogen atoms in particular fluorine, chlorine or bromine.
  • the fluorinated, in particular the perfluorinated alkyl and aryl carboxylates mentioned above, such as the trifluoromethane carboxylate (trifluoroacetate; CF COO " ) are particularly preferred.
  • the acetate and benzoate groups are to be mentioned as non-halogenated representatives, as are all other carboxylates known in the prior art
  • the C 1 -C 6 -alkyl groups mentioned in connection with the substituents can each be replaced independently of one another by C 2 -C 4 alkyl groups -C 6 alkoxy groups are each independently replaced by C 2 -C 4 alkoxy groups
  • the C 5 -C 2 aryl groups mentioned in connection with the substituents can each be replaced independently of one another by C 6 - Cio-aryl groups
  • the C 3 -Cs heteroaryl groups are each independently replaced by C 3 -C 6 heteroaryl groups.
  • the halogen atoms with which the alkyl, alkoxy and aryl groups can be substituted are selected from fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
  • a preferred embodiment is the radical R 'is a linear or branched 1 to 8 carbon atoms containing aliphatic or alicyclic alkyl or a C 6 -C 0 aryl, C 6 -C aro-C 1 -C 4 alkyl or Ci - C 4 alkyl-C 6 -C ⁇ o-aryl radical, which can be substituted by halogen atoms.
  • the cations [A] are selected, for example, from trimethylphenylammo ⁇ ium, methyltrioctylammonium, tetrabutylphosphonium, 3-butyl-l-methylimidazolium, 3-ethyl-l-methylimidazolium, N-butylpyridinium, N-ethylpyridinium, diethylpyrazolium, 1-ethyl -3-methylimidazolium, l-butyl-3-methylimidazolium, l-hexyl-3-methylimidazolium, l-octyl-3-methylimidazolium, l-decyl-3-methylimidazolium, l-butyl-4-methylpyridinium, l-butyl-3 - methylpyridinium, l-butyl-2-methylpyridinium, l-butyl-pyridinium, .butyl-methyl-imidazolium
  • Ionic liquids and their production are known in the prior art.
  • the halide salt is reacted by adding a metal salt MY (with precipitation or separation of the salt MX or the product [A] + [Y] " from the solvent used in each case) - where [Y] " is a hexafluorophosphate, tetrafluoroborate, bis (trifluoromethylsulfonyl) amide, perfluoroalkylsulfonate and perfluoroalkylcarboxylate ion and M + stands for an alkaline application (JS Wilkes, MJ Zaworotko, J. Chem. Soc. Chem. Commun. 1992, 965-967; Y. Chauvin, L. Mußmann , H.
  • Bromophenol blue has a melting point of 273 ° C. The boiling point is over 350 ° C.
  • concentrations of the bromophenol blue were determined photometrically at a wavelength of 590 nm and the concentrations of the ionic liquid by conductivity measurements.
  • a) simple filtration composition of the solution to be filtered 29.8 ml of a 10 mM aqueous [BMIM] BF 4 solution are mixed with 200 ⁇ l of commercially available bromophenol blue solution, of which 20 ml are filtered.
  • Membrane Desal 5 DVA 000 nanofiltration membrane, amafilter, in RZ 75 stirred cell from Schleicher & Schüll, pressure 5 bar. A retention of 99% is obtained for bromophenol blue and 33% for [BMIM] BF 4 . Then the proportion of the dye is gradually increased. Instead of 200 ⁇ l, 300 and 400 ⁇ l of dye solution are added. The retention of the dye remains unchanged.
  • Example 1 b With solution 4 from Table 2, a multiple filtration is carried out as in Example 1 b). The result is summarized in Table 4. The ionic liquid can thus be washed out completely, while the lactose remains in the retentate.
  • [BMIM] BF 4 is a non-volatile substance, ie it has an immeasurably low vapor pressure.
  • concentrations of the ionic liquid were determined by conductivity measurements.
  • Membrane Desal DVA 032 nanofiltration membrane, Amafilter, in RZ 75 stirred cell from Schleicher & Schüll.
  • [BMIM] BF 4 is a non-volatile substance, ie it has an immeasurably low vapor pressure.
  • Bromophenol blue has a melting point of 273 ° C. The boiling point is above 350 ° C.
  • concentrations of the ionic liquid were determined by conductivity measurements. The concentration of bromophenol blue was determined photometrically at a wavelength of 600 nm.
  • Bromophenol blue solution containing was filtered. A retention of 98% was found for bromophenol blue and for the ionic liquid found by 25%. The dye is retained while the ionic liquid permeates.

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  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Health & Medical Sciences (AREA)
  • Urology & Nephrology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne un procédé d'extraction de substances non volatiles ou peu volatiles à partir de solutions contenant des liquides ioniques, au moyen d'une membrane.
PCT/EP2002/012253 2001-11-05 2002-11-03 Procede d'extraction de substances a partir de solutions contenant des liquides ioniques au moyen d'une membrane WO2003039719A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002363375A AU2002363375A1 (en) 2001-11-05 2002-11-03 Method for separating substances from solutions containing ionic liquids by means of a membrane

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10154209.7 2001-11-05
DE10154209A DE10154209A1 (de) 2001-11-07 2001-11-07 Verfahren zur Abtrennung von Substanzen aus Lösungen mit ionischen Flüssigkeiten unter Verwendung einer Membran

Publications (2)

Publication Number Publication Date
WO2003039719A2 true WO2003039719A2 (fr) 2003-05-15
WO2003039719A3 WO2003039719A3 (fr) 2004-06-17

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PCT/EP2002/012253 WO2003039719A2 (fr) 2001-11-05 2002-11-03 Procede d'extraction de substances a partir de solutions contenant des liquides ioniques au moyen d'une membrane

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Country Link
AU (1) AU2002363375A1 (fr)
DE (1) DE10154209A1 (fr)
WO (1) WO2003039719A2 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007076979A1 (fr) * 2005-12-23 2007-07-12 Basf Se Solution a base de liquides ioniques fondus, sa fabrication et son utilisation pour la fabrication d'hydrates de carbone regeneres
US8936719B2 (en) 2006-03-22 2015-01-20 Ultraclean Fuel Pty Ltd. Process for removing sulphur from liquid hydrocarbons
US9441169B2 (en) 2013-03-15 2016-09-13 Ultraclean Fuel Pty Ltd Process for removing sulphur compounds from hydrocarbons
US10214697B2 (en) 2013-03-15 2019-02-26 Ultraclean Fuel Pty Limited Process for removing sulphur compounds from hydrocarbons

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006024397B3 (de) * 2006-05-24 2007-10-11 Universität Rostock Mehrphasen-Membran

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL243758A (fr) * 1958-09-26
US3462362A (en) * 1966-07-26 1969-08-19 Paul Kollsman Method of reverse osmosis
US5510125A (en) * 1988-05-04 1996-04-23 Bucher-Guyer Ag Maschinenfabrik Process for selective removal of sugar from beverages
BR8906214A (pt) * 1988-11-29 1990-06-26 Dow Chemical Co Solucao aquosa e processo para purificacao de dioxido de enxofre
EP1182197A1 (fr) * 2000-08-24 2002-02-27 Solvent Innovation GmbH Procédé de préparation en une étape de fluides ioniques

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007076979A1 (fr) * 2005-12-23 2007-07-12 Basf Se Solution a base de liquides ioniques fondus, sa fabrication et son utilisation pour la fabrication d'hydrates de carbone regeneres
JP2009520846A (ja) * 2005-12-23 2009-05-28 ビーエーエスエフ ソシエタス・ヨーロピア 溶融イオン性液体に基づく溶媒系、その生成及び再生炭水化物を生成するためのその使用
US8163215B2 (en) 2005-12-23 2012-04-24 Basf Aktiengesellschaft Method of forming regenerated carbohydrates with solvent systems based on molten ionic liquids
KR101370200B1 (ko) 2005-12-23 2014-03-05 바스프 에스이 용융 이온액 기재 용액계, 그의 제조 및 재생 탄수화물의제조를 위한 용도
US8936719B2 (en) 2006-03-22 2015-01-20 Ultraclean Fuel Pty Ltd. Process for removing sulphur from liquid hydrocarbons
US9441169B2 (en) 2013-03-15 2016-09-13 Ultraclean Fuel Pty Ltd Process for removing sulphur compounds from hydrocarbons
US10214697B2 (en) 2013-03-15 2019-02-26 Ultraclean Fuel Pty Limited Process for removing sulphur compounds from hydrocarbons

Also Published As

Publication number Publication date
DE10154209A1 (de) 2003-05-15
WO2003039719A3 (fr) 2004-06-17
AU2002363375A1 (en) 2003-05-19
AU2002363375A8 (en) 2003-05-19

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