WO2013041402A1 - Procédé de purification de liquides ioniques - Google Patents

Procédé de purification de liquides ioniques Download PDF

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Publication number
WO2013041402A1
WO2013041402A1 PCT/EP2012/067687 EP2012067687W WO2013041402A1 WO 2013041402 A1 WO2013041402 A1 WO 2013041402A1 EP 2012067687 W EP2012067687 W EP 2012067687W WO 2013041402 A1 WO2013041402 A1 WO 2013041402A1
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WO
WIPO (PCT)
Prior art keywords
salts
organic
anion
water
acids
Prior art date
Application number
PCT/EP2012/067687
Other languages
German (de)
English (en)
Inventor
Michael Siemer
Michael Klein
Sunghee Son
Klemens Massonne
Uwe Vagt
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
Application filed by Basf Se filed Critical Basf Se
Publication of WO2013041402A1 publication Critical patent/WO2013041402A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C07D233/08—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms
    • C07D233/10—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring nitrogen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
    • B01D15/361—Ion-exchange
    • B01D15/363—Anion-exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/05—Processes using organic exchangers in the strongly basic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/05—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds
    • B01J49/07—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds containing anionic exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
    • B01J49/57—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for anionic exchangers

Definitions

  • ionic liquids there are a large number of technical uses, for example as a solvent.
  • ionic liquids are generally not consumed but only contaminated. Since these are high-priced salts, there is a need for particularly effective and inexpensive processes for working up the mixtures obtained during use so that they can be reused.
  • ionic liquids for the dissolution of cellulose for example, mixtures are formed which, in addition to the ionic liquid, contain solvents, in particular water, introduced impurities, for example introduced acids, salts or decomposition products of the cellulose and the ionic liquid.
  • Degradation products of cellulose are in particular short-chain carboxylic acids, which are then present by equilibrium reactions as an ion associated with the cation of the ionic liquid.
  • the salts K + X- have a melting point below 100 ° C (1 bar, atmospheric pressure); therefore, the salts K + X- are ionic liquids.
  • the salts K + X- under normal conditions are liquid.
  • Suitable organic cations K + are in particular organic compounds with heteroatoms, such as nitrogen, sulfur, oxygen or phosphorus.
  • Suitable compounds are monocyclic, bicyclic, aromatic or non-aromatic ring systems.
  • Examples include bicyclic systems, as described in WO 2008/043837.
  • the bicyclic systems of WO 2008/043837 are diazabicyclo derivatives, preferably from a 7- and a 6-membered ring which contain an amidinium group; in particular the 1,8-diazabicyclo (5.4.0) undec-7-enium cation may be mentioned.
  • Very particularly preferred are cations which contain a heterocyclic ring system having one or two nitrogen atoms as part of the ring system.
  • the carbon atoms of the ring system can also be substituted by organic groups having generally not more than 20 carbon atoms, preferably a hydrocarbon group, in particular a C1 to C16 alkyl group, in particular a C1 to C10, more preferably a C1 to C4 alkyl groups.
  • R1 is an organic radical having 1 to 20 carbon atoms and
  • R 1 and R 3 are preferably independently an organic radical having 1 to 10 C atoms.
  • R 1 and R 3 are an aliphatic radical, in particular an aliphatic radical without further heteroatoms, e.g. for an alkyl group.
  • Particular preference is given to R1 and R3 independently of one another being a C1 to C10 or a C1 to C4 alkyl group.
  • C 6 -C 20 -alkanoates (carboxylates of alkanecarboxylic acids, in particular C 8 -C 16 -alkanoates.
  • organic anions its e.g. those with a maximum of 8 carbon atoms, in particular with a maximum of 6 carbon atoms or a maximum of 4 carbon atoms called.
  • the composition may contain various salts (K + ) n Y n - , in particular it may contain different salts with inorganic anion Y n_ and simultaneously different salts with organic anion Y n_ .
  • the entire composition is passed over a strongly basic anion exchanger.
  • a strongly basic anion exchanger binds anions and in turn releases OH. So be the anions X and Y n bound "and released OH.
  • the composition then after passing through the strongly basic anion exchanger the corresponding hydroxide salts K + OH _.
  • Usual strongly basic Anion exchangers are well known and commercially available.
  • the pks value is the negative decadic logarithm of the acid constants, KS.
  • (H + ) m Z m - is preferably added in such amounts that the entire amount of X- is completely converted to HX.
  • the aqueous and organic phases obtained in d) can be easily separated, e.g. by decanting a phase.
  • an extractant e.g. an organic solvent which is miscible with HX can be added.
  • HX e.g. an organic solvent which is miscible with HX
  • step f the organic phase (containing HX) separated off into e) and the aqueous mixture (containing K + OH) obtained in b), if appropriate with the addition of further HX, are converted to K + X- and H2O.
  • the reaction of K + OH- with HX to K + X- + H2O occurs immediately at room temperature; a temperature increase is not necessary.
  • Pre-separated acids HX can be reused in the process according to the invention.
  • the bound in the weakly basic ion exchanger HX must be recovered.
  • the HX-loaded, weakly basic anion exchanger is first rinsed with a base, for example NaOH; This initially produces the corresponding salt of the base, eg NaX.
  • the salt (NaX) can be easily converted to HX by adding an acid and optionally organic solvent.
  • HX if appropriate also together with organic solvent, can then be added in process step f) as a further HX (see above).
  • the process according to the invention is a simple and very effective process for purifying salts K + X-, where K + X- are in particular ionic liquids.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de purification de sels K+X-, K+ représentant un cation quelconque et X- représentant un anion organique comprenant au moins 6 atomes de carbone. Ledit procédé est caractérisé en ce que : a) les sels K+X- sont présents dans des compositions qui contiennent des sels hydrosolubles (K+)n Yn- sous forme d'impuretés, K+ représentant le cation ci-dessus, Yn- représentant un anion inorganique ou un anion organique différent de X- comprenant au maximum 10 atomes de carbone et n représentant 1, 2 ou 3 ; b) la composition est amenée par un échangeur d'anions fortement basique, lequel se lie aux anions X- et Yn- et libère OH-, de sorte qu'un mélange aqueux, contenant K+ OH-, soit obtenu ; c) l'échangeur d'anions fortement basique est régénéré, ce qui signifie que les anions X- et Yn- liés sont libérés par rinçage de l'échangeur d'anions fortement basique avec une base M+OH- avec formation simultanée d'une solution aqueuse, contenant M+X- et (M+)nYn-, M+ représentant un cation quelconque différent de K+ ; d) les anions X- des sels M+X- sont convertis par ajout d'un hydracide hydrosoluble (H+)mZm-, m représentant 1, 2 ou 3, en les acides HX, deux phases se formant, une phase organique qui contient HX, et une phase aqueuse qui contient les sels hydrosolubles (M+)mZm- et (M+)n Yn- ou les acides (H+)n Yn- ; e) la phase organique est séparée ; et f) la phase organique (contenant HX) et le mélange aqueux obtenu dans b) (contenant KOH), éventuellement à l'aide d'un ajout de HX supplémentaire, sont transformés en K+X- et H2O.
PCT/EP2012/067687 2011-09-20 2012-09-11 Procédé de purification de liquides ioniques WO2013041402A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP11181912 2011-09-20
EP11181912.4 2011-09-20

Publications (1)

Publication Number Publication Date
WO2013041402A1 true WO2013041402A1 (fr) 2013-03-28

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2012/067687 WO2013041402A1 (fr) 2011-09-20 2012-09-11 Procédé de purification de liquides ioniques

Country Status (1)

Country Link
WO (1) WO2013041402A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1115818A1 (fr) 1998-09-21 2001-07-18 Gérard Auberger Concentre hydrosoluble obtenu a partir d'une phase emulgatrice ou hydrosolubilisante et d'un complexe de matieres lipophiles liquides d'origine vegetale
EP1470846A1 (fr) * 2003-03-25 2004-10-27 Basf Aktiengesellschaft Purification ou régénération de fluides ioniques à l'aide d'une méthode d'adsorption
WO2005113702A1 (fr) 2004-05-21 2005-12-01 Basf Aktiengesellschaft Nouvelles paires de substances pour des pompes a chaleur a absorption, des machines frigorifiques a absorption et des transformateurs thermiques
WO2008043837A1 (fr) 2006-10-13 2008-04-17 Basf Se Liquides ioniques servant à solubiliser des polymères
WO2009027250A2 (fr) 2007-08-31 2009-03-05 Basf Se Distillation de fluides ioniques

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1115818A1 (fr) 1998-09-21 2001-07-18 Gérard Auberger Concentre hydrosoluble obtenu a partir d'une phase emulgatrice ou hydrosolubilisante et d'un complexe de matieres lipophiles liquides d'origine vegetale
EP1470846A1 (fr) * 2003-03-25 2004-10-27 Basf Aktiengesellschaft Purification ou régénération de fluides ioniques à l'aide d'une méthode d'adsorption
WO2005113702A1 (fr) 2004-05-21 2005-12-01 Basf Aktiengesellschaft Nouvelles paires de substances pour des pompes a chaleur a absorption, des machines frigorifiques a absorption et des transformateurs thermiques
WO2008043837A1 (fr) 2006-10-13 2008-04-17 Basf Se Liquides ioniques servant à solubiliser des polymères
WO2009027250A2 (fr) 2007-08-31 2009-03-05 Basf Se Distillation de fluides ioniques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BRENNECKE J F ET AL: "SEPARATION OF SPECIES FROM IONIC LIQUIDS", WATER-SOLUBLE POLYMERS: SYNTHESIS, SOLUTION PROPERTIES AND APPLICATIONS, AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC, US, no. 812, 1 January 2002 (2002-01-01), pages 82 - 96, XP008031714, ISBN: 978-0-541-23408-9 *

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