US20170355680A1 - Method of preparing a high purity imidazolium salt - Google Patents

Method of preparing a high purity imidazolium salt Download PDF

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US20170355680A1
US20170355680A1 US15/619,567 US201715619567A US2017355680A1 US 20170355680 A1 US20170355680 A1 US 20170355680A1 US 201715619567 A US201715619567 A US 201715619567A US 2017355680 A1 US2017355680 A1 US 2017355680A1
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compound
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water
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Xinming Wang
Olivier Zehnacker
Benjamin Willy
Rolf Schneider
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Evonik Operations GmbH
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Evonik Degussa GmbH
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    • 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
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • 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
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/20—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids

Definitions

  • the invention relates to a method of preparing a high purity imidazolium salt.
  • the air In air conditioning systems for the aeration and conditioning of buildings or vehicles, the air generally not only has to be cooled, but also dehumidified since the air to be cooled often has such a high humidity that, upon cooling to the desired temperature, the dew point is fallen below.
  • dehumidification of the air accounts for a large part of the electricity consumption.
  • One option of reducing the electricity consumption of air conditioning systems for buildings is the dehumidification of air by adsorption or absorption of water using a drying medium and a regeneration of the drying medium laden with water by heating to a temperature at which the water is desorbed again.
  • the advantage of absorption in a liquid absorption medium is that drying of air can be performed with reduced equipment complexity and with less drying medium and that regeneration of the water-laden drying medium using solar heat is easier to carry out.
  • aqueous solutions of lithium bromide, lithium chloride or calcium chloride hitherto employed as liquid absorption media in commercial air conditioning systems have the disadvantage that they are corrosive towards the metallic materials of construction typically employed in air conditioning systems and that they thus necessitate the use of expensive specific materials of construction. These solutions can additionally cause problems due to salt crystallizing out of the absorption medium.
  • Ionic liquids comprising dialkylimidazolium ions (as described in WO 2004/016631 A1) have been described as alternatives to lithium salts in the prior art for similar applications.
  • US 2011/0247494 A1 proposes, in paragraph [0145], the use of trimethylammonium acetate or 1-ethyl-3-methylimidazolium acetate as liquid drying agent instead of aqueous lithium chloride solution.
  • Example 3 compares water uptake from humid air for a series of further ionic liquids.
  • ionic liquids comprising dialkylimidazolium ions
  • they often comprise impurities, which lead to substances that are odour-intensive or are injurious to health entering the dehumidified air upon a dehumidification of air using the ionic liquid.
  • odour-intensive decomposition products are formed which, in the event of a subsequent use of the ionic liquid for the dehumidification of air, enter the dehumidified air.
  • the problem to be solved by the present invention is hence provision of a process for the production of ionic liquids comprising dialkylimidazolium ions, wherein the level of volatile compounds is brought to a minimum.
  • the invention hence provides a process for preparing a high purity compound of formula (I):
  • step a) of the process according to the invention a compound of formula (II) with a compound of formula (III) is reacted, giving a crude product comprising a compound of formula (I).
  • the skilled person is familiar with the reaction conditions, which are described in WO 2004/016631 A1, for example.
  • step a) of the process according to the invention is preferably carried out at a temperature in the range of from 130° C. to 200° C., more preferably 140° C. to 190° C., even more preferably 150° C. to 175° C.
  • the pressure of the reaction is not critical and may be for example atmospheric pressure, preferably under an inert atmosphere, such as nitrogen.
  • reaction is exothermic, it may be desirable to control the rate of addition in some cases and/or to apply external cooling during the addition step.
  • the compounds of formula (II) and (III) are present in stoichiometric amounts, i.e. the molar relation of compound (II) to compound (III) is in the range 0.9:1 to 1.1:1, more preferably 1:1.
  • the imidazole compound (II) in a slight excess to the phosphate ester (III), for example in the range of 1.01 to 1.4 molar equivalents, preferable 1.02 to 1.4.
  • reaction time is not particularly limited. Typically, the reaction is continued until at least 90% of the compounds (II) or (III) has reacted to form compound (I).
  • the progress of the reaction can be conveniently controlled by methods known to the skilled person, such as NMR
  • the reaction in step a) can be carried out in the presence or absence of a solvent and is preferably carried out in the absence of a solvent.
  • solvent means water or organic solvents which are known to the skilled person, preferably it means water. These organic solvents are preferably selected from the group consisting of aliphatic solvents, preferably pentane, hexane, heptane, octane, decane, cyclohexane, tetramethylsilane; aromatic solvents, preferably benzene, toluene, xylene; ether compounds, preferably diethyl ether, dipropyl ether, dibutyl ether, methyl tert-butyl ether; halogenated solvents, preferably dichloromethane, chloroform, tetrachloromethane; alcohols, preferably methanol, ethanol, propanol, iso-propanol, butanol, tert-butanol; esters, preferably methyl acetate, ethyl acetate, propyl acetate, butyl acetate
  • “Absence of a solvent” means particularly that the overall content of all solvents in the reaction mixture is below 10 weight-% based on the sum of the weights of compounds (II) and (III), preferably below 5 weight-% based on the sum of the weights of compounds (II) and (III), more preferably below 1 weight-% based on the sum of the weights of compounds (II) and (III).
  • Presence of a solvent means that the sum of all solvents present in the reaction mixture is at least 1.0 weight-%, based on the combined masses of compounds (II) and (III). Even more preferred, it means that the sum of all solvents present in the reaction mixture is at least 3.7 weight-%, based on the combined masses of compounds (II) and (III). Even more preferred, it means that the sum of all solvents present in the reaction mixture is at least 7.4 weight-%, based on the combined masses of compounds (II) and (III). Even more preferred, it means that the sum of all solvents present in the reaction mixture is at least 10.0 weight-%, based on the combined masses of compounds (II) and (III).
  • the sum of all solvents present in the reaction mixture is at least 20.0 weight-%, based on the combined masses of compounds (II) and (III). Even more preferred, it means that the sum of all solvents present in the reaction mixture is at least 40.0 weight-%, based on the combined masses of compounds (II) and (III). Even more preferred, it means that the sum of all solvents present in the reaction mixture is at least 80 weight-%, based on the combined masses of compounds (II) and (III). Even more preferred, it means that the sum of all solvents present in the reaction mixture is at least 100 weight-%, based on the combined masses of compounds (II) and (III). Even more preferred, it means that the sum of all solvents present in the reaction mixture is at least 150 weight-%, based on the combined masses of compounds (II) and (III).
  • step a) in which the step a) is carried out in the presence of a solvent, it is preferred that the solvent is at least partially removed after step a) before step b) is carried out.
  • Such at least partial removal can be carried out by extraction, stripping, distillation or any other process known to the skilled person, preferably by extraction, stripping, distillation.
  • partial removal means in particular, that at least 50% of the solvent added in step a) is removed, preferably at least 70%, even more preferably at least 90%, even more preferably 99% of the solvent is removed.
  • step a) is carried out in the presence of a solvent comprising water
  • the partial removal of the solvent is preferably carried out by distillation at a temperature T 2 in the range of 30-180° C., preferably 37° C.-178° C., even more preferably 50° C.-150° C., even more preferably 60° C.-120° C., even more preferably 70° C.-99° C., and at a pressure p 2 which is lower than the saturated vapour pressure of compound (III) at the temperature T 2 .
  • step a) of the method according to the invention is a crude product comprising a compound of formula (I).
  • the term “crude product” means the reaction mixture which is obtained after the reaction has taken place [step a) of the process according to the invention] and is then submitted to step b).
  • step a) is carried out in presence of a solvent, such solvent can be optionally removed at least partially from the crude product obtained after step a) before step b) is carried out.
  • step b) The crude product obtained in step a) is then further processed in step b).
  • step b) water is added to the crude product of formula (I) from step a), preferably in an amount of at least 1 weight-% based on the amount of compounds (II) and (III) used in step a), giving a diluted crude product comprising a compound of formula (I).
  • step b) water is added to the crude product of formula (I) from step a) in an amount in the range of 1 to 200, more preferably 5 to 100, even more preferably 7 to 75, even more preferably 10 to 50, most preferably 15 to 20 weight-% based on the amount of compounds (II) and (III) used in step a).
  • diluted crude product means the mixture which is obtained after the addition of water according to step b) and is then submitted to step c).
  • step c) of the process the water added in step b) is then at least partially removed from the diluted crude, wherein special temperature and pressure conditions are applied. Namely, it is essential to the invention that the water is removed by distillation at a temperature T 1 in the range of 30-180° C., preferably 37° C.-178° C., even more preferably 50° C.-150° C., even more preferably 60° C.-120° C., even more preferably 70° C.-99° C., and at a pressure p 1 which is lower than the saturated vapour pressure of compound (III) at the temperature T 1 .
  • At least partially removed in the context of the invention with respect to claim c) means, that at least 50% of the water added in step b) is removed, preferably at least 70%, even more preferably at least 90%, even more preferably 99% of the water added in step b) is removed.
  • all apparatuses known to the person skilled in the art can be used, thus e.g. a stirred reactor, a falling-film evaporator or a thin-film evaporator, in each case in combination with a suitable distillation column or another apparatus suitable for the distillation.
  • the pressure p 1 at which the distillation takes place has to be lower than the saturated vapour pressure of compound (III) at the temperature T 1 , wherein T 1 is in the range of 30-180° C.
  • “Saturated vapour pressure” of a certain substance or mixture is defined as the pressure exerted by a vapour of this substance or mixture in thermodynamic equilibrium with its condensed phases (solid or liquid) at a given temperature in a closed system.
  • the saturated vapour pressure at the respective temperature can be determined by the skilled person by methods known in the art.
  • the saturated vapour pressures of a certain substance or mixture is determined as set forth in the OECD Guidelines for the Testing of Chemicals (1981): Test No. 104, items 14-19 “Static Method”, adopted Mar. 23, 2006.
  • steps b) and c) are carried out at least twice, even more preferably at least three times, wherein step b) is carried out with the high purity compound of formula (I) obtained in directly antecedent step c).
  • step c) has as unexpectedly low level of odour-intensive and smelly substances. This is even more surprising as a skilled person would not have treated the crude product (I) obtained after step a) with water, especially because compound (I) is in fact to be used as water-absorbing material.
  • the method of the present invention thus provides as a product a highly pure imidazolium salt.
  • N-methylimidazole (CAS number: 616-47-7) and triethylphosphate (CAS number: 78-40-0) were purchased from Sigma Aldrich.
  • p is the pressure in hPa
  • T is the temperature in ° C.
  • log 10 is the common logarithm.
  • the residuals in each sample were determined by olfactory analysis.
  • the residuals in samples obtained in V1-V4 and E1-E3 were determined by headspace GC/MS as follows: 0.1 g of the sample was incubated for 20 minutes at 70° C. in a sampler. The composition of the gas phase was analyzed directly with gas chromatography (“GC”) and mass spectrometry (“MS”). GC is performed with an apparatus of Hewlett Packard (“HP 6890”; sampler: Turbomatrix 40, Perkin Elmer). MS is performed with an apparatus of Hewlett-Packard (“HP 5973”).
  • GC gas chromatography
  • MS mass spectrometry
  • the quantity of the residuals are determined based on the peak height observed in the chromatogram.
  • Triethylphosphate (929 g, 5.0 mole) was added dropwise to a reaction vessel containing N-methylimidazole (411 g, 5.0 mole). Afterwards the reaction mixture was heated up to 150° C. and stirred under reflux for 14 h. Then, the mixture was diluted with 20 weight-% of water (based on the sum of the masses of the starting materials triethylphosphate and N-methylimidazole) and the water was distilled of at different pressures as summarized in the following table.
  • the water was removed at 50° C. and a pressure of 5 hPa, which is above the saturated vapour pressure of triethylphosphate at the respective temperature (4.1 hPa).
  • the water was removed at 60° C. and a pressure of 14 hPa, which is above the saturated vapour pressure of triethylphosphate at the respective temperature (12.2 hPa).
  • the water was removed at 70° C. and a pressure of 37 hPa, which is above the saturated vapour pressure of triethylphosphate at the respective temperature (34.14 hPa).
  • the water was removed at 99° C. and a pressure of 540 hPa, which is above the saturated vapour pressure of triethylphosphate at the respective temperature (493.5 hPa).
  • inventive examples E1-E3 water was added, and the water was removed at 60° C. (E1, E2) or 85° C. (E3) and a pressure of 5 and 20 hPa, respectively, which is below the saturated vapour pressure of triethylphosphate at the respective temperatures (12.2 hPa at 60° C. and 143.5 hPa at 85° C.).
  • the water was removed at 50° C. and a pressure of 3 hPa, which is below the saturated vapour pressure of triethylphosphate at the respective temperature (4.1 hPa).
  • the water was removed at 60° C. and a pressure of 10 hPa, which is below the saturated vapour pressure of triethylphosphate at the respective temperature (12.2 hPa).
  • the water was removed at 70° C. and a pressure of 31 hPa, which is below the saturated vapour pressure of triethylphosphate at the respective temperature (34.1 hPa).
  • the water was removed at 99° C. and a pressure of 440 hPa, which is below the saturated vapour pressure of triethylphosphate at the respective temperature (493.5 hPa).
  • the water was removed at 120° C. and a pressure of 1000 hPa, which is below the saturated vapour pressure of triethylphosphate at the respective temperature (2669.9 hPa).

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  • Organic Chemistry (AREA)
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Abstract

The present invention encompasses a novel method for synthesizing highly pure salts of the general formula Q+A−, wherein Q+ is:
Figure US20170355680A1-20171214-C00001
and wherein A− is
Figure US20170355680A1-20171214-C00002

Description

    CROSS REFERENCE TO RELATED APPLICATIONS
  • The present application claims priority under 35 USC §119 to European application, EP16174303.4, filed on Jun. 14, 2016, the contents of which is incorporated herein by reference in its entirety.
    • FIELD OF THE INVENTION
  • The invention relates to a method of preparing a high purity imidazolium salt.
    • BACKGROUND OF THE INVENTION
  • In air conditioning systems for the aeration and conditioning of buildings or vehicles, the air generally not only has to be cooled, but also dehumidified since the air to be cooled often has such a high humidity that, upon cooling to the desired temperature, the dew point is fallen below. Hence in conventional air conditioning systems dehumidification of the air accounts for a large part of the electricity consumption.
  • One option of reducing the electricity consumption of air conditioning systems for buildings is the dehumidification of air by adsorption or absorption of water using a drying medium and a regeneration of the drying medium laden with water by heating to a temperature at which the water is desorbed again. Compared to adsorption on a solid adsorbent, the advantage of absorption in a liquid absorption medium is that drying of air can be performed with reduced equipment complexity and with less drying medium and that regeneration of the water-laden drying medium using solar heat is easier to carry out.
  • The aqueous solutions of lithium bromide, lithium chloride or calcium chloride hitherto employed as liquid absorption media in commercial air conditioning systems have the disadvantage that they are corrosive towards the metallic materials of construction typically employed in air conditioning systems and that they thus necessitate the use of expensive specific materials of construction. These solutions can additionally cause problems due to salt crystallizing out of the absorption medium.
  • Ionic liquids comprising dialkylimidazolium ions (as described in WO 2004/016631 A1) have been described as alternatives to lithium salts in the prior art for similar applications. Y. Luo et al., Appl. Thermal Eng. 31 (2011) 2772-2777 proposes the ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate in place of aqueous solutions of lithium bromide for drying of air.
  • Y. Luo et al., Solar Energy 86 (2012) 2718-2724 proposes the ionic liquid 1,3-dimethyimidazolium acetate as an alternative to 1-ethyl-3-methylimidazolium tetrafluoroborate for drying of air.
  • US 2011/0247494 A1 proposes, in paragraph [0145], the use of trimethylammonium acetate or 1-ethyl-3-methylimidazolium acetate as liquid drying agent instead of aqueous lithium chloride solution. Example 3 compares water uptake from humid air for a series of further ionic liquids.
  • However, a problem of ionic liquids comprising dialkylimidazolium ions is that they often comprise impurities, which lead to substances that are odour-intensive or are injurious to health entering the dehumidified air upon a dehumidification of air using the ionic liquid. Moreover, it has been found that during the desorption of water from ionic liquids which contain a basic anion, such as, for example, a carboxylate ion, odour-intensive decomposition products are formed which, in the event of a subsequent use of the ionic liquid for the dehumidification of air, enter the dehumidified air.
  • Therefore, there remains a need for ionic liquids comprising imidazolium ions, which do not display the disadvantages described above. The problem to be solved by the present invention is hence provision of a process for the production of ionic liquids comprising dialkylimidazolium ions, wherein the level of volatile compounds is brought to a minimum.
    • DETAILED DESCRIPTION OF THE INVENTION
  • It has been surprisingly found that the above problem is solved by the process described hereinafter.
  • The invention hence provides a process for preparing a high purity compound of formula (I):

  • Q + A −,
  • wherein Q+ is
  • Figure US20170355680A1-20171214-C00003
  • and wherein A− is
  • Figure US20170355680A1-20171214-C00004
  • the process comprising:
    • a) reacting a compound of formula (II) with a compound of formula (III), wherein (II) and (III) are:
  • Figure US20170355680A1-20171214-C00005
      • to give a crude product comprising a compound of formula (I);
    • b) adding water to the crude product of formula (I) from step a), to give a diluted crude product comprising a compound of formula (I);
    • c) at least partial removal of the water added in step b) from the diluted crude product by distillation of the diluted crude product at a temperature T1 in the range of 30-180° C. and at a pressure p1 which is lower than the saturated vapour pressure of compound (III) at the temperature T1, giving a high purity compound of formula (I);
      wherein:
      each of R1, R2, R3 are independently a hydrogen or alkyl of 1 to 4 carbon atoms,
      each of R4, R5, R6, R7 are independently alkyl of 1 to 4 carbon atoms.
  • In a preferred embodiment of the present invention, R1=R2=R3=hydrogen and each of R4, R5, R6, R7 are independently methyl or ethyl. In a more preferred embodiment of the present invention, R1=R2=R3=hydrogen, R5=methyl and each of R4, R6, R7 are independently methyl or ethyl. In an even more preferred embodiment of the present invention, R1=R2=R3=hydrogen, R5=methyl and R4=R6=R7=ethyl.
  • In step a) of the process according to the invention, a compound of formula (II) with a compound of formula (III) is reacted, giving a crude product comprising a compound of formula (I). The skilled person is familiar with the reaction conditions, which are described in WO 2004/016631 A1, for example.
  • In particular, step a) of the process according to the invention is preferably carried out at a temperature in the range of from 130° C. to 200° C., more preferably 140° C. to 190° C., even more preferably 150° C. to 175° C.
  • The pressure of the reaction is not critical and may be for example atmospheric pressure, preferably under an inert atmosphere, such as nitrogen.
  • As the reaction is exothermic, it may be desirable to control the rate of addition in some cases and/or to apply external cooling during the addition step.
  • In general, the compounds of formula (II) and (III) are present in stoichiometric amounts, i.e. the molar relation of compound (II) to compound (III) is in the range 0.9:1 to 1.1:1, more preferably 1:1. In some cases, it might be advantageous to use the imidazole compound (II) in a slight excess to the phosphate ester (III), for example in the range of 1.01 to 1.4 molar equivalents, preferable 1.02 to 1.4.
  • The reaction time is not particularly limited. Typically, the reaction is continued until at least 90% of the compounds (II) or (III) has reacted to form compound (I). The progress of the reaction can be conveniently controlled by methods known to the skilled person, such as NMR
  • The reaction in step a) can be carried out in the presence or absence of a solvent and is preferably carried out in the absence of a solvent.
  • “Solvent” means water or organic solvents which are known to the skilled person, preferably it means water. These organic solvents are preferably selected from the group consisting of aliphatic solvents, preferably pentane, hexane, heptane, octane, decane, cyclohexane, tetramethylsilane; aromatic solvents, preferably benzene, toluene, xylene; ether compounds, preferably diethyl ether, dipropyl ether, dibutyl ether, methyl tert-butyl ether; halogenated solvents, preferably dichloromethane, chloroform, tetrachloromethane; alcohols, preferably methanol, ethanol, propanol, iso-propanol, butanol, tert-butanol; esters, preferably methyl acetate, ethyl acetate, propyl acetate, butyl acetate; acetone. Especially preferred organic solvents are selected from esters, alcohols.
  • “Absence of a solvent” means particularly that the overall content of all solvents in the reaction mixture is below 10 weight-% based on the sum of the weights of compounds (II) and (III), preferably below 5 weight-% based on the sum of the weights of compounds (II) and (III), more preferably below 1 weight-% based on the sum of the weights of compounds (II) and (III).
  • “Presence of a solvent” means that the sum of all solvents present in the reaction mixture is at least 1.0 weight-%, based on the combined masses of compounds (II) and (III). Even more preferred, it means that the sum of all solvents present in the reaction mixture is at least 3.7 weight-%, based on the combined masses of compounds (II) and (III). Even more preferred, it means that the sum of all solvents present in the reaction mixture is at least 7.4 weight-%, based on the combined masses of compounds (II) and (III). Even more preferred, it means that the sum of all solvents present in the reaction mixture is at least 10.0 weight-%, based on the combined masses of compounds (II) and (III). Even more preferred, it means that the sum of all solvents present in the reaction mixture is at least 20.0 weight-%, based on the combined masses of compounds (II) and (III). Even more preferred, it means that the sum of all solvents present in the reaction mixture is at least 40.0 weight-%, based on the combined masses of compounds (II) and (III). Even more preferred, it means that the sum of all solvents present in the reaction mixture is at least 80 weight-%, based on the combined masses of compounds (II) and (III). Even more preferred, it means that the sum of all solvents present in the reaction mixture is at least 100 weight-%, based on the combined masses of compounds (II) and (III). Even more preferred, it means that the sum of all solvents present in the reaction mixture is at least 150 weight-%, based on the combined masses of compounds (II) and (III).
  • In the embodiment of the invention in which the step a) is carried out in the presence of a solvent, it is preferred that the solvent is at least partially removed after step a) before step b) is carried out. Such at least partial removal can be carried out by extraction, stripping, distillation or any other process known to the skilled person, preferably by extraction, stripping, distillation. In this context, “partial removal” means in particular, that at least 50% of the solvent added in step a) is removed, preferably at least 70%, even more preferably at least 90%, even more preferably 99% of the solvent is removed.
  • In case step a) is carried out in the presence of a solvent comprising water, the partial removal of the solvent is preferably carried out by distillation at a temperature T2 in the range of 30-180° C., preferably 37° C.-178° C., even more preferably 50° C.-150° C., even more preferably 60° C.-120° C., even more preferably 70° C.-99° C., and at a pressure p2 which is lower than the saturated vapour pressure of compound (III) at the temperature T2.
  • In a preferred embodiment, the pressure p2 is also higher than the saturated vapour pressure of the compound (I), even more preferably higher than the saturated vapour pressure of a mixture of compound (I):water=99:1, even more preferably 98:2, even more preferably 97:3.
  • The result of the reaction of step a) of the method according to the invention is a crude product comprising a compound of formula (I).
  • Within the context of the invention, the term “crude product” means the reaction mixture which is obtained after the reaction has taken place [step a) of the process according to the invention] and is then submitted to step b). As stated above, in case step a) is carried out in presence of a solvent, such solvent can be optionally removed at least partially from the crude product obtained after step a) before step b) is carried out.
  • The crude product obtained in step a) is then further processed in step b). In step b), water is added to the crude product of formula (I) from step a), preferably in an amount of at least 1 weight-% based on the amount of compounds (II) and (III) used in step a), giving a diluted crude product comprising a compound of formula (I).
  • Preferably, in step b) water is added to the crude product of formula (I) from step a) in an amount in the range of 1 to 200, more preferably 5 to 100, even more preferably 7 to 75, even more preferably 10 to 50, most preferably 15 to 20 weight-% based on the amount of compounds (II) and (III) used in step a).
  • Within the context of the invention, the term “diluted crude product” means the mixture which is obtained after the addition of water according to step b) and is then submitted to step c).
  • In step c) of the process, the water added in step b) is then at least partially removed from the diluted crude, wherein special temperature and pressure conditions are applied. Namely, it is essential to the invention that the water is removed by distillation at a temperature T1 in the range of 30-180° C., preferably 37° C.-178° C., even more preferably 50° C.-150° C., even more preferably 60° C.-120° C., even more preferably 70° C.-99° C., and at a pressure p1 which is lower than the saturated vapour pressure of compound (III) at the temperature T1.
  • “At least partially removed” in the context of the invention with respect to claim c) means, that at least 50% of the water added in step b) is removed, preferably at least 70%, even more preferably at least 90%, even more preferably 99% of the water added in step b) is removed. For carrying out the distillation, all apparatuses known to the person skilled in the art can be used, thus e.g. a stirred reactor, a falling-film evaporator or a thin-film evaporator, in each case in combination with a suitable distillation column or another apparatus suitable for the distillation.
  • The pressure p1 at which the distillation takes place has to be lower than the saturated vapour pressure of compound (III) at the temperature T1, wherein T1 is in the range of 30-180° C.
  • In a preferred embodiment, the pressure p1 is also higher than the saturated vapour pressure of the compound (I), even more preferably higher than the saturated vapour pressure of a mixture of compound (I):water=99:1, even more preferably 98:2, even more preferably 97:3.
  • “Saturated vapour pressure” of a certain substance or mixture is defined as the pressure exerted by a vapour of this substance or mixture in thermodynamic equilibrium with its condensed phases (solid or liquid) at a given temperature in a closed system.
  • The saturated vapour pressure at the respective temperature can be determined by the skilled person by methods known in the art. For example, and according to the invention, the saturated vapour pressures of a certain substance or mixture is determined as set forth in the OECD Guidelines for the Testing of Chemicals (1981): Test No. 104, items 14-19 “Static Method”, adopted Mar. 23, 2006.
  • In a preferred embodiment of the method according to the present invention, steps b) and c) are carried out at least twice, even more preferably at least three times, wherein step b) is carried out with the high purity compound of formula (I) obtained in directly antecedent step c).
  • It has now surprisingly been found that, only when the combination of the water addition step b) and the distillation step c) according to the method of the invention is carried out, the product obtained at the end of step c) has as unexpectedly low level of odour-intensive and smelly substances. This is even more surprising as a skilled person would not have treated the crude product (I) obtained after step a) with water, especially because compound (I) is in fact to be used as water-absorbing material.
  • The method of the present invention thus provides as a product a highly pure imidazolium salt.
  • The following examples illustrate the invention.
    • EXAMPLES Materials
  • In the following examples, N-methylimidazole (CAS number: 616-47-7) and triethylphosphate (CAS number: 78-40-0) were purchased from Sigma Aldrich.
    • Methods
  • The saturated vapour pressures were determined by the method described in: OECD Guidelines for the Testing of Chemicals (1981): Test No. 104, items 14-19 “Static Method”, adopted Mar. 23, 2006.
  • The saturated vapour pressure determined by this method for triethylphosphate follow the formula <1> wherein

  • log10(p)=16.42−5108.4/(273.15+T)  <1>.
  • In formula <1>, p is the pressure in hPa, T is the temperature in ° C., “log10” is the common logarithm.
  • The saturated vapour pressure of triethylphosphate at 150° C.=22268 hPa, at 140° C.=11363 hPa, at 120° C.=2669.9 hPa, at 99° C.=493.5, at 85° C.=143.5 hPa, at 70° C.=34.1 hPa, at 60° C.=12.2 hPa, at 50° C.=4.1 hPa.
  • The saturated vapour pressure of a mixture of 99 parts of 1-ethyl-3-methylimidazolium diethylphosphate (=EMIM DEP) and 1 part of water are as follows: at 150° C.=380 hPa, at 140° C.=254 hPa, at 85° C.=18.6 hPa, at 60° C.=4.2 hPa.
  • The residuals in each sample were determined by olfactory analysis.
  • In addition, the residuals in samples obtained in V1-V4 and E1-E3 were determined by headspace GC/MS as follows: 0.1 g of the sample was incubated for 20 minutes at 70° C. in a sampler. The composition of the gas phase was analyzed directly with gas chromatography (“GC”) and mass spectrometry (“MS”). GC is performed with an apparatus of Hewlett Packard (“HP 6890”; sampler: Turbomatrix 40, Perkin Elmer). MS is performed with an apparatus of Hewlett-Packard (“HP 5973”).
  • The quantity of the residuals are determined based on the peak height observed in the chromatogram.
    • General Procedure for Inventive Examples E1-E8 and Comparative Examples V1-V8
  • Triethylphosphate (929 g, 5.0 mole) was added dropwise to a reaction vessel containing N-methylimidazole (411 g, 5.0 mole). Afterwards the reaction mixture was heated up to 150° C. and stirred under reflux for 14 h. Then, the mixture was diluted with 20 weight-% of water (based on the sum of the masses of the starting materials triethylphosphate and N-methylimidazole) and the water was distilled of at different pressures as summarized in the following table.
  • In comparative example V1, the treatment with water was omitted and the mixture merely moved to a rotary evaporator.
  • In all examples except V1, 93.8 g water (=7 weight-% based on the combined masses of triethylphosphate and N-methylimidazole used in the general procedure) were added. In examples V2-V4, the water was removed at 60° C. and a pressure of 20 hPa, which is above the saturated vapour pressure of triethylphosphate at the respective temperature (12.2 hPa).
  • In example V5, the water was removed at 50° C. and a pressure of 5 hPa, which is above the saturated vapour pressure of triethylphosphate at the respective temperature (4.1 hPa).
  • In example V6, the water was removed at 60° C. and a pressure of 14 hPa, which is above the saturated vapour pressure of triethylphosphate at the respective temperature (12.2 hPa).
  • In example V7, the water was removed at 70° C. and a pressure of 37 hPa, which is above the saturated vapour pressure of triethylphosphate at the respective temperature (34.14 hPa).
  • In example V8, the water was removed at 99° C. and a pressure of 540 hPa, which is above the saturated vapour pressure of triethylphosphate at the respective temperature (493.5 hPa).
  • In inventive examples E1-E3, water was added, and the water was removed at 60° C. (E1, E2) or 85° C. (E3) and a pressure of 5 and 20 hPa, respectively, which is below the saturated vapour pressure of triethylphosphate at the respective temperatures (12.2 hPa at 60° C. and 143.5 hPa at 85° C.).
  • In example E4, the water was removed at 50° C. and a pressure of 3 hPa, which is below the saturated vapour pressure of triethylphosphate at the respective temperature (4.1 hPa).
  • In example E5, the water was removed at 60° C. and a pressure of 10 hPa, which is below the saturated vapour pressure of triethylphosphate at the respective temperature (12.2 hPa).
  • In example E6, the water was removed at 70° C. and a pressure of 31 hPa, which is below the saturated vapour pressure of triethylphosphate at the respective temperature (34.1 hPa).
  • In example E7, the water was removed at 99° C. and a pressure of 440 hPa, which is below the saturated vapour pressure of triethylphosphate at the respective temperature (493.5 hPa).
  • In example E8, the water was removed at 120° C. and a pressure of 1000 hPa, which is below the saturated vapour pressure of triethylphosphate at the respective temperature (2669.9 hPa).
  • Distillation
    at Repetitions of
    Water T [° C.]/p adding water und Residual
    Example added? [hPa] distillation [ng/g] odor
    V1 No 150/50  0 3049 sweet and slightly
    fishy
    V2 Yes 60/20 1 1021 slightly fishy
    V3 Yes 60/20 2 407 slightly fishy
    V4 Yes 60/20 3 297 very slightly fishy
    V5 Yes 50/5  1 slight sweet
    V6 Yes 60/14 1 slight sweet
    V7 Yes 70/37 1 slight sweet
    V8 Yes  99/540 1 slight sweet
    E1 Yes 60/5  1 70 No smell
    E2 Yes 60/5  3 n.d.* (<10) No smell
    E3 Yes 85/20 3 n.d.* (<10) No smell
    E4 Yes 50/3  1 No smell
    E5 Yes 60/10 1 No smell
    E6 Yes 70/31 1 No smell
    E7 Yes  99/440 1 No smell
    E8 Yes  120/1000 1 No smell
    *“n.d.” = “not detectable”
  • The above summarized result show that only when the combination of the water addition step b) and the removal step c), only when carried out under the distillation conditions according to the invention, lead to the highly pure imidazolium salt.
  • All references cited herein are fully incorporated by reference. Having now fully described the invention, it will be understood by those of skill in the art that the invention may be practiced within a wide and equivalent range of conditions, parameters and the like, without affecting the spirit or scope of the invention

Claims (20)

What is claimed is:
1. A process for preparing a high purity compound of formula (I):

Q + A −,
wherein Q+ is:
Figure US20170355680A1-20171214-C00006
and wherein A− is:
Figure US20170355680A1-20171214-C00007
the process comprising:
a) reacting a compound of formula (II) with a compound of formula (III), wherein (II) and (III) are:
Figure US20170355680A1-20171214-C00008
to give a crude product comprising a compound of formula (I);
b) adding water to the crude product of formula (I) from step a), to give a diluted crude product comprising a compound of formula (I);
c) at least partial removal of the water added in step b) from the diluted crude product by distillation of the diluted crude product at a temperature T1 in the range of 30-180° C. and at a pressure p1 which is lower than the saturated vapour pressure of compound (III) at the temperature T1, giving a high purity compound of formula (I);
wherein:
each of R1, R2, R3 are independently a hydrogen or alkyl of 1 to 4 carbon atoms;
each of R4, R5, R6, R7 are independently alkyl of 1 to 4 carbon atoms.
2. The process of claim 1, wherein R1=R2=R3=hydrogen and wherein each of R4, R5, R6, R7 are independently methyl or ethyl.
3. The process of claim 2, wherein R1=R2=R3=hydrogen, R5=methyl and wherein each of R4, R6, R7 are independently methyl or ethyl.
4. The process of claim 1, wherein step a) is carried out in the absence of a solvent.
5. The process of claim 1, wherein step a) is carried out in the presence of a solvent.
6. The process of claim 5, wherein the solvent is at least partially removed between steps a) and b).
7. The process of claim 1, wherein, in step b), water is added in an amount of at least 1 weight-% based on the amount of compounds (II) and (III) used in step a).
8. The process of claim 1, wherein “partial removal” in step c) means removal of at least 50% of the water added in step b).
9. The process of claim 1, wherein pressure p1 is lower than the saturated vapour pressure of compound (III) at the temperature T1 and higher than the saturated vapour pressure of (I) at the temperature T1.
10. The process of claim 1, wherein steps b) and c) are carried out at least twice, and wherein step b) is carried out with the high purity compound of formula (I) obtained in directly antecedent step c).
11. The process of claim 2, wherein said process is carried out in the absence of an organic solvent.
12. The process of claim 11, wherein in step b) water is added in an amount of at least 1 weight-% based on the amount of compounds (II) and (III) used in step a).
13. The process of claim 12, wherein “partial removal” in step c) means removal of at least 50% of the water added in step b).
14. The process of claim 13, wherein pressure p1 is lower than the saturated vapour pressure of compound (III) at the temperature T1 and higher than the saturated vapour pressure of (I) at the temperature T1.
15. The process of claim 14, wherein steps b) and c) are carried out at least twice, and wherein step b) is carried out with the high purity compound of formula (I) obtained in directly antecedent step c).
16. The process of claim 3, wherein said process is carried out in the absence of an organic solvent.
17. The process of claim 16, wherein in step b) water is added in an amount of at least 1 weight-% based on the amount of compounds (II) and (III) used in step a).
18. The process of claim 17, wherein “partial removal” in step c) means removal of at least 50% of the water added in step b).
19. The process of claim 18, wherein pressure p1 is lower than the saturated vapour pressure of compound (III) at the temperature T1 and higher than the saturated vapour pressure of (I) at the temperature T1.
20. The process of claim 19, wherein steps b) and c) are carried out at least twice, and wherein step b) is carried out with the high purity compound of formula (I) obtained in directly antecedent step c).
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10105644B2 (en) 2016-06-14 2018-10-23 Evonik Degussa Gmbh Process and absorbent for dehumidifying moist gas mixtures
US10138209B2 (en) 2016-06-14 2018-11-27 Evonik Degussa Gmbh Process for purifying an ionic liquid
US10493400B2 (en) 2016-06-14 2019-12-03 Evonik Degussa Gmbh Process for dehumidifying moist gas mixtures
US10500540B2 (en) 2015-07-08 2019-12-10 Evonik Degussa Gmbh Method for dehumidifying humid gas mixtures using ionic liquids
US10512883B2 (en) 2016-06-14 2019-12-24 Evonik Degussa Gmbh Process for dehumidifying moist gas mixtures
US10512881B2 (en) 2016-06-14 2019-12-24 Evonik Degussa Gmbh Process for dehumidifying moist gas mixtures

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11217828B2 (en) * 2016-12-05 2022-01-04 Massachusetts Institute Of Technology Flame-retardant, non-toxic phosphate ester ionic liquid electrolytes and method of making
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CN116217620A (en) * 2023-01-10 2023-06-06 合肥学院 Phosphorus-containing porphyrin and preparation method and application thereof

Family Cites Families (190)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE400488C (en) 1922-10-24 1924-08-11 Hans Hylander Absorption refrigeration machine
FR670497A (en) 1928-06-19 1929-11-29 Thermal installation for vehicles, flying machines, boats and other marine craft
US1882258A (en) 1930-09-10 1932-10-11 Randel Bo Folke Means and method of refrigeration
DE633146C (en) 1933-06-01 1936-07-20 Sachsenberg Akt Ges Geb Absorption apparatus
DE737031C (en) 1940-03-30 1943-07-06 Koppers Gmbh Heinrich Wet gas cleaning method
US2516625A (en) 1946-12-02 1950-07-25 Shell Dev Derivatives of dihydropyridine
US2601673A (en) 1951-04-09 1952-06-24 Shell Dev Shortstopping the addition polymerization of unsaturated organic compounds
US2802344A (en) 1953-07-08 1957-08-13 Eureka Williams Corp Electrodialysis of solutions in absorption refrigeration
US3317654A (en) 1964-12-16 1967-05-02 Joslyn Mfg & Supply Co Electrical cable terminal
US3276217A (en) 1965-11-09 1966-10-04 Carrier Corp Maintaining the effectiveness of an additive in absorption refrigeration systems
US4524587A (en) 1967-01-10 1985-06-25 Kantor Frederick W Rotary thermodynamic apparatus and method
US3609087A (en) 1968-02-01 1971-09-28 American Gas Ass Inc The Secondary alcohol additives for lithium bromide-water absorption refrigeration system
US3580759A (en) 1968-06-25 1971-05-25 Borg Warner Heat transfer additives for absorbent solutions
GB1306853A (en) 1970-05-13 1973-02-14 Ici Ltd Process for separating and recovering acid gases from gaseous mixtures
GB1491625A (en) 1974-03-18 1977-11-09 Inoue Japax Res Electric power generation
IT1024575B (en) 1974-05-28 1978-07-20 Giammarco G IMPROVED PROCEDURE FOR THE ABSORPTION OF C02 E. OR H2S BY SOLUTION OF ALKALINE CARBONATE ADDED OF GLYCINE TO OTHER AMINOACES OF
AU506199B2 (en) 1975-06-26 1979-12-20 Exxon Research And Engineering Company Absorbtion of co2 from gaseous feeds
SE409054B (en) 1975-12-30 1979-07-23 Munters Ab Carl DEVICE FOR HEAT PUMP IN WHICH A WORKING MEDIUM IN A CLOSED PROCESS CIRCULATES IN A CIRCUIT UNDER DIFFERENT PRESSURES AND TEMPERATURE
US4022785A (en) 1976-01-08 1977-05-10 Petrolite Corporation Substituted pyridines and dihydropyridines
US4201721A (en) 1976-10-12 1980-05-06 General Electric Company Catalytic aromatic carbonate process
US4094957A (en) 1976-12-14 1978-06-13 Exxon Research & Engineering Co. Process for removing acid gases with hindered amines and amino acids
US4152900A (en) 1978-04-04 1979-05-08 Kramer Trenton Co. Refrigeration cooling unit with non-uniform heat input for defrost
GB2047681A (en) 1979-04-30 1980-12-03 Argus Chem Preparation of 2,2,6,6- tetramethyl-4-oxopiperidine
US4251494A (en) 1979-12-21 1981-02-17 Exxon Research & Engineering Co. Process for removing acidic compounds from gaseous mixtures using a two liquid phase scrubbing solution
DE3003843A1 (en) 1980-02-02 1981-08-13 Chemische Werke Hüls AG, 4370 Marl METHOD FOR PRODUCING 4-AMINO-2,2,6,6-TETRAMETHYL PIPERIDINE
AU7424681A (en) 1980-09-10 1982-03-18 B.F. Goodrich Company, The Piperidine derivatives as u.v. stabilisers
JPS57191407A (en) 1981-05-20 1982-11-25 Hitachi Ltd Rankine cycle system
IN163391B (en) 1981-11-13 1988-09-17 Exxon Research Engineering Co
US4525294A (en) 1981-11-13 1985-06-25 Exxon Research And Engineering Co. Amino acid mixtures, their alkali metal salts and process for preparing same
US4405579A (en) 1981-11-13 1983-09-20 Exxon Research And Engineering Co. Sterically hindered amino acids and tertiary amino acids as promoters in acid gas scrubbing processes
US4405586A (en) 1981-11-13 1983-09-20 Exxon Research And Engineering Co. N-Secondary butyl glycine promoted acid gas scrubbing process
US4360363A (en) 1982-02-16 1982-11-23 Combustion Engineering, Inc. Physical solvent for gas sweetening
US4489563A (en) 1982-08-06 1984-12-25 Kalina Alexander Ifaevich Generation of energy
US4466915A (en) 1982-09-29 1984-08-21 The B. F. Goodrich Company Non-catalytic ketoform syntheses
NL8403517A (en) 1984-11-19 1986-06-16 Rendamax Ag ABSORPTION-RESORPTION HEAT PUMP.
JPS61129019A (en) 1984-11-26 1986-06-17 Hitachi Ltd Absorbing type temperature circuit
HUT41715A (en) 1984-12-28 1987-05-28 Monsanto Co Process for preparing n-substituted alpha-aminoacids and derivatives thereof
EP0193327A1 (en) 1985-02-19 1986-09-03 The Dow Chemical Company Low viscosity gas dehydrating agents and gas sweetening agents
US4605743A (en) 1985-04-16 1986-08-12 Uniroyal Chemical Company, Inc. Process for the production of 2,2,6,6-tetraalkyl-4-piperidylamines
JPS6273055A (en) 1985-09-25 1987-04-03 日本鋼管株式会社 Absorption type heat pump
US4701530A (en) 1985-11-12 1987-10-20 The Dow Chemical Company Two-stage process for making trimethyl pyridine
US5016445A (en) 1986-07-07 1991-05-21 Darrell H. Williams Absorption apparatus, method for producing a refrigerant effect, and an absorbent-refrigerant solution
US5186010A (en) 1985-11-18 1993-02-16 Darrel H. Williams Absorbent-refrigerant solution
US4714597A (en) 1986-06-26 1987-12-22 Hylsa, S.A. Corrosion inhibitor for CO2 absorption process using alkanolamines
DE3623680A1 (en) 1986-07-12 1988-01-14 Univ Essen Materials systems for sorption processes
US5186009A (en) 1987-04-14 1993-02-16 Gas Research Institute Aqueous absorption fluids
US5126189A (en) 1987-04-21 1992-06-30 Gelman Sciences, Inc. Hydrophobic microporous membrane
IT1222394B (en) 1987-07-30 1990-09-05 Ciba Geigy Spa PROCESS FOR THE PREPARATION OF 2,2,6,6 TETRAMETHY 4 PIPERIDYLAMINS
EP0303569A3 (en) 1987-08-12 1990-06-13 Ciba-Geigy Ag 1,4-oxathianones and 1,4-oxathiepanones and their use as additives in functional liquids
DD266799A1 (en) 1987-10-20 1989-04-12 Leuna Werke Veb PROCESS FOR THE ISOLATION OF HIGH-PURITY 4-AMINO-2,2,6,6-TETRAMETHYLPIPERIDINE
JPH07111287B2 (en) 1987-11-18 1995-11-29 日立電線株式会社 Heat transfer tube for absorber
JPH02298767A (en) 1989-05-12 1990-12-11 Nissin Electric Co Ltd Absorption refrigerator
JP2959141B2 (en) 1991-02-22 1999-10-06 ダイキン工業株式会社 Absorption refrigeration equipment
US5390509A (en) 1991-11-27 1995-02-21 Rocky Research Triple effect absorption cycle apparatus
JPH0784965B2 (en) 1991-12-24 1995-09-13 誠之 渡辺 Solar cooling system
DE69306829T3 (en) 1992-02-27 2006-08-31 The Kansai Electric Power Co., Inc. Process for removing carbon dioxide from combustion exhaust gases
CN1055872C (en) 1992-03-14 2000-08-30 南京化学工业(集团)公司研究院 Removing carbon dioxide in mixed gas by composite activating agent
US5255534A (en) 1992-06-25 1993-10-26 Gas Research Institute System and process for operating and absorption cycle around a crystallization curve of the solution
US5303565A (en) 1993-03-11 1994-04-19 Conserve Resources, Inc. Rotary absorption heat pump of improved performance
JP3236402B2 (en) 1993-04-22 2001-12-10 大阪瓦斯株式会社 Absorption refrigerator
JPH07167521A (en) 1993-12-15 1995-07-04 Asahi Glass Co Ltd Absorption type refrigerator
DE19511709A1 (en) 1995-03-30 1996-10-02 Klement Arne Generating cold and heat with aid of absorption cooling machine
DE29516319U1 (en) 1995-10-14 1996-02-01 ABSOTECH Energiesparsysteme GmbH & Co. KG, 83646 Bad Tölz Absorption heat transformation system with additional components to increase the useful output or extend the limits for the drive, useful or cooling temperatures
RU2101625C1 (en) 1995-10-24 1998-01-10 Марат Шавкатович Гадельшин Absorption refrigerator
RU2122642C1 (en) 1996-05-28 1998-11-27 Акционерное общество открытого типа "Энергетический научно-исследовательский институт им.Г.М.Кржижановского" Combined-cycle steam power plant
US6331289B1 (en) 1996-10-28 2001-12-18 Nycomed Imaging As Targeted diagnostic/therapeutic agents having more than one different vectors
RU2183003C2 (en) 1997-01-08 2002-05-27 Дзе Бок Груп ПЛС Cooler for cooling of liquid in vessel for keeping of liquid and vessel for keeping of liquid
US6117963A (en) 1997-03-26 2000-09-12 Th Goldschmidt Ag Tetrahydrofuran-containing silicone polyethers
US5873260A (en) 1997-04-02 1999-02-23 Linhardt; Hans D. Refrigeration apparatus and method
TW538055B (en) 1997-04-14 2003-06-21 Nippon Catalytic Chem Ind Pressure-resistant absorbent resin, disposable diaper using the resin and absorbent resin, and method for production thereof
RU2191621C2 (en) 1998-04-06 2002-10-27 Ниппон Ниюказаи Ко., Лтд. Method of regenerating fluid absorbing acid gas containing methyl diethanolamine and derivative of piperazine of lower alkyls
DE19850624A1 (en) 1998-11-03 2000-05-04 Basf Ag Process for the preparation of cyanoacetic acid esters
US6155057A (en) 1999-03-01 2000-12-05 Arizona Board Of Regents Refrigerant fluid crystallization control and prevention
WO2000061698A1 (en) 1999-04-12 2000-10-19 Arizona Board Of Regents Two-phase refrigeration fluid for an absorption refrigeration apparatus and a method of preventing corrosion
US6165433A (en) 1999-06-10 2000-12-26 Praxair Technology, Inc. Carbon dioxide recovery with composite amine blends
JP2001074322A (en) 1999-09-03 2001-03-23 Daikin Ind Ltd Refrigerating system
DE19949347A1 (en) 1999-10-13 2001-04-19 Basf Ag Fuel cell
JP2001219164A (en) 2000-02-08 2001-08-14 Toyobo Co Ltd Water cleaning unit and water cleaning equipment
JP2002047258A (en) 2000-08-01 2002-02-12 Showa Denko Kk Method for manufacturing n-isopropylglycine
DE10040402A1 (en) 2000-08-18 2002-02-28 Degussa Process for the preparation of 2-hydroxy-4-methyl mercaptobutyric acid (MHA)
WO2002074718A2 (en) 2001-03-20 2002-09-26 Basf Aktiengesellschaft Ionic liquids as selective additives for the separation of close-boiling or azeotropic mixtures
DE10208822A1 (en) 2002-03-01 2003-09-11 Solvent Innovation Gmbh Halogen-free ionic liquids
JP2004044945A (en) 2002-07-12 2004-02-12 Daikin Ind Ltd Absorption accelerator for absorption-type refrigeration unit
US7052582B2 (en) 2002-07-23 2006-05-30 Madkour Yousry E Wave powered evaporation desalination system
CA2598156C (en) * 2002-08-16 2011-02-08 Cytec Canada Inc. Phosphonium and imidazolium salts and methods of their preparation
GB0306432D0 (en) 2003-03-20 2003-04-23 Bp Exploration Operating Process
DE10314203B4 (en) 2003-03-28 2005-10-06 Stockhausen Gmbh Process for the separation of (meth) acrylic acid from a (meth) acrylic acid-containing composition
DE10316418A1 (en) 2003-04-10 2004-10-21 Basf Ag Use an ionic liquid
DE10324300B4 (en) 2003-05-21 2006-06-14 Thomas Dr. Weimer Thermodynamic machine and method for absorbing heat
DE10333546A1 (en) 2003-07-23 2005-02-17 Linde Ag Production of olefins, especially ethylene and propylene, from hydrocarbon feed streams involves steam cracking followed by contact with an ionic liquid to give a paraffin-rich stream and an olefin-rich stream
US20050129598A1 (en) 2003-12-16 2005-06-16 Chevron U.S.A. Inc. CO2 removal from gas using ionic liquid absorbents
DE102004002420A1 (en) 2004-01-16 2005-08-11 Basf Ag Distillation of ionic liquids
US20050164082A1 (en) 2004-01-27 2005-07-28 Takashi Kishi Nonaqueous electrolyte battery
DE102004011427A1 (en) 2004-03-09 2005-09-29 Basf Ag Absorbent with improved oxidation resistance and process for deacidifying fluid streams
DE102004021129A1 (en) 2004-04-29 2005-11-24 Degussa Ag Process for the isolation of highly pure 2-methoxypropene
DE102004024967A1 (en) 2004-05-21 2005-12-08 Basf Ag New absorption media for absorption heat pumps, absorption chillers and heat transformers
US20050285078A1 (en) 2004-06-29 2005-12-29 Minor Barbara H Refrigerant compositions comprising functionalized organic compounds and uses thereof
DE102004053167A1 (en) 2004-11-01 2006-05-04 Degussa Ag Polymeric absorbent for gas absorption and absorption process
FR2877858B1 (en) 2004-11-12 2007-01-12 Inst Francais Du Petrole METHOD FOR DEACIDIFYING A GAS WITH A FRACTIONED REGENERATION ABSORBENT SOLUTION
CN100344380C (en) * 2004-12-08 2007-10-24 北京化工大学 Room temperature ionic liquid and its preparation method
US8715521B2 (en) 2005-02-04 2014-05-06 E I Du Pont De Nemours And Company Absorption cycle utilizing ionic liquid as working fluid
JP2006239516A (en) 2005-03-01 2006-09-14 Shigeo Fujii Absorption liquid composition for removal of volatile organic solvent and process for removal of volatile organic solvent using the same
DE102005013030A1 (en) 2005-03-22 2006-09-28 Bayer Technology Services Gmbh Process for the distillative purification of low-volatile fluids
JP2006282525A (en) 2005-03-31 2006-10-19 Nisshinbo Ind Inc Ionic liquid having benzoic acid derivative as anion
DE102005028451B4 (en) 2005-06-17 2017-02-16 Evonik Degussa Gmbh Method of transporting heat
PE20071048A1 (en) 2005-12-12 2007-10-18 Basf Ag PROCESS FOR THE RECOVERY OF CARBON DIOXIDE
US8506839B2 (en) 2005-12-14 2013-08-13 E I Du Pont De Nemours And Company Absorption cycle utilizing ionic liquids and water as working fluids
FR2895273B1 (en) 2005-12-22 2008-08-08 Inst Francais Du Petrole METHOD FOR DEACIDIFYING A GAS WITH A FRACTIONED REGENERATION ABSORBER SOLUTION WITH CONTROL OF THE WATER CONTENT OF THE SOLUTION
WO2007099041A1 (en) 2006-02-28 2007-09-07 Evonik Degussa Gmbh Working media for cooling processes
FR2898284B1 (en) 2006-03-10 2009-06-05 Inst Francais Du Petrole METHOD FOR DEACIDIFYING GAS BY ABSORBENT SOLUTION WITH HEATED FRACTIONAL REGENERATION.
CN101405146A (en) 2006-03-20 2009-04-08 巴斯夫欧洲公司 Nanoparticulate metal boride composition and its use for identification-marking plastic parts
FR2900842B1 (en) 2006-05-10 2009-01-23 Inst Francais Du Petrole PROCESS FOR DEACIDIFYING A GASEOUS EFFLUENT WITH EXTRACTION OF PRODUCTS TO BE REGENERATED
FR2900843B1 (en) 2006-05-10 2008-07-04 Inst Francais Du Petrole PROCESS FOR DEACIDIFYING GAS WITH PARTIALLY NEUTRALIZED MULTIAMINES
FR2900841B1 (en) 2006-05-10 2008-07-04 Inst Francais Du Petrole PROCESS FOR DEACIDIFYING WITH EXTRACTION OF REACTIVE COMPOUNDS
DE102006031952A1 (en) 2006-07-11 2008-01-17 Goldschmidt Gmbh Use of ionic liquids or solutions of metal salts in ionic liquids as antistatic agents for plastics
DE102006036228A1 (en) 2006-08-03 2008-02-07 Universität Dortmund Process for separating CO2 from gas mixtures
DE102007058320A1 (en) 2006-12-23 2008-06-26 Evonik Degussa Gmbh Membranes for the separation of gases
DE102007034353A1 (en) 2007-07-24 2009-01-29 Evonik Goldschmidt Gmbh Use of ionic liquids for chipless forming of metallic workpieces
EP2022840A3 (en) 2007-08-03 2009-11-25 Evonik Goldschmidt GmbH Use of ionic liquids for lubrication of components in wind farms
DE102007041416A1 (en) 2007-08-31 2009-03-05 Basf Se Distillation of ionic liquids
US20090139232A1 (en) 2007-12-03 2009-06-04 Collis Matthew P Ambient Temperature Energy Generating System
ES2536636T3 (en) 2007-12-12 2015-05-27 Basf Se Procedure for the preparation of disubstituted imidazolium salts
DE102007063149A1 (en) 2007-12-29 2009-07-02 Evonik Goldschmidt Gmbh Novel low melting point imidazolinium salts, process for their preparation and their use as lubricants
EP2087930A1 (en) 2008-02-05 2009-08-12 Evonik Degussa GmbH Method for the absorption of volatile material in a fluid absorption agent
EP2088389B1 (en) 2008-02-05 2017-05-10 Evonik Degussa GmbH Absorption cooling machine
EP2087931A3 (en) 2008-02-05 2011-08-31 Evonik Goldschmidt GmbH Defoaming of ionic fluids
EP2093278A1 (en) 2008-02-05 2009-08-26 Evonik Goldschmidt GmbH Performance additive for improving the sprinkling characteristics of ionic fluids on solid surfaces
WO2009133059A2 (en) 2008-05-02 2009-11-05 Evonik Degussa Gmbh Nanofiber matrices formed from electrospun hyperbranched polymers
US8318117B2 (en) 2008-06-23 2012-11-27 Basf Se Absorption medium and method for removing sour gases from fluid streams, in particular from flue gases
AU2009264389B2 (en) 2008-06-23 2014-05-29 Basf Se Absorption medium and method for removing sour gases from fluid streams, in particular from flue gases
DE102008040193A1 (en) 2008-07-04 2010-01-07 Evonik Röhm Gmbh Process for the preparation of free carboxylic acids
DE102008040415A1 (en) 2008-07-15 2010-01-21 Evonik Röhm Gmbh Thermal salt splitting of ammonium carboxylates
DE102008040486A1 (en) 2008-07-17 2010-01-21 Evonik Goldschmidt Gmbh Use of ionic liquids as additive for cleaning processes in liquefied and / or supercritical gas
FR2934172B1 (en) 2008-07-28 2011-10-28 Inst Francais Du Petrole ABSORBENT SOLUTION BASED ON N, N, N'N'-TETRAMETHYLHEXANE -1,6-DIAMINE AND PROCESS FOR REMOVING ACIDIC COMPOUNDS FROM A GASEOUS EFFLUENT
FR2936165B1 (en) 2008-09-23 2011-04-08 Inst Francais Du Petrole METHOD FOR DEACIDIFYING GAS BY ABSORBENT SOLUTION WITH CONTROL OF HALF
CN102232004A (en) 2008-09-29 2011-11-02 埃克民公司 Process for accelerated capture of carbon dioxide
EP2174700A1 (en) 2008-10-13 2010-04-14 Siemens Aktiengesellschaft Absorbent, method for manufacturing an absorbent and application of an absorbent
FR2938452B1 (en) 2008-11-20 2012-02-03 Inst Francais Du Petrole PROCESS FOR DEACIDIFYING GAS BY ABSORBENT SOLUTION WITH HALF OF DEMIXING DURING REGENERATION
ES2428236T3 (en) 2009-01-29 2013-11-06 Basf Se Absorbent agent containing amino acid and acid promoter for the elimination of acid gases
DE102009000543A1 (en) 2009-02-02 2010-08-12 Evonik Degussa Gmbh Process, absorption media and apparatus for absorbing CO2 from gas mixtures
DE102009009580A1 (en) 2009-02-19 2010-08-26 Evonik Degussa Gmbh Process for the preparation of free acids from their salts
FR2942972B1 (en) 2009-03-10 2012-04-06 Inst Francais Du Petrole METHOD FOR DEACIDIFYING GAS BY ABSORBENT SOLUTION WITH VAPORIZATION AND / OR PURIFICATION OF A FRACTION OF THE REGENERATED ABSORBENT SOLUTION
CN102449101A (en) 2009-03-31 2012-05-09 纳幕尔杜邦公司 Ionic compounds in lithium bromide/water absorption cycle systems
ES2382236T3 (en) 2009-06-05 2012-06-06 Evonik Degussa Gmbh Procedure, absorption medium and device for CO2 absorption from gas mixtures
CN102481513B (en) 2009-06-25 2015-11-25 Vtu控股有限责任公司 For the ionic liquid of gas adsorption and the using method of device
FR2948679B1 (en) 2009-07-28 2011-08-19 Arkema France HEAT TRANSFER METHOD
DE102009047564A1 (en) 2009-12-07 2011-06-09 Evonik Degussa Gmbh Working medium for an absorption chiller
FR2953736B1 (en) 2009-12-16 2012-02-24 Inst Francais Du Petrole PROCESS FOR REMOVING ACIDIC COMPOUNDS FROM A GASEOUS EFFLUENT WITH AN ABSORBENT SOLUTION BASED ON TRIAMINES III / II / III
FR2953735B1 (en) 2009-12-16 2013-03-29 Inst Francais Du Petrole PROCESS FOR REMOVING ACIDIC COMPOUNDS FROM A GASEOUS EFFLUENT WITH AN ABSORBENT SOLUTION BASED ON DIAMINS I, II / III
WO2011076625A1 (en) 2009-12-23 2011-06-30 Evonik Degussa Gmbh Sweetener and method for the production thereof
DE102010004779A1 (en) 2010-01-14 2011-07-21 Heym, Florian, 95444 Drying gas, comprises contacting gas containing water vapor with an ionic liquid, which absorbs the water vapor of gas
DE102010001070A1 (en) 2010-01-21 2011-07-28 Evonik Goldschmidt GmbH, 45127 Lubricant composition, useful to reduce friction between moving surfaces e.g. metallic surface, standing in contact with each part, comprises ionic liquids, phosphoric acid esters, and optionally solvents, and additives e.g. bactericides
US8318114B2 (en) 2010-04-16 2012-11-27 Nalco Company Composition for treating acid gas
EP2380941A1 (en) 2010-04-20 2011-10-26 Evonik Degussa GmbH Absorption heat pump with absorption agent comprising a lithium chloride and an organic salt with the same anion
EP2380940A1 (en) 2010-04-20 2011-10-26 Evonik Degussa GmbH Absorption heat pump with absorption agent comprising lithium chloride and an organic chloride salt
CN102335545B (en) 2010-07-22 2013-11-06 中国科学院理化技术研究所 Dehumidifying agent for air dehumidification, method and device for air dehumidification
KR101404833B1 (en) 2010-11-08 2014-06-09 에보니크 데구사 게엠베하 Working medium for absorption heat pumps
DE102011077377A1 (en) 2010-11-12 2012-05-16 Evonik Degussa Gmbh Process for the absorption of acid gases from gas mixtures
WO2012110987A1 (en) 2011-02-19 2012-08-23 Devendra Purohit Environmental energy conversion device
DE102011100772A1 (en) 2011-05-05 2012-11-08 Evonik Degussa Gmbh Process for the preparation of isomaltulose from plant juices
EP2532414A1 (en) 2011-06-10 2012-12-12 Evonik Degussa GmbH Method for absorbing CO2 from a gas mixture
EP2532412A1 (en) 2011-06-10 2012-12-12 Evonik Degussa GmbH Absorption medium and method for absorbing an acidic gas from a gas mixture
EP2532413A1 (en) 2011-06-10 2012-12-12 Evonik Degussa GmbH Method for absorbing CO2 from a gas mixture
JP2013051238A (en) 2011-08-30 2013-03-14 Sanyo Chem Ind Ltd Electrolyte for aluminum electrolytic capacitor, and aluminum electrolytic capacitor including the same
DE102011083030A1 (en) 2011-09-20 2013-03-21 Evonik Degussa Gmbh Mixture composition and its use as a sweetener
DE102011083974A1 (en) 2011-10-04 2013-04-04 Evonik Degussa Gmbh Working medium for absorption heat pumps
DE102011083976A1 (en) 2011-10-04 2013-04-04 Evonik Degussa Gmbh Sorbent for absorption heat pumps
MX2014005746A (en) 2011-11-14 2014-07-09 Evonik Degussa Gmbh Method and device for the separation of acidic gases from a gas mixture.
US8783035B2 (en) 2011-11-15 2014-07-22 Shell Oil Company System and process for generation of electrical power
DE102011055859A1 (en) 2011-11-30 2013-06-06 Universität Rostock Sulfur-free transition metal isocyanate-based ionic liquids
DE102012200566A1 (en) 2012-01-16 2013-07-18 Evonik Degussa Gmbh Method for absorbing CO2 from a gas mixture
DE102012200907A1 (en) 2012-01-23 2013-07-25 Evonik Industries Ag Method and absorption medium for absorbing CO2 from a gas mixture
DE102012202193A1 (en) 2012-02-14 2013-08-14 Evonik Degussa Gmbh pH-adjusted sweetener
EP2636715B1 (en) 2012-03-08 2016-06-29 Evonik Degussa GmbH Working fluid for absorption heat pumps
DE102012207509A1 (en) 2012-05-07 2013-11-07 Evonik Degussa Gmbh Method for absorbing CO2 from a gas mixture
DE102012211323A1 (en) 2012-06-29 2014-01-02 Evonik Industries Ag Hardener for epoxy resin systems and their use
EP2735820A1 (en) 2012-11-21 2014-05-28 Evonik Industries AG Absorption heat pump, and absorption agent for an absorption heat pump comprising methanesulfonic acid
DE102012222157A1 (en) 2012-12-04 2014-06-05 Evonik Industries Ag Method for absorbing CO2 from a gas mixture
DE102013010035A1 (en) 2013-06-17 2014-12-18 Evonik Degussa Gmbh Absorption medium and method for absorbing CO2 from a gas mixture
DE102013212805A1 (en) 2013-07-01 2015-01-08 Evonik Industries Ag Use of highly efficient working media for heat engines
KR102071269B1 (en) 2013-07-17 2020-01-30 엔티에이치 디그리 테크놀로지스 월드와이드 인코포레이티드 Printed silver oxide batteries
DE102013226613A1 (en) 2013-12-19 2015-06-25 Evonik Industries Ag Processing-friendly dianhydride hardener for epoxy resin systems based on 5,5'-oxybis (isobenzofuran-1,3-dione)
DE102013226601A1 (en) 2013-12-19 2015-06-25 Evonik Industries Ag Processing-friendly dianhydride hardener for epoxy resin systems based on 5,5'-carbonylbis (isobenzofuran-1,3-dione)
GB2528494B (en) 2014-07-24 2018-01-03 Worn Again Footwear And Accessories Ltd Process for extracting polyester and dyes from fabric
DE102014214682A1 (en) 2014-07-25 2016-01-28 Evonik Degussa Gmbh Simplified method for the synthesis of heterocycles
DE102014214670A1 (en) 2014-07-25 2016-01-28 Evonik Degussa Gmbh Simplified method for the synthesis of heterocycles
DE102014214674A1 (en) 2014-07-25 2016-01-28 Evonik Degussa Gmbh Process for the preparation of substituted imidazolium salts
DE102014226441A1 (en) 2014-12-18 2016-06-23 Evonik Degussa Gmbh Process for cleaning an ionic liquid and method for dehumidifying air
DE102015212749A1 (en) 2015-07-08 2017-01-12 Evonik Degussa Gmbh Method for dehumidifying moist gas mixtures
DE102016210481B3 (en) 2016-06-14 2017-06-08 Evonik Degussa Gmbh Process for purifying an ionic liquid

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10500540B2 (en) 2015-07-08 2019-12-10 Evonik Degussa Gmbh Method for dehumidifying humid gas mixtures using ionic liquids
US10105644B2 (en) 2016-06-14 2018-10-23 Evonik Degussa Gmbh Process and absorbent for dehumidifying moist gas mixtures
US10138209B2 (en) 2016-06-14 2018-11-27 Evonik Degussa Gmbh Process for purifying an ionic liquid
US10493400B2 (en) 2016-06-14 2019-12-03 Evonik Degussa Gmbh Process for dehumidifying moist gas mixtures
US10512883B2 (en) 2016-06-14 2019-12-24 Evonik Degussa Gmbh Process for dehumidifying moist gas mixtures
US10512881B2 (en) 2016-06-14 2019-12-24 Evonik Degussa Gmbh Process for dehumidifying moist gas mixtures

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