EP2051788A1 - Procédé d'extraction utilisant un liquide ionique - Google Patents

Procédé d'extraction utilisant un liquide ionique

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Publication number
EP2051788A1
EP2051788A1 EP07814141A EP07814141A EP2051788A1 EP 2051788 A1 EP2051788 A1 EP 2051788A1 EP 07814141 A EP07814141 A EP 07814141A EP 07814141 A EP07814141 A EP 07814141A EP 2051788 A1 EP2051788 A1 EP 2051788A1
Authority
EP
European Patent Office
Prior art keywords
cycloalkane
separation
ionic liquid
cycloalkanone
cycloalkanol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07814141A
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German (de)
English (en)
Inventor
Keith Whiston
Kenneth Richard Seddon
Stewart Alexander Forsyth
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Invista Technologies Sarl
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Invista Technologies SARL Switzerland
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Filing date
Publication date
Application filed by Invista Technologies SARL Switzerland filed Critical Invista Technologies SARL Switzerland
Publication of EP2051788A1 publication Critical patent/EP2051788A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0492—Applications, solvents used
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/86—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/125—Monohydroxylic acyclic alcohols containing five to twenty-two carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to the separation of alcohols and ketones in a mixture with a non-polar solvent, such as an alkane, using an ionic liquid.
  • the invention particularly relates to the separation of cycloalkanols, cycloalkanones and cycloalkanes.
  • the oxidation of cyclohexane and subsequent separation of a mixture of cyclohexanone and cyclohexanol from unreacted cyclohexane is a key step in the manufacture of both adipic acid and caprolactam.
  • the primary industrial use of caprolactam is as a monomer in the production of nylon-6.
  • Adipic acid is a monomer used in the production of nylon-6,6 amongst other applications.
  • the oxidation of cyclohexane is carried out at a relatively low conversion of less than 10%.
  • the primary oxidation products of cyclohexane are cyclohexane hydroperoxide, cyclohexanol and cyclohexanone.
  • cyclohexyl hydroperoxide is then decomposed to cyclohexanol and cyclohexanone, either in the reactor or in a separate unit operation. This process as a whole can be described for the purposes of the present invention as the cyclohexane oxidation process.
  • the desired final oxidation product after decomposition of cyclohexyl hydroperoxide is a mixture of primarily cyclohexanone and cyclohexanol.
  • the mixture must then be separated from the unreacted cyclohexane whereby the unreacted cyclohexane can then typically be recycled to the oxidation reaction.
  • caprolactam requires cyclohexanone as a starting material that is substantially free of cyclohexanol.
  • this level of purity is achieved commercially through distillation, which again is an energy intensive process.
  • Liquid-liquid or solvent separation also known as liquid-liquid or solvent extraction processes are well known in the art as processes for the separation of components of a mixture.
  • Liquid-liquid separation is based on the transfer of component(s) from one liquid phase into another liquid phase and is used to separate component(s) selectively from a mixture.
  • Mixing two immiscible liquids leads to a phase separation, and the formation of two liquid layers, also known as phases or fractions. The less dense liquid will form the upper layer, and the more dense liquid will form the lower layer.
  • Liquid-liquid separation relies on the different relative solubilities of a component in two immiscible liquids.
  • liquid- liquid separation utilises a water-based, or aqueous, phase and an organic phase (comprising an organic solvent) that is substantially immiscible in water.
  • an organic phase comprising an organic solvent
  • the aqueous phase and the organic phase are mixed with, for example, an aqueous solution of two separable components, if one of the separable components is more soluble in the organic phase it will be separated and become dissolved in the organic phase.
  • Liquid- liquid separation can be a powerful technique provided suitable liquids are used.
  • the traditional aqueous phase / organic phase separation would not be possible for the separation of a cycloalkanol and a cycloalkanone from a cycloalkane because all three of these components would dissolve more readily in the organic phase.
  • Liquid-liquid extraction technology can also be carried out using two organic phases which are substantially immiscible with each other and in one of which the solubility of the component to be extracted is much greater than the other.
  • a disadvantage of liquid-liquid extraction technology is that final recovery of the components extracted from the initial mixture can be complicated by the volatility of the extracting solvent. Typically final recovery of the components of interest is earned out by distillation, but often the extracting solvent is of comparable volatility to the desired product. Therefore, recovery of the component of interest can be very difficult, and process may also be energy intensive in terms of steam requirements. It is a feature of the present invention that such limitations are avoided by the use of Ionic Liquid(s) as the extracting solvent.
  • Ionic Liquids are substantially non-volatile, they do not interfere with the recovery of the component of interest during final recovery. Recovery of said component may, therefore, be effected by simple flash recovery without the need for complicated separation technology with a corresponding reduction in energy (e.g., steam) requirements.
  • caprolactam manufacture requires only cyclohexanone as a starting material.
  • this separation is carried out by distillation wherein the separation of cyclohexanone from cyclohexanol requires significant energy and a high capital investment in the distillation column required.
  • Liquid-liquid extraction technology is not conventionally used for the separation of cyclohexanone and cyclohexanol since, for this application, it is a requirement of the extraction solvent that it selectively removes one component only from the mixture.
  • Conventional solvents which are suitable for use in a solvent extraction process will not selectively extract cyclohexanol from cyclohexanone.
  • a distribution coefficient for a given separable component can be quoted as a measure of the extent to which a separable component is separated.
  • the distribution coefficient is equal to the concentration of the separable component in the organic-based phase divided by the concentration of the separable component in the aqueous phase.
  • the distribution coefficient can be a function of a number of different parameters e.g. temperature.
  • the object of the present invention is to provide an improved method for the separation of an alcohol from a ketone in a mixture of these compounds in a non-polar solvent, and for the separation of an alcohol and/or a ketone from a non-polar solvent. It is a particular object of this invention to provide an improved method for the separation of a cycloalkanol from a cycloalkanone in a mixture of these compounds in a non-polar solvent (such as a cycloalkane), and for the separation of a cycloalkanol and/or a cycloalkanone from a non-polar solvent (such as a cycloalkane).
  • a non-polar solvent such as a cycloalkane
  • alcohol encompasses acyclic and cyclic aliphatic alcohols, and in one embodiment refers to an (alkyl-OH) group, and in an alternative embodiment to a (cycloalkyl-OH) group, i.e. a "cycloalkanol”.
  • alkane refers to (alkyl-H) and the term “cycloalkane” refers to (cycloalkyl-H).
  • alkyl refers to a straight-chain or branched-chain saturated monovalent hydrocarbon radical, and particularly one having from 1 to 20 carbon atoms.
  • suitable alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, dodecyl and eicosyl.
  • Said alkyl groups may be substituted by one or more halogen atoms, the same or different, but are preferably unsubstituted.
  • cycloalkyl refers to a cyclic saturated monovalent hydrocarbon radical, having 3-20 carbon atoms.
  • suitable cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclododecyl.
  • the cycloalkyl groups contain from 5 to 12 carbon atoms.
  • Said cycloalkyl groups may be substituted by one or more halogen atoms, the same or different, but are preferably unsubstituted.
  • non-polar solvent refers to a compound which is immiscible with an ionic liquid.
  • non-polar solvent refers to a solvent which has a dielectric constant of no more than 5, preferably no more than 3.0, more preferably no more than 2.5, measured at 20 0 C and atmospheric pressure according to ASTM D924-92.
  • non-polar solvent refers to cyclic and acyclic aliphatic hydrocarbons, and particularly cyclic and acyclic saturated aliphatic hydrocarbons, i.e.
  • alkanes and cycloalkanes such as pentanes, hexanes, heptanes, octanes and cyclohexane etc.
  • Said non-polar aliphatic hydrocarbons may be substituted by one or more halogen atoms, the same or different, but are preferably unsubstituted.
  • said alcohol contains a number of carbon atoms which may be different to, but is preferably the same as, the number of carbon atoms in the ketone and/or alkane present in the mixture to be separated
  • said ketone has a number of carbon atoms which may be different to, but is preferably the same as, the number of carbon atoms in the alcohol and/or the alkane present in the mixture to be separated.
  • said cycloalkanol contains a number of carbon atoms which may be different to, but is preferably the same as, the number of carbon atoms in the cycloalkanone and/or cycloalkane present in the mixture to be separated
  • said cycloalkanone has a number of carbon atoms which may be different to, but is preferably the same as, the number of carbon atoms in the cycloalkanol and/or the cycloalkane present in the mixture to be separated.
  • the invention encompasses:
  • said alcohol and said ketone may themselves have different numbers of carbon atoms to each other, but typically they will have the same number of carbon atoms.
  • a method for the use of at least one ionic liquid for the separation of an alcohol and/or ketone from a non- polar solvent, or for the separation of an alcohol from a ketone in a mixture of these compounds in a non-polar solvent particularly when said alcohol is a cycloalkanol and said ketone is a cycloalkanone, and particularly when said alcohol is a cycloalkanol and said ketone is a cycloalkanone and said non-polar solvent is a cycloalkane.
  • the cycloalkyl groups contain 6 carbon atoms, in which case the separation process described herein is particularly concerned with the separation of a cyclohexanol and/or a cyclohexanone from a cyclohexane, and with the separation of a cyclohexanol from a cyclohexanone and a cyclohexane.
  • the cycloalkyl groups contain 12 carbon atoms, in which case the separation process described herein is particularly concerned with the separation of a cyclododecanol and/or a cyclododecanone from a cyclododecane, and with the separation of a cyclododecanol from a cyclododecanone and a cyclododecane.
  • the mixture to be separated can therefore comprise, for instance, a cycloalkanol and a cycloalkane; or a cycloalkanone and a cycloalkane; or a cycloalkanol and a cycloalkanone and a cycloalkane.
  • the process of the present invention involves a liquid-liquid separation wherein one of the liquid phases is an ionic liquid-based phase and the other is a non-polar solvent phase, such as an organic hydrocarbon-based phase, that is substantially immiscible in the ionic liquid-based phase.
  • a non-polar solvent phase such as an organic hydrocarbon-based phase
  • substantially immiscible is intended to mean immiscible to the extent that two separate phases are formed.
  • the process of the present invention thus relies upon the different relative solubility/solubilities of the component/components to be separated, i.e. the separable component(s), in the ionic liquid-based phase and the non-polar solvent phase.
  • a separable component will partition itself between the ionic liquid-based phase and the non-polar solvent phase in such a way that more of the or each separable component will be dissolved in the ionic liquid-based phase.
  • the ionic liquid(s) and the mixture comprising an alcohol and/or a ketone in a non-polar solvent is referred to herein as the "separation mixture”.
  • the term "contacting" is intended to mean the bringing together of the ionic liquid(s) with said mixture comprising an alcohol and/or a ketone in a non-polar solvent to form the separation mixture.
  • the ionic liquid(s) and said mixture comprising an alcohol and/or a ketone in a non-polar solvent can be contacted in a container (i.e., reaction vessel) that is suitable for said contact.
  • the separation mixture is shaken, mixed or stirred vigorously for a period of time, hereinafter referred to as the contacting time, to allow thorough dispersion of the ionic liquid(s) throughout said mixture comprising an alcohol and/or a ketone in a non-polar solvent.
  • the contacting time is too short, the ionic liquid(s) will not be fully dispersed throughout said mixture comprising an alcohol and/or a ketone in a non-polar solvent, and separation of the separable component(s) will be inefficient, i.e. only a small proportion of the separable component(s) present in the separation mixture will be separated.
  • the contacting time of the separation mixture will increase the dispersion of the ionic liquid(s) and said mixture comprising an alcohol and/or a ketone in a non-polar solvent, and the efficiency of the separation will be increased, i.e. a larger proportion of the separable component(s) in the separation mixture will be separated.
  • This increase of separation efficiency with contacting time will occur until a maximum possible proportion of the total volume of separable component(s) has been separated for the separation conditions used (e.g. type of ionic liquid, temperature etc) i.e. maximum separation has been obtained.
  • the contacting time is preferably greater than 30 seconds, more preferably greater than 60 seconds and typically not greater than 5 minutes, although longer times periods may be used with satisfactory results.
  • the separation mixture is allowed to settle for another period of time, hereinafter referred to as the "settling time".
  • the separation mixture will separate into an ionic-liquid based phase and a non-polar solvent-based phase.
  • the settling time should be long enough to allow the ionic liquid-based phase and the non-polar solvent-based phase to fully separate, at which point the system is described as being in equilibrium.
  • the settling time is preferably longer than 1 minute, more preferably longer than 2 minutes and typically no longer than 10 minutes, although longer times periods may be used with satisfactory results.
  • the mixture comprising an alcohol and/or a ketone in a non-polar solvent, and particularly at least one of a cycloalkanol and a cycloalkanone in a cycloalkane may be formed by an oxidation step preceding the separation process.
  • the oxidation step may be, but is not limited to, oxidation with air alone or in the presence of a cobalt or other transition metal catalyst followed by decomposition of the resulting cyclohexyl hydroperoxide, either thermally or through other catalytic means.
  • an oxidation step followed by a cyclohexyl hydroperoxide decomposition step followed by a separation, or contacting, step is defined as one oxidation and separation cycle.
  • a plurality of oxidation and separation cycles can be carried out.
  • a cycloalkane-based phase or fraction resulting from the separation may be recycled for further oxidation.
  • the ionic liquid-based phase can be physically separated from the non-polar solvent-based phase.
  • This physical separation can be earned out using any suitable apparatus
  • the separable component(s) e.g. a cycloalkanol and/or a cycloalkanone, can be removed from the ionic liquid-based phase and said ionic liquid(s) can be recycled and re-used, for example, in a further separation step.
  • Stage-wise operations typically involve a mixing step followed by a phase separation, or settling, step in devices generally known as mixer-settlers. Operations can be carried out in sequential batch fashion, in which case it is common for the same vessel to serve alternating functions of mixing and settling. Operations can also be carried out with continuous flow, for which the mixing and settling steps are usually, but not always performed in separate vessels. In continuous flow systems the necessary mixing time and settling time are obtained by proper sizing of equipment volume or holdup.
  • Examples of commercial mixing equipment known to those skilled in the art includes in-line static mixers, jet mixers, injectors, orifices or mixing nozzles, valves, centrifugal pumps, agitated line mixers, packed tubes, mechanically agitated vessels, gas or vapor agitated vessels, and vessels with circulating flow loops.
  • Examples of commercial settling equipment known to those skilled in the art includes gravity settlers, decanters, centrifugal cyclones, centrifuges, and settler auxiliaries such as coalescers, separating membranes, and electrical field devices (for electrically conducting emulsions or dispersions). Any type of mixer and settler can be combined to produce a stage. Stages can be arranged in a multi-stage cascade to achieve additional separation efficiency. Multi-stage arrangements can employ a variety of liquid flow schemes such as counter-current flow, co-current flow, cross-current flow, staged-flow, and so forth. Compact equipment consisting of alternative mixing and settling elements can be constructed.
  • Continuous (differential) contacting equipment is usually arranged for multistage counter-current contact of insoluble liquids without repeated complete separation of the liquids from each other between stages. However it may also be arranged co- current or cross current. The liquids remain in continuous contact with each other throughout the equipment. Counter-current flow is maintained by differences in densities of the liquids in conjunction with gravity or centrifugal force.
  • gravity-operated extractors such as spray towers, packed towers, or sieve tray towers
  • gravity-operated extractors with mechanical agitation such as towers with rotating stirrers, rotary-disk contactors, Mixco (Oldshue-Rushton) multiple-mixer columns, Scheibel columns, Kuhni contactor columns, liquid pulsed towers, and reciprocating plate columns
  • centrifugal extractors such as spray towers, packed towers, or sieve tray towers
  • gravity-operated extractors with mechanical agitation such as towers with rotating stirrers, rotary-disk contactors, Mixco (Oldshue-Rushton) multiple-mixer columns, Scheibel columns, Kuhni contactor columns, liquid pulsed towers, and reciprocating plate columns
  • centrifugal extractors such as spray towers, packed towers, or sieve tray towers
  • gravity-operated extractors with mechanical agitation such as towers with rotating stirrers, rotary-
  • the separation process of the present invention may form one or more separation steps in the manufacture of adipic acid or caprolactam.
  • the separation steps of these processes have traditionally been performed by distillation.
  • the separable component is a cycloalkanone which is separated from a cycloalkane.
  • the ionic liquid(s) is contacted with a mixture of the cycloalkanone and the cycloalkane.
  • the ionic liquid(s) and the mixture of the cycloalkanone and the cycloalkane is known as separation mixture (a).
  • the process of this embodiment involves a liquid-liquid separation wherein one of the liquid phases is an ionic liquid-based phase and the other is a cycloalkane-based phase that is substantially immiscible in the ionic liquid-based phase.
  • the distribution coefficient of the cycloalkanone between the ionic liquid-based phase and the cycloalkane-based phase is greater than 1.5 and preferably greater than 3.
  • the separable component is a cycloalkanol which is separated from a cycloalkane.
  • the ionic liquid(s) is contacted with a mixture of the cycloalkanol and the cycloalkane.
  • the ionic liquid(s) and the mixture of the cycloalkanol and the cycloalkane is known as separation mixture (b).
  • the process of this embodiment involves a liquid-liquid separation wherein one of the liquid phases is an ionic liquid-based phase and the other is a cycloalkane-based phase that is substantially immiscible in the ionic liquid-based phase.
  • the distribution coefficient of the cycloalkanol between the ionic liquid-based phase and the cycloalkane-based phase is greater than 1.5 and preferably greater than 3.
  • the separable component is a cycloalkanol which is separated from a mixture of a cycloalkanone and a cycloalkane.
  • the ionic liquid(s) is contacted with a mixture of the cycloalkanol, the cycloalkanone and the cycloalkane.
  • the ionic liquid(s) and the mixture of the cycloalkanol, the cycloalkanone and the cycloalkane is known as separation mixture (c).
  • the process of this embodiment involves a liquid-liquid separation wherein one of the liquid phases is an ionic liquid- based phase, and the other liquid phase is a cycloalkane-based phase that is substantially immiscible in the ionic liquid-based phase.
  • the separation of a cycloalkanol from a cycloalkanone and a cycloalkane according to the process in this embodiment can be achieved when the distribution coefficient for the cycloalkanol between the ionic liquid- based phase and the cycloalkane- -based phase is greater than 1, and the distribution coefficient for the cycloalkanone between the ionic liquid-based phase and the cycloalkane-based phase is less than 1.
  • This embodiment has application to the separation of cyclohexanol from cyclohexanone for caprolactam manufacture.
  • the distribution coefficient of the cycloalkanol between the ionic liquid- based phase and the cycloalkane-based is greater than 1.5 and preferably greater than 3.
  • the separable components are a mixture of a cycloalkanone and a cycloalkanol which are separated from a cycloalkane.
  • the ionic liquid(s) is contacted with a mixture of the cycloalkanol, the cycloalkanone and the cycloalkane.
  • the ionic liquid(s) and the mixture of the cycloalkanol, the cycloalkanone and the cycloalkane is known as separation mixture (d).
  • the process of this embodiment involves a liquid-liquid separation wherein one of the liquid phases is an ionic liquid-based phase and the other is a cycloalkane-based phase that is substantially immiscible in the ionic liquid-based phase.
  • the distribution coefficient of the cycloalkanol and the cycloalkanone between the ionic liquid-based phase and the cycloalkane-based phase is greater than 1.5 and preferably greater than 3.
  • the mixtures to be separated may also contain materials other than the cycloalkanol, cycloalkanone and cycloalkane components.
  • these other materials will either remain in the cycloalkane-based phase or be separated into the ionic liquid-based phase along with the separable component.
  • cyclohexylhydroperoxide (CHHP) may be present in the separation mixture of cyclohexanol, cyclohexanone and cyclohexane. In these circumstances, CHHP would be separated with the cyclohexanol and/or cyclohexanone into the ionic liquid-based phase.
  • ionic liquid(s) of the present invention may consist of a single ionic liquid or a mixture of two or more ionic liquids, i.e. a mixture of 2, 3, 4, 5, 6 etc different ionic liquids. Typically, one or two, and typically only one ionic liquid is used.
  • the ionic liquid(s) comprises a cation selected from one or more of 1- alkylpyridinium, alkyl- or poly-alkylpyridinium, phosphonium (PR 4 + ), alkyl- or polyalkylphosphonium, imidazolium, alkyl- or polyalkylimidazolium, ammonium (NR 4 + ), alkyl- or polyalkylammonium, alkyl- or polyalkylpyrazolium, alkyl- or polyalkylpyrrolidinium, alkyl or polyalkylazepinium, alkyloxonium or alkysulfonium.
  • a cation selected from one or more of 1- alkylpyridinium, alkyl- or poly-alkylpyridinium, phosphonium (PR 4 + ), alkyl- or polyalkylphosphonium, imidazolium, alkyl- or polyalkylimidazolium, ammonium (NR 4 +
  • Each R group of the phosphonium and ammonium cations may be separately selected from the group of substituents consisting of hydrogen, hydroxyl, alkyl, alkyl ethers, alkyl esters, alkyl amides, alkyl carboxylic acids, or sulfonate.
  • the ionic liquid(s) comprises a cation selected from one or more of 1-alkylpyridinium, alkyl- or poly-alkylpyridinium, imidazolium, alkyl- or polyalkylimidazolium.
  • the cations of each of the ionic liquids present in the mixture may be the same or different.
  • the anion of the ionic liquid(s) is selected from one or more of a halide, preferably chloride, bromide or iodide, a nitrate, an alkylsulfate or alkyl polyalkoxysulfate, such as methanesulfonate, trifluoromethanesulfonate and hydrogensulfonate, anions based on nitrogen, phosphorous, boron, silicon, selenium, tellurium, halogens, and oxoanions of metals.
  • a halide preferably chloride, bromide or iodide
  • a nitrate such as methanesulfonate, trifluoromethanesulfonate and hydrogensulfonate
  • anions based on nitrogen, phosphorous, boron, silicon, selenium, tellurium, halogens, and oxoanions of metals preferably one or more of a halide, preferably chlor
  • Suitable anions include, but are not limited to bis(trifluoromethylsulfonyl)amide (NTf 2 " ), tetrafluoroborate (BF 4 " ), trifluoromethylsulfonyl (Tf), methoxyethylsulfonate, 2-methoxyethylsulfonate, ethoxyethylsulfonate, 2-ethoxyethylsulfonate, (methoxypropoxy)propylsulfonate, 1-(1- methoxypropoxy)-propylsulfonate, (methoxyethoxy)-ethylsulfonate, 1-(1- methoxyethoxy)-ethylsulfonate, methyl (diethoxy)ethylsulfonate, 1- methyl(diethoxy)ethylsulfonate, carboxylate, formate, acetate, dicyanimide and trifluoromethanesul
  • the anion of the ionic liquid(s) is selected from one or more of an alkylsulfate or alkyl polyalkoxysulfate, bis(trifluoromethylsulfonyl)amide (NTf 2 " ) and tetrafluoroborate (BF 4 " ).
  • the anion of each of the ionic liquids present in the mixture may be the same or different.
  • the ionic liquid(s) will comprise at least one C 2 - C 6 alkyl group.
  • the C 2 - C 6 alkyl group may be a substituent on either the anion or the cation of the ionic liquid(s). More preferably the C 2 - C 6 alkyl group is a substituent on the cation of the ionic liquid(s).
  • the ionic liquid(s) consists of a single ionic liquid
  • the single ionic liquid present preferably contains at least one C 2 - C 6 alkyl group substituent.
  • the ionic liquid(s) consists of two or more ionic liquids
  • at least one of the ionic liquids present contains at least one C 2 - C 6 alkyl group substituent
  • more preferably two or more of the ionic liquids present contain at least one C 2 - C 6 alkyl group substituent, i.e. 2, 3, 4, 5 etc of the ionic liquids present contain at least one C 2 - C 6 alkyl group substituent.
  • all the ionic liquids present in the at least on ionic liquid contain at least one C 2 - C 6 alkyl group substituent.
  • the ionic liquid(s) of the present invention is preferably selected from the group consisting of N-ethylpyridinium bis(trifluoromethanesulfonyl)amide;
  • N-Methyl-N'-butylimidazolium bromide N-Methyl-N'-butylimidazolium 2-ethoxyethylsulfonate;
  • the ionic liquid(s) is N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)amide or N-Methyl-N'-butylimidazolium 1-(1- methoxypropoxy)-propylsulfonate.
  • Ionic liquids most suitable for the separation of an alcohol from a non-polar solvent are:
  • Ionic liquids most suitable for the separation of an alcohol from a mixture of a non-polar solvent and a ketone, particularly wherein said alcohol is a cycloalkanol
  • Ionic liquids most suitable for the separation of a ketone from a non-polar solvent are: N-ethylpyridinium bis(trifluoromethanesulfonyl)amide;
  • Ionic liquids most suitable for the separation of a mixture of an alcohol and a ketone from a non-polar solvent particularly when said alcohol is a cycloalkanol (and particularly cyclohexanol) and said ketone is a cycloalkanone (particularly cyclohexanone) and said non-polar solvent is a cycloalkane (particularly a cyclohexane) are:
  • ionic liquid refers to an ionic compound which is liquid below 100 0 C.
  • the term "distribution coefficient" referring to the liquid-liquid separation refers to the concentration of the separable component in the ionic liquid- based phase divided by the concentration of the separable component in the non-polar solvent-based phase. These concentrations are measured subsequent to settling, i.e. when the separation mixture has reached equilibrium subsequent to the vigorous shaking.
  • the present invention is exemplified through separation of cyclohexanol and cyclohexanone from cyclohexane using a general method followed by calculation of the resulting distribution coefficient.
  • equal volumes of cyclohexane and ionic liquid have been used.
  • the volume of ionic liquid used would preferably be a small fraction of the volume of cyclohexane.
  • the distribution coefficient is independent of volume, the data obtained for equivolume experiments will be relevant to industrial application in which the volumes of ionic liquid and cyclohexane may not be equivalent.
  • the general method used for all the examples was as follows.
  • Hnmr Hydrophilicity-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl
  • Table 1 details the results of the specific examples with comparisons to water and DMSO (dimethyl sulfoxide), where D is the distribution coefficient.

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

Abstract

Procédé de séparation d'un alcool d'un solvant non polaire; d'une cétone d'un solvant non polaire; d'un alcool d'un mélange d'une cétone et d'un solvant non polaire; ou d'un mélange d'un alcool et d'une cétone d'un solvant non polaire; ledit procédé comprenant la mise en contact d'au moins un liquide ionique avec un mélange comprenant un solvant non polaire et au moins un parmi un alcool et une cétone.
EP07814141A 2006-08-18 2007-08-16 Procédé d'extraction utilisant un liquide ionique Withdrawn EP2051788A1 (fr)

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RU2492161C2 (ru) * 2008-05-26 2013-09-10 Мерк Патент Гмбх Применение ионных жидкостей с анионами тетрацианобората в качестве растворителя для экстракции спиртов из водных растворов
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US6320083B1 (en) * 1998-09-10 2001-11-20 Exxonmobil Chemical Co. Process for making aromatic aldehydes using ionic liquids
WO2002074718A2 (fr) * 2001-03-20 2002-09-26 Basf Aktiengesellschaft Liquides ioniques comme additifs selectifs pour la separation de melanges azeotropiques a plage d'ebullition etroite
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EP1797953B1 (fr) * 2004-07-20 2011-01-05 Sumitomo Chemical Company, Limited Procede pour la preparation de 4-azasteroides
FR2875235B1 (fr) * 2004-09-10 2006-11-24 Inst Francais Du Petrole Procede de separation des composes oxygenes contenus dans une charge hydrocarbonee, mettant en oeuvre un liquide ionique
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TW200815339A (en) 2008-04-01
KR101474209B1 (ko) 2014-12-17
WO2008022233A1 (fr) 2008-02-21
KR20140130241A (ko) 2014-11-07
KR20090057389A (ko) 2009-06-05

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