TW200815339A - Extraction process - Google Patents

Abstract

A process for the separation of an alcohol from a non-polar solvent; a ketone from a non-polar solvent; an alcohol from a mixture of a ketone and a non-polar solvent; or a mixture of an alcohol and a ketone from a non-polar solvent; said process comprising contacting at least one ionic liquid with a mixture comprising a non-polar solvent and at least one of an alcohol and a ketone.

Description

200815339 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to the separation of alcohols and ketones using an ionic liquid in a mixed liquid having a non-polar solvent such as a hydrocarbon. The present invention is related to the separation of alcohols, cycloalkanones and naphthenes.衣坑 [Prior Art] The oxidation of the ring hexagram and the subsequent separation of the mixture of cyclohexanyl and cyclohexanol and the reaction of the hexyl hexanolate into adipic acid and caprolactam are reversed. The main industrial use of caprolactam is as a slave to manufacture. In addition to other applications, adipic acid is used in the manufacture of monomers resistant to _6,6. . Oxidation of cyclohexene is known to be less than 10% of the relatively low conversion of cyclohexanyl to the main oxidation product of chloroperoxide cyclohexanol, cyclohexanol cut into the commercial ring enthalpy oxidation method, and then in the reaction ... _ . In the early stage, the hydroperoxide ring group was decomposed into cyclohexanol and cyclohexene. The method was generally described as a cyclohexane oxidation method. Bifurcation of cyclohexyl hydroperoxide The desired final oxidation product after cleavage is mainly a mixture of hexanone and cyclohexanol. The separator must be separated from the unreacted cyclohexane of the mixture, so that the cyclohexane is usually recycled to the oxidation reaction, and is carried out by After the "bad", the process is used in a high proportion of process steam.

OOH

〇 ^ 123833.doc 200815339 Therefore, there is a need for alternative separation techniques that reduce steam use and thereby reduce the large amount of energy associated with separation via base distillation. In addition, the use of cyclohexanone which is substantially free of cyclohexanol is used as a starting material for the manufacture of caprolactam. Currently, business,! This level of purity is achieved by steaming, which is also an energy intensive method.

〇 + separation

—^

Liquid-liquid or solvent separation (also known as liquid-liquid or solvent extraction) methods are well known in the art as methods for separating components of a mixture. The liquid-liquid fractionation is based on the transfer of the components from the liquid phase to the other liquid phase and is used to selectively separate the components from the mixture. Two immiscible

The mixing of the liquid of U results in phase separation and the formation of two layers of liquid (also referred to as phases or portions). The lower density liquid will form the upper layer, while the higher density liquid will form the lower relative solubility of the lower ["body-liquid separation dependent component in the two unpleasant liquids. In particular, if the soluble component is capable of: freely mixing with two immiscible liquids, it will dissolve between the two liquid phases thus formed, such that the component will generally be compared to one The liquid phase and the more soluble solubility are dissolved in the other liquid phase. In general, liquid-liquid separation employs a water-based (or aqueous) phase and an organic phase (including an organic solvent) that is substantially immiscible in water. In this case, when 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 separate and dissolve in The organic phase τ 〇 123 123833.doc 200815339 The other separable component is more soluble in the aqueous phase, then the two separable components can be separated. If a suitable body, <, night body is used, the liquid-liquid separation can be powerful = surgery. It is impossible to pass the (four) phase/organic phase separation for the separation of the rings (4) and (iv) _ with the ring-burning smoke and the ancient gland-derived 又· 隹 and 5, because it dissolves in the organic phase _. ^Easier::: Extraction techniques can also use two types that are generally not miscible with each other. "Into π" and the components to be extracted are in the organic phase - the material is much larger than in the other Solubility. Liquid_Liquid Extraction Technique 2: The final recovery of the component extracted from the initial mixture can be complicated by the volatility of the agent. The final component of the m component is usually by the total; 隹彡- y _ ^ The matter is quite similar. Because: the volatility of the solvent is often very difficult to recover from the product to be produced, and it may be difficult to use it. The method may also be energy intensive. The ionic liquid of the solvent is drawn to avoid such restrictions. Since the body is generally non-volatile, it does not interfere with the θ of the component of interest in the final recovery period. Therefore, by simply and quickly recovering the components to reduce the oxidization of caprolactam without the need for complex separation techniques and energy (eg, steam) requirements, the step must be straight spot, I and cyclohexane. Mixture of ketones or cyclohexanol in the presence of cyclohexane: 1R separation. This is because the production of caprolactam only requires = L. The separation is carried out by the steaming hall, wherein the ring is required to leave a large amount of energy and high capital for the desired steaming tower. Liquid liquid extraction techniques are not conventionally used for cyclohexanone and cyclohexanol: 123833.doc 200815339 Separation, because for the application, the extraction solvent must only be removed from the mixture _ # , τ a ” component. The conventional solvent suitable for solvent extraction method will selectively extract cyclohexanol from the ring. The number is as follows: the night body knife can be used to quote the distribution of a given separable component. Separation of the separation range of the eight-/separate component. In the conventional liquid-liquid system, the number is equal to 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 different parameters of the right stem, such as temperature. MA [Description of the Invention] The objective of the invention is to provide a method for the non-polar dissolution of alcohols and ketones; for the separation of alcohols from ketones, and for the use of alcohols and/or ketones with non-polar rings m. A particular object of the present invention is to provide for the separation of a mixture of such compounds in a non-polar hydrocarbon, and for the use of a cyclic alcohol and/or a polar solvent (such as An improved method of separation of naphthenic hydrocarbons. [Embodiment] According to the present invention, there is provided a method for the separation of: an alcohol separated from a non-polar solvent; a ketone separated from a non-polar solvent; a mixture of an alcohol and a ketone and a non-polar solvent, or a hand And a mixture of non-polar solvents. The method comprises contacting at least one ionic liquid with a mixture comprising at least one of a non-polar and a ketone. Hydrazine and alcohol as used herein, the term "alcohol" encompasses non-indolenol and cycloaliphatic alcohol, 123833.doc 200815339: °, the term used to cover acyclic aliphatic ketones and cycloaliphatic ketones And - in the examples, refers to a (calcinyl-(c=0)-alkyl) group, and in an alternative embodiment refers to a group in which the (CH2) group is replaced by a ((iv)) group. a cyclic compound of a cycloalkane, that is, "cycloalkane §,, r, \ ij as used herein, the term "smoke" refers to (hospital-H), and the term "ring-burning hydrocarbon" Refers to (cycloalkyl-H). As used herein, the term "alkyl" refers to a linear or branched saturated monovalent, and specifically a straight or branched saturated monovalent hydrocarbon radical having (1) (iv) carbon atoms. By way of non-limiting example, suitable alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl and decyl. The alkyl groups may be substituted by one or more identical or different functional atoms, but are preferably unsubstituted. The term "cycloalkyl," as used herein, refers to a cyclic saturated monovalent hydrocarbon radical having from 3 to 2 carbon atoms. Non-limiting, by way of example, suitable cycloalkyl groups include cyclopropyl, cyclobutyl, Cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl and cyclododecyl. The cycloalkyl group preferably has 5 to 2 carbon atoms. The cycloalkyl groups may be passed through one or more Substituted by the same or different halogen atoms, but preferably unsubstituted. As used herein, the term "non-polar solvent" means a compound which is immiscible with an ionic liquid. In one embodiment, the term "non-polar solvent" means having (measured at 20 ° C and atmospheric pressure according to ASTM D924-92) not higher than 5, preferably not higher than 3.0, more preferably not higher than 2.5. The solvent of the dielectric constant. In a 123833.doc 200815339 (4) 2 'the term "non-polar solvent" means a cyclic and acyclic fat, and the U is a cyclic and acyclic saturated waxy hydrocarbon, that is, Hydrocarbons and such as pentyl, hexan, gypsum, octyl, and cyclohexane. The I. sulphate hydrocarbons may be substituted by one or more of the same or different atoms, but the car is not Therefore, in one embodiment of the present invention, there is provided a method for separating: Π 环 环 烧 与 与 与 与 与 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; 与 与 与 与 与 与 与 与 与 与 与 与 与 与Separating a mixture of solvents; or separating a mixture of a cycloalkanol and a cycloalkanone from a non-polar solvent; the method comprising contacting at least one ionic liquid with a mixture comprising a non-polar solvent and at least one of a cycloalkanol and a cycloalkanone Provided in another embodiment of the invention for the following separation Separating an alcohol from an alkane; separating the ketone from the alkane; the method comprising separating at least one of the mixture of the alcohol from the mixture of the ketone and the alkane; or separating the mixture of the alcohol and the ketone from the alkane; in particular, the alcohol and the ketone An acyclic liquid that is acyclic and contains an alkane and an alcohol with an I. In this embodiment, the alcohol contains a different number of carbon atoms than the ketone and/or alkane present in the mixture to be separated (but preferably The number of carbon atoms which are the same), 123833.doc -10· 200815339 and the _ contains a different number of carbon atoms to be separated: the alcohol and/or the alkane which are present in the mouth is one of the present inventions The number of sub-genus. The method of ································································································ Separation of the mixture of hydrazine; or the separation of the scorpion scorpion and the naphthenic g, and the separation of the sulphate and the cycloalkane, · δ hai method contains at least $ 与 and 垸 _ at least: liquid and contains a ring burning hydrocarbon And a mixture of a cyclic alcohol/one of the mixture. In the embodiment, ～ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ The number of sub-mersibles in the mixture containing the mixture to be separated. The reason why the anti-atomic number of the stone in the work is different (but preferably the same) is that the present invention covers: (1) for the alcohol and/or the same phase Separation of alkane or cycloalkane; separation of aliphatic hydrocarbons (ie, methods having the corresponding number of carbon atoms, and for the alcohol and the corresponding ketone and (η) for alcohols and/or ketones a method of separating from a fatty tobacco having a carbon number of the same carbon atom (for example, a hospital smoke or a cycloalkane), and a method for separating the alcohol from the ketone and the aliphatic hydrocarbon; and (iii) for an alcohol and/or a ketone A method of separation from a non-polar solvent as defined herein, and a method for the separation of the alcohol from the corresponding ketone and non-polar solvent, Method 123833.doc 200815339. Further, in the methods described under (ii) and (4) above, the alcohol and the oxime may have different numbers of carbon atoms from each other, but usually they will have the same number of anodic atoms. According to the present invention, there is further provided a specific ^ σ σ; when the alcohol is a nonalkanol and the ketone is a cyclo ketone, and in particular, 忒 之 之 之 为 is a cycloalkanol and the ketone is a cycloalkanol And when the non-polar solvent is a cycloalkane, at least one ionic liquid η is used.

U A method in which an alcohol and/or a ketone is separated from a non-polar solvent or a mixture of an alcohol and a ketone in a mixture of an alcohol and a ketone in a non-polar solvent. In an embodiment, the ring-based group contains 6 carbon atoms, in which case the separation method described herein specifically relates to the separation of cyclohexanol and/or cyclohexanone from cyclohexanol. Cyclohexanol is separated from cyclohexan and cyclohexane. Knife In another embodiment, the cycloalkyl group contains 12 carbon atoms, in which case the separation method described herein is specific to the female compound. The system relates to the separation of cyclododecanol and/or cycloundecone from cyclodextrin, and # relates to the separation of indolyl alcohol from cyclododecan and cyclododecane. Therefore, the mixture to be separated can be whitened. t, 1 thus comprises, for example, a cycloalkanol and a naphthenic fumes; or a ring (iv) and a cyclic oxime; or a ring (iv) and a ketone ketone and a cyclic oxime. The method of the present invention comprises liquid-liquid separation wherein one of the liquid phases is based on the phase of the ionic liquid and the other is substantially non-polar solvent phase (eg based on organic) that is miscible with the ionic liquid. Hydrocarbon phase). As used herein, the term "substantially unintentional clocks are immiscible to the extent that two separate phases are formed. The method of the present invention is therefore dependent on the desire to divide 123833.doc -12. 200815339, and The wound (also available as a separate component) differs in the relative solubility of the ionic liquid-based phase and the non-polar solvent phase. In particular, the separable component will be present in the ionic liquid-based phase and the non-polar solvent phase. Or the various separable components will be themselves soluble in the ionic liquid-based phase. Knife • Once the ionic liquid is mixed with the alcohol and/or ketone contained in the non-polar solvent (eg, cycloalkanol in % alkane and / Or a mixture of cycloalkanones, which is referred to herein as a separation mixture " as used herein, the term "contact" is intended to bring an ionic liquid and the alcohol and/or ketone contained in the non-polar solvent. The complex aggregates to form a separation mixture. The ionic liquid and the mixture of the alcohol and/or ketone contained in the 2 polar solvent may be contacted in a container (i.e., a reaction vessel) suitable for the contact. The separation mixture is vigorously shaken, mixed or stirred for a period of time (hereinafter referred to as contact time) to allow the ionic liquid to be dispersed throughout the mixture of alcohol and/or ketone contained in the cold enthalpy. It should be understood that if the contact 〜1过^', the ionic liquid will not be completely distributed in the mixture of the alcohol and/or ketone contained in the non-polar hydrazine solvent, and the separation of the separable components will be inefficient, that is, Only a small fraction of the separable components present in the separation mixture will be separated. Increasing the contact time of the separation mixture will increase the dispersion of the ionic liquid '胄 and the mixture of the alcohol and/or ketone contained in the non-polar solvent, and the efficiency of the separation will increase, that is, the larger part of the mixture can be separated. The components will be separated. The separation efficiency will increase with the increase of contact time until the maximum possible amount of the total volume of the separable components has been separated for the separation conditions used (ie, the type of ionic liquid, temperature =, etc.) Great separation. In this regard, continued contact with the separation mixture will not provide any benefit to the separation of the separable components. Therefore, the contact time as used herein is preferably greater than 30 seconds, more preferably greater than 60 seconds' and usually no greater than 5 minutes, although use of longer periods may be a satisfactory result.

w w /to ψ/J Time (hereinafter referred to as "precipitation time") after violent shaking, mixing or stirring. During the precipitation time, the separation mixture will separate into an ionic liquid-based phase and a non-polar solvent-based phase.

phase. The precipitation time should be long enough to completely separate the ionic liquid-based phase and the non-polar bath-based phase, at which point the system is described as being in equilibrium. The aging time is preferably greater than 1 minute, more preferably greater than 2 minutes and usually no greater than 1 〇 minute, although longer periods of use may have satisfactory results. Mixtures comprising at least one of an alcohol and/or a ketone and, in particular, a cycloalkane = decyl alcohol and a cyclone in a non-polar solvent can be formed by performing an oxidation step in the separation. By way of example, t, in the case of oxidation of an alkane such as cyclohexane as described above, the oxidation step can be (not limited to) use of air alone or in cobalt or other transition metal catalyst: oxidation It is then decomposed thermally or via other catalytic methods: = cyclohexyl. Based on the invention (4), the oxidation step is followed by a step of decomposing the cyclohexyl group, followed by separation (or contact), and an emulsification and separation cycle. A plurality of oxidations and fractions may be carried out. In this case, the phase derived from the (tetra) hydrocarbon or the fraction obtained from the separation may be recycled for further oxidation. Non: Γ After the separation step, the phase based on the ionic liquid can be physically separated based on the phase of the non-polar solvent. This physical separation can be performed using any of the 123833.doc 14 200815339 settings. Further, the separable component (eg, a cycloalkanol and/or a cycloalkanone may be removed from the ionic liquid-based phase, and the ionic liquid may be recycled and reused, for example, in another separation step. Commercial equipment for liquid-liquid extraction contact and separation generally can be divided into two types: knife-level and continuous (differential) contacts. The staged operation usually involves a mixing step in a device commonly referred to as a mixer/precipitator, dust Perform 2 separation (or sink; temple) steps. It can be operated in sequential batch mode. In this case, the same capacity H-channel f-series alternately provide the functions of mixing and sag. It can also be operated in the flow mode. In this case, the mixing and precipitation steps are usually (but not always) carried out in separate vessels. In a continuous flow system, the necessary 'days' and precipitation times are obtained by appropriately setting the equipment volume and holdup size. Examples of commercial mixing equipment known to those skilled in the art include in-line static mixers, jet mixers, syringes, orifices or mixing nozzles 1, centrifugal pumps, activated pipe mixers, packing tubes Mechanically disturbed containers, gas or vapor-operated containers, and containers having a circulating process circuit. Examples of commercial sinking devices known to those skilled in the art include gravity precipitators, decanters, centrifugal cyclones, centrifugal separators, and The auxiliary equipment of the Shen Dian is such as a coalescer, separation membrane and electric field device (for conductive emulsion or dispersion). It can be combined with any type of mixer and killer; one or two: can be arranged in multiple stages in series Level to achieve additional separation. 2::: A variety of liquid flow schemes can be used, such as countercurrent flow, cross flow, grading flow, etc. It is possible to construct a compact device consisting of alternative mixing and difficult components. The difference) contact equipment is usually not 123833.doc -15 - 200815339 without repeating the configuration of the liquid between the levels is completely separated from each other. However, it can also be configured as parallel flow or cross flow. Liquid is guaranteed throughout the equipment Continuous contact. By the difference in liquid density along with gravity or centrifugal force: holding countercurrent flow. Commercial equipment known to those skilled in the art includes Gravity operated extractor, such as a spray tower, packed column or (iv) tower n-assisted gravity operated extractor, such as a rotary actuator / turntable contactor, Mixe () _shue_Rushtc) n) multi-mixer column , (iv) Scheibel column, Kuhni contact $column, liquid pulsation tower and multi-plate column; and centrifugal extractor. This month's knife separation method can be used in the manufacture of adipic acid or caprolactone in one or more separation steps. Let Rong Gu’s thank you. The separation step of the method has been conventionally carried out by means of a separable component in the shell (4), which is etched with an ionic liquid, p w A r W, and a knife. In the middle, the ionic liquid is θ θ Θ % ϋ compound (4). ^ and the mixture of hydrocarbons is called separation and mixing () mouth haibei application method includes liquid 俨, 舻 舻 私 私 “ “ “ 液体 液体 液体 液体 液体 液体 液体 液体 液体 液体 液体 液体 液体 液体 液体 液体 液体 液体 液体 液体 液体 液体 液体 液体 液体 液体The phase is soluble in the phase 2 > the horse is substantially unmixable, based on the phase of the scorpion liquid, based on the phase of the cycloalkane _ household # T sinking. In this embodiment, the octupon* soil is in the ionic liquid. The knives coefficient of the phase and the naphthenic-based phase is greater than U and preferably greater than 3. The phase between the phases (b) can be combined with the sterol. The ionic liquid ring hydrocarbon separation In the case of a mixture of a liquid limb and a paraffin and a cycloalkane, it will be in contact with the liquid. The liquid is applied to the liquid and the mixture of the cycloalkanol and the ring (VII). The method of this embodiment comprises a wide liquid: 5 is called separation friend 3 Liquid-liquid separation, in which liquid J23833.doc 16 200815339 is one based on the ionic liquid phase, and additionally miscible in the ionic liquid, , and i based on the naphthol-based phase In the middle, the alcohol in the phase is based on the ionic liquid. The distribution coefficient of the implementation is greater than U and preferably greater than 3. The fraction of %^ is divided into two groups. The separable component is a mixture with ring-burning and ring-smoothing. The figure is m ° ionic liquid and ring alcohol L and ring furnace, θ "Do not touch. In the examples, 'the ionic liquid: a mixture of hydrazine and a ring-house hydrocarbon is referred to as a separation mixture (4). The actual =w contains a liquid-liquid separation, wherein one of the liquid phases is the phase of the method, and the other liquid The phase of the large r is not based on the lyophilized phase in the ionic liquid-based phase in the ionic liquid. According to the method in the ionic liquid-based phase plate 'when the ring alcohol ^ m , based on % burning The distribution coefficient between the phases is large; and when the distribution coefficient of the ketone-based ketone based on the ionic liquid-like phase and the naphthenic-based is less than 1, the cleavage of the 丄t8-M-perkanol with the cycloalkanone and the cycloalkane This example is applied to the separation of cyclohexanol, ketone, and ruthenium, which is used to make kimono 酉 & 月 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 :: The coefficient of the knives in the phase based on the ionic liquid is greater than 15 and preferably greater than 3. In the embodiment (d) The component is _ detached, and the damage is the contact of the mixed ionic liquid of the ketone ketone and the ketone separated from the % of the hydrocarbon, and the contact of the cycloalcohol, the ring and the ring-burning hydrocarbon. In this embodiment, the ion is A liquid and a mixture of a cyclic alcohol, a cyclopentanone and a cycloalkane are referred to as a knife-off mixture (d). The side of this embodiment is a fine-liquid separation in which one of the liquid phases is based on an ionic liquid. The other phase is a ring-burning hydrocarbon-based phase which is immiscible in the ionic liquid-based phase of the large 髀p body. In this embodiment, the cycloalcohol and the cyclaze are at 123833.doc -17· 200815339 The fraction between the ionic liquid-based phase and the phase-based smoke-based phase is 1.5 and preferably greater than 3. "The number is greater than

In each of the embodiments (4) to (4), the substance to be separated is mixed with a substance other than a cycloalkanol, a cycloalkanone, and a cycloalkane component: the substance is between the phase based on the ionic liquid and the phase based on the ring (iv) Depending on the coefficient, these other substances will remain in the phase based on the ring-burning: together with the separable component - separate into the ionic liquid-based phase. Specifically, ''Oxidized cyclohexyl (CHHP) may be present in a separate mixture of cyclohexanol, cyclohexane = %. In these cases 'CHHP will be separated from cyclohexanol and/or cyclohexanone to a In the phase of the ionic liquid. ^, It should be understood that the methods of Examples (4) to (4) are also applicable to the general case, in which the reference to the fermentation, the ® ij and the non-polar solvent are substituted for the above-mentioned cyclobutanol, cycloalkanone and ring, respectively. The ionic liquid of the present invention may be composed of a single ionic liquid or a mixture of two or more ionic liquids (that is, two, three, four, five, six, etc. different ionic liquids). Typically, one or two (and usually only one) ionic liquids are used. The ionic liquid preferably comprises a cation selected from one or more of the following: an alkyl group, an alkyl pyridinium or a polyalkylpyridine rust, ruthenium. (PR4+), alkyl scale or polyalkyl hydrazine, imipenyl rust, alkyl imidazole rust or polyalkyl imidazole rust, ammonium (NR4), alkyl ammonium or polyalkyl ammonium, alkyl. Alkyl carbazole 1 alkyl pyrrolidine rust or polyalkyl pyrrolidine rust, alkyl nitrogen rust or polyalkyl nitrogen rust Alkyloxygen or alkylhydrazine. Each R group of the scaly and the hydroxy cation may be independently selected from the group consisting of the following substituent groups 123833.doc -18-200815339: hydrogen, hydroxy, alkyl, alkyl An ether group, an alkyl ester group, an alkyl decylamino group, an alkyl carboxylate group or a sulfonate group. The ionic liquid more preferably comprises a cation selected from the group consisting of: pyridyl pyridine rust, alkyl pyridinium or polyalkylene Pyridinium, imidazole rust, alkyl mer: rust or polyalkyl odor 当. When a mixture of two or more ionic liquids is used, the cations of each of the plasma liquids present in the mixture may be the same Or different. The anion of the ionic liquid is preferably selected from one or more of the following: an ion (preferably a gas ion, a bromide ion or an iodide ion); a nitrate; an alkyl sulfate or an alkyl polyalkoxy sulfate; Such as mesylate, trifluoromethanesulfonate and sulphate, based on nitrogen, lin, phenanthrene, stagnation, sun, hoof, halogen anions and metal oxyanions. Suitable anions include, but are not limited to, bis ( Trifluoromethanesulfonyl) guanamine (NTf〆), Tetrafluoroborate (BFV), trifluoromethanesulfonyl (hydrazine), methoxyethylsulfonate, 2-methoxyethylsulfonate, ethoxyethylsulfonate, 2-ethoxyethylsulfonate, (methoxypropoxy)propanesulfonate, 1-(1-methoxypropoxy)-propanesulfonate, (decyloxyethoxy)-ethanesulfonate, 1-(1-methoxy Ethoxyethanesulfonate, methyl (diethoxy)ethanesulfonate, 1-methyl(monoethoxy)methionate, acidified acid, formate, acetate, dicyandiimide and three Fluoromethanesulfonate. The anion of the ionic liquid is more preferably selected from one or more of the following: alkyl sulfate or alkyl polyoxyalkyl sulfate, bis(trifluoromethyl) decylamine (NTf2·) And tetrafluoroborate (bf4-). When a mixture of two or more ionic liquids is used, the anions of each of the plasma liquids present in the mixture may be the same or different. 123833.doc -19- 200815339 The ionic liquid will preferably comprise at least one C2_C0 alkyl group. The c2_c6 alkyl group may be an anion or a substituent on the ionic liquid. The (2<6 alkyl group is more preferably a substituent on the cation of the ionic liquid. When the ionic liquid system consists of a single ionic liquid, the single ionic liquid present preferably contains less than one C2_C0 alkyl substituent. When the ionic liquid system consists of two or more ionic liquids, at least one of the ionic liquids present preferably contains at least one C2-C0 alkyl substituent, more preferably two or more ionic liquids are present At least one C2_C6 alkyl substituent, that is, 2, 3, 4, 5, etc. of the plasma liquid present contains at least one qc:6 alkyl substituent. Optimally, at least one ionic liquid All ionic liquids present contain at least one C2_C6 alkyl substituent. The ionic liquids of the present invention are preferably selected from the group consisting of bis(difluoromethanthine xanthyl) decylamine N-ethyl. Rust; N-methyl-N,-butylimidazole rust of tetrafluoroborate; bis(difluoroanthracene fluorescein) decylamine N-methyl-N,-butylan η sitting rust; double (three Fluoromethanesulfonyl) decyl trimethyl _ (2-hydroxyethyl) ammonium; 2-A Oxalyl sulfonate-fluorenyl-hydrazinyl-indole,-ethylimidazole rust; (difluoroantimony-burning sulfhydryl) g-anilinium-butylmethylpyrrolidine rust; 2-methoxyethylsulfonate oxime -methyl-ν'-butylimidazole rust; bismuth bromide-methyl-hydrazine, -butylimidazole rust; 2-ethoxyethyl tartaric acid bismuth-fluorenyl-hydrazine, -butylimidazole rust; -Methoxypropoxy)·丙 黄 Ν 曱 曱 曱 曱 曱 - - - - - - - 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- Ν' - butyl-salmon, 1-methyl(diethoxy)ethanesulfonate-yl-indole, butyl imidazole rust; or 123833.doc -20- 200815339 trifluorodecane sulfonate N- Benzyl-N-(butyl-4-sulfonic acid). Bipyridinium or a mixture thereof 0 The ionic liquid is preferably bis(trifluoromethanesulfonyl) decylamine butyl Ν 甲基 甲基 甲基 甲基 甲基Rust or bismuth 1-(1-methoxypropoxy)-propanesulfonate-methyl-oxime,-butyl methoxide. In particular, when the alcohol is a cyclohexane alcohol (and especially cyclohexanol) Non-polar solvent

When the ring is a hydrocarbon (especially cyclohexane), the ionic liquid most suitable for the separation of the alcohol from the non-polar solvent is: bis(trifluoromethanestone) guanamine ethylpyridine rust; tetrafluoroborate N-methyl -N, butyl imidazole rust; bis(trifluoroanthracene sulphate) amidoxime _N, _butyl saponin; bis (difluoromethane) decyl trimethyl _ (2 hydroxy Ethyl)ammonium; 2-methoxyethylsulfonic acid N-methyl-N,-ethylimidazole rust; bis(difluoromethanesulfonyl)decylamine N•butylmethylpyrrolidine rust·2-methoxyB N-fluorenyl-N,-butylimidazole rust of sulfonic acid; >Smelling N-methyl-Ν'-butyl taste.镌 镌; 2· ethoxyethyl sulfonate methyl-hydrazine, -butylimidazolium; 1-(1-methyllacylpropoxy)-propanesulfonic acid Ν 曱 Ν Ν - - - 4; (4)-Methyl ethoxy ethoxy acenaphthyl succinyl methyl ^-butyl sulphate; 1-: yl (diethoxy) ethane sulfonic acid methyl _ ΝΙ _ butyl imidazole 镔 two gas甲 Ν Ν 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基The ionic liquid of "the hexanol" and the ketone is cycloalkane (especially I23833.doc 200815339 cyclohexanone) and the non-polar solvent is cyclohexane (especially 35 hexane): brominated N -Methyl-N,-butylimidazole rust; Bu (1-methoxyethoxy)-ethanesulfonic acid N•methyl_N,-butylimidazolium; or 2-ethoxyethylsulfonic acid N _Methyl_N, butyl imidazole rust, or a mixture thereof. Most suitable for the separation of ketones from non-polar solvents (specifically where the ketone is a cycloalkanone (especially cyclohexanone) and the non-polar solvent is a cycloalkane ( Especially for the production of alkane)) ionic liquid is ·· & double (three Methanesulfonyl) decylamine N-ethyl acridine hydrazine; tetrafluoroboric acid N-methyl-N,-butylimidazole rust; bis(trifluoromethanesulfonyl) guanamine ^^-methyl-N, _butyl imidazole rust; bis(trifluoromethanesulfonyl) decyl tridecyl-(2-hydroxyethyl)ammonium; 2-methoxyethylsulfonic acid N-methyl-N, _ethyl imidazole rust ; bis(trifluoromethanesulfonyl) guanamine butyl _N•methylpyrrolidine rust; 2-methoxyethylsulfonic acid N_methyl_N,-butylimidazole rust; 1-(1-曱oxypropoxy)-propanesulfonic acid N•mercapto_N,-butylimidazole rust; y-yl (diethoxy)ethanesulfonic acid N-fluorenyl N, butyl butyl imidazole rust; or Trifluoroantimonic acid N-methyl-Ν·(butyl·4_钱) bite iron, or a mixture thereof. 英寸 U的_ The alcohol is a cycloalcohol (especially cyclohexanol) and the ketone (especially When it is cyclohexanone) and the non-polar solvent is a ring-burning hydrocarbon (especially sinter), it is most suitable for the mixture of alcohol and _ and the non-polar solvent from the two-component liquid: eagle 123833.doc -22- 200815339 bis(trifluoromethane Sulfhydryl) decylamine N_ethylpyridine rust; tetrafluoroboric acid N-methyl-Ν'-butylimidazole rust; bis(trifluoromethyl) Amidoxime-Ν'-butyl meth. sitting rust; bis(trifluoroanthracene sulphate) guanamine tridecyl-(2-ethyl)ammonium; Methyl-anthracene-ethylimidazole rust; bis(trifluorodecanesulfonyl) amidoxime-butylpyridylpyrrolidine rust; 2-methoxyethylsulfonate-fluorenyl-Nf-butyl Imidazole rust; 1-(1-methyllacylpropoxy)-propane sulphate N-methyl-oxime-butyl styrene. Sitting rust; 1-methyl(diethoxy)ethanesulfonic acid N- Methylbutylimidazolium; or N-methyl-N-(butyl-4-sulfonic acid) pyrrolidine rust of trifluoromethanesulfonate or a mixture thereof. The term "ionic liquid," as used herein, refers to an ionic compound that is a liquid below 1 〇〇t. As used herein, the term liquid-liquid separation, the distribution coefficient, refers to the concentration of the separable component in the ionic liquid-based phase divided by the separable group ☆ ☆ the concentration in the non-polar solvent-based phase . These concentrations were measured after precipitation, i.e., when the 7 knives had reached equilibrium after violent shaking. The invention is illustrated by the following examples. It is to be understood that the examples are merely for the purpose of deletion and are not intended to limit the invention as described above. The details may be modified without departing from the scope of the invention. EXAMPLES (I) Lysohexanol/cyclohexanone/cyclohexanol was further exemplified by separating the % hexanol and cyclohexan with cyclohexane and then arranging the distribution coefficient to exemplify the present invention. To simplify these examples, 123833.doc -23- 200815339 has used equal volumes of cyclohexane and ionic liquids. However, it should be noted that the volume of ionic liquid used in practice should preferably be a fraction of the volume of cyclohexane. :: It should be noted that since the distribution coefficient is independent of volume, the equivalent volume of the bead material will be related to industrial applications where the volume of ionic liquid and cyclohexane may not be equal. The general method used for all examples is as follows. Storage, solution: 250 mg cyclohexanol (molecular weight = 1 〇〇 gm 〇 i ' and 25 〇 mg cyclohexyl (molecular weight = 98 handsome. 1.1) in 1 〇 g cyclohexane (molecular weight = 84 gm〇i ·]). Go to 1 mL (〇.8g) stock solution (2〇mg of cyclohexanol and add to the 1st liquid and shake vigorously. At the precipitation time and 6

After that, 3 drops of the supernatant were added to the -bottle and filled with J-I% bulk chromatographic analysis to obtain the number of moles of the separable component in each liquid phase. The separated distribution coefficients are then calculated. Hnmr (hydrogen nuclear magnetic resonance) is performed on the second layer of the lower jaw. In all cases in most: the ketone layer contains less than 5 mol% of ionic liquid. “The amount of ionic liquid in the layer based on the ring is undetectable: a detailed description of the distribution coefficient compared to water and DMS0 (four) u fruit. 123833.doc •24- 200815339 Table 1 Example extraction solvent ring ί Cyclohexanone D Log DD Log D 1 H20 0.86 -0.07 0.34 -0.47 2 NTf2' k 1.60 0.20 3.40 0.53 3 1 "N> Ln+/ bf4-\ 1.77 0.24 2.11 0.32 4 \ L〆bf4-1 2.32 0.36 1.51 0.18 5 —n+^\^〇h 1 NTf2· 2.91 0.46 3.00 0.478 6 rN> L〆NTf2. 1 4.10 0.61 4.38 0.64 7 \ NTf2' 5.12 0.71 5.00 0.7 123833.doc -25- 200815339

So3h 8 [V \ cf3so3- 5.96 0.78 0.21 -0.69 [' f 9 break 6.29 0.8 1.89 0.28 + > s Λ , N/ NTf2-1 10 $ [N>/ Bf 6.29 0.8 0.39 -0.41 11 [N> 坆N+ 8.02 0.90 0.92 -0.04 | ,〇x^^oso3- 12 8.19 0.91 0.24 -0.62 123833.doc -26- 200815339 Ο γν> 1 13 ----- ΓΝ>/ 1 18.27 1.26 — 1.33 0.12 14 DMSO 24.79 1.39 2.80 The difference in the distribution coefficient of 0.45 cyclohexanol and cyclohexanone in the plasma liquid shows the separation efficiency of the cyclopropanol. The separation of cyclohexanol from cyclohexane and the separation of cyclohexanol from cyclohexanone and cyclohexane by &

(II) Octanol/octanone/octane The corresponding experimental group was studied to extract octyl and 2-octanone from octane using an ionic liquid. The result table _ y, ^, in Table 2 below, according to the matrix in n

The concentration in the middle is divided by the matrix at xin and at 1L. The concentration of decane is used to calculate the IL/octane distribution system. 123833.doc -27- 200815339 Example ionic liquid IL/octane octanol 2-octanone 15 ίΓΛ NTf2 1.06 2.08 16 ^〇x^^OS〇3 2.39 0.24 17 \N々N+^ '~^ Br 1.44 0.16 18 /^\ 6.93 0.64 19 DMSO 7.67 0.89 The difference in the distribution coefficient between octanol and 2-octanone in the plasma liquid proves that octanol and / or 2-octanone and octane The separability of (Example 15) and the separability of the mixture of octanol with 2-octanone and octane (Examples 16 to 18). 123833.doc 28-

Claims (1)

200815339 Patent application scope: 1 · A method for the separation of: separating an alcohol from a non-polar solvent; separating a ketone from a non-polar solvent; separating an alcohol from a mixture of a ketone and a non-polar solvent; or an alcohol and a ketone The mixture is separated from the non-polar solvent; the 5H method comprises contacting at least one early liquid with a mixture comprising a non-polar solvent and at least one of a scorpion and a ketone. 2. The method of claim 1, wherein the ketone is a cycloalkane- and the beta non-polar solvent is a cycloalkane. 3. The method of claim 2, which is applied to the face m 4 such as 5 for separating the decyl ketone from the cycloalkane. 4* The method of δ Month No. 2, which is used for the face hydrocarbon, e \ ^ ', and the separation of the % alkanol from the cycloalkanone and the cycloalkane compound. 5. The method of claim 2 is separated from the naphthenes. The method of claim 2, which is used for mixing a mixture of a ring and a ring of alcohol. 6. It is used to mix a cyclopentane with a cycloalkane, a metanol or a cycloalkanone or a mixture thereof. Separation of spleen i >, decane _ and cycloalkane, and a naphthenic phase in a wide range of ionic liquids and at least one of an alcohol and a cycloalkanone in a decane. Upon contact with one another, two separate hydrocarbons are formed. ...based on an ionic liquid and a second phase system according to the method of claim 6, which is a hydrocarbon separation, 1A 7 ketol and a cycloalkanone and a cycloalkane-T ace 4 in two independent phase states, the if alkane To the balance, and in the equilibrium state, the distribution coefficient of the ionic liquid basket-based phase and the naphthenic-based 123833.doc 200815339 is greater than 15. 8. The method of claim 7, which is for use in hydrocarbon separation, wherein the distribution coefficient is greater than 3.4. The method of claim 6 is a hydrocarbon separation, wherein the β 4 is Knowing that the two independent phases are in a state with % alkanone and naphthenic monomethyl, the distribution coefficient of the cyclodextrin between the ionic liquid-based and ruthenium-rich phases is greater than! ,two! The person should base the ring-based hydrocarbon liquid phase with the ring-based smoke (IV) based on the separation. The distribution coefficient between the two is less than 10. The method of claim 6, wherein the two independent phases are brought to equilibrium and separated from the ring smoke, and the loop is in the ionic liquid based ==: balance state, the The distribution system (4) is greater than 1.5. ...^ between the phases of the smoke. 11. If the method of claim 〇, Α where the distribution coefficient is greater than 3. %(10) is separated from the ring-house hydrocarbon, wherein it is used to separate the ring-shaped ketone from the ring-burning tobacco, and the distribution coefficient of the phase of the soil ionic liquid and the base is greater than h5. & between the phases of the clothing 13 13 · If the h distribution coefficient ^ is greater than the square of the request item 12, 3 will separate the ring and the burning of the ring 'material magic: two 6 'method' is used to burn the ring The mixture of hydrazine and cycloalcohol is separated from the % alkane, in the equilibrium state of ^/tb π in the 〜;: the two-phase system reaches equilibrium and lies in the phase based on the ionic liquid and the phase based on 123833.doc 200815339 The distribution coefficient between them is greater than Μ. 15. The method of claim 14 which is for separating a cycloalkanone and a hydrocarbon, wherein the coefficient of distribution is greater than 3. The method of any one of the items 2 to 15, wherein the ketone and the ring-burning hydrocarbon each contain 3 to 2 carbon atoms. The method of any one of claims 2 to 15, wherein the r\ leaven, the ring ketone is cyclohexanone and the ring hydrocarbon is cyclohexanyl^ is a ring I The method of any one of claims 2 to 15, wherein the diol, the (4) _ is a material _, and the material (4) is a ring ^ is a ring XX 19. The method of any one of claims 2 to 15 ,its::. Further, the step of oxidizing the ring (tetra) is carried out, followed by the hexyl decomposition step, followed by the contacting step, the epoxidation and the separation cycle. A method of claim 2 = method 19 which comprises a plurality of oxidations such that the ring-based hydrocarbons ::: produced by the separation is used in oxidation. The method of claim 20, wherein after the equilibrium is reached, the phase based on the at least one ionic liquid is physically separated from the phase-based hydrocarbon-based phase, and the ring is burned with alcohol and/or Or cyclospan (iv) is removed from the at least one ionic liquid and the at least one ionic liquid is recycled. The method of any one of claims 1 to 15, wherein the at least one ionic liquid system is composed of a mixture of two or more ionic liquids. The cation of the at least one ionic liquid is selected from the following ones or more: 烧 吼 吼 定 定 院 院 院 院 院 833 833 833 833 833 833 833 833 833 833 833 833 833 833 833 833 833 833 833 833 833 833 833 833 833 833 833 833 833 Alkyl town, bismuth rust, pyrimidine rust or polyalkylimidazole rust, ammonium, alkyl ammonium or polyalkylammonium, :): complete carbazole rust or polyalkyl oxazole rust, alkyl σ ratio a method of any one of claims 1 to 5, wherein the method of any one of claims 1 to 15 is carried out, or the method of any one of claims 1 to 15, Wherein the anion of the at least one ionic liquid is selected from one or more of the following: a tooth ion (chloride, bromide or iodide) or a nitrate; an alkyl sulfate or an alkyl polyalkoxy sulfate such as a sulfonate , trifluoromethanesulfonate and hydrogen sulfonate; based on nitrogen, phosphorus, boron, antimony, selenium, tellurium, _ anion and metal The method of any one of claims 1 to 5, wherein at least one of the at least one ionic liquid comprises at least one C2_c6 alkyl group, wherein the alkyl group may be present in the at least one ionic liquid The method of any one of the preceding claims, wherein the at least one ionic liquid is: bis(trifluoromethanesulfonyl) decylamine N-ethylacridinium; Tetrafluoroborate > 1-methyl-N,-butylimidazole rust; bis(trifluorodecanesulfonyl)decylamine N-methyl-hydrazide-butylimidazole rust; bis(trifluoromethanesulfonate)醯 曱 曱 曱 - - (2-hydroxyethyl) ammonium; 2 - methoxyethyl sulfonate - methyl - Ν '-ethyl imidazole rust; bis (trifluorodecane sulfonyl) acid amine Ν-butyl-hydrazine-methylpyrrolidine rust; 2_methoxyethyl sulfonate-methyl-Ν'-butyl imidazole rust; 123833.doc 200815339 Desertification N-mercapto-Ν'- Base η m bite; 2-ethoxyethyl sulfonate-methyl-Ν1-ethyl imidazole rust; iU-methoxypropoxy)-propane sulfonate-fluorenyl, butyl imidazole rust; h (l-decyloxyethoxy)-ethene Ν_曱基-Ν'_butylimidazole rust; 1-methyl(diethoxy)ethanesulfonate-fluorenyl-fluorenyl-hydrazine-butylimidazole rust; - Ν-(butylsulfonic acid) pyrrolidine rust, or a mixture thereof. The method of claim 26, wherein the at least one ionic liquid is bis(trifluoromethane yellow S-basid) amidoxime-butyl-fluorene-fluorenyl sigma sigma slag. The method of claim 26, wherein the at least one ionic liquid is! ^Methoxypropoxy)-propionic acid N-methyl-oxime- - butyl oxime. 29. A method of separating at least one ionic liquid to separate an alcohol and/or a ketone from a non-polar solvent, or separating the alcohol from _ in a mixture of an alcohol and a ketone in a non-polar solvent. \ / 3 0 · If the method of claim 29 is the same. Wherein the alcohol is a cyclononanol and the ketone is a ring-fired gas. The method of claim 29, wherein the alcohol is a cyclo ketone, and the non-polar solvent is a cycloalkane. Alcohol, and the ketone is cycloalkane 123833.doc 200815339 VII. Designated representative figure · (1) The representative figure of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 8. If there is a chemical formula in this case , please reveal the chemical formula that best shows the characteristics of the invention: (none) 123833.doc