JP2015048337A - Method for producing epoxy compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an epoxy compound suitably applicable to an industrial production process while using a tungsten peroxide compound as a catalyst.SOLUTION: Provided is a method for producing an epoxy compound comprising: an epoxidation step in which an epoxy compound-containing reaction mixture is obtained by the epoxidation reaction of an olefin compound using a tungsten peroxide compound as a catalyst and hydrogen peroxide as an oxidizer; a solvent removal step in which the solvent is removed from the reaction mixture by atmospheric distillation or reduced-pressure distillation; a first thin film distillation step in which, from the reaction mixture subjected to the solvent removal step, the unreacted olefin compound is separated by thin film distillation; and a second thin film distillation step in which, from the reaction mixture subjected to the first thin film distillation step, the epoxy compound is separated by thin film distillation.

Description

  The present invention relates to a method for producing an epoxy compound using a tungsten peroxide compound.

  Various catalyst systems have been developed for the epoxidation reaction of olefin compounds. For example, (1) a method of epoxidation with hydrogen peroxide in the presence of polyoxometalate which is a phase transfer catalyst (for example, Patent Documents 1 and 2), (2) a tungsten compound and α-aminomethylphosphone as a phase transfer catalyst A method of epoxidizing with an acid (for example, Patent Document 2), (3) a method of epoxidizing with hydrogen peroxide without a phase transfer catalyst in the presence of a tungsten compound and a phosphorus compound (for example, Patent Document 3), etc. Are known. Among these, in an epoxidation reaction using a tungsten peroxide catalyst, a reaction with a high epoxide selectivity can be advanced (for example, Non-Patent Document 1).

  By the way, in the separation of the product of the epoxidation reaction, in Patent Document 4, a separation method using silica gel column chromatography is used.

JP 2004-115455 A JP-A-8-27136 JP 2010-168330 A JP 2013-133339 A

Inorg. Chem. 46, 2007, p. 3768-3774

  In the epoxidation reaction, it is necessary to separate the target epoxy compound from the reaction mixture after the reaction. However, in the epoxidation reaction using a tungsten peroxide compound as a catalyst, when the epoxy compound is separated from the reaction mixture by a normal distillation operation, the epoxy compound is decomposed by the action of the tungsten peroxide compound contained in the reaction mixture, resulting in a yield. May decrease.

  Patent Document 4 describes a separation method using silica gel column chromatography, but such a separation method has a problem that it is difficult to apply to an industrial production process.

  Then, this invention aims at providing the manufacturing method of an epoxy compound which can be applied suitably for an industrial manufacturing process, using a tungsten peroxide compound as a catalyst.

  As a result of diligent research to solve the above problems, the present inventors have found that the yield of the epoxy compound can be remarkably improved by separating the epoxy compound through a specific process, and the present invention has been completed. It came to do.

  That is, one aspect of the present invention is an epoxidation step of obtaining a reaction mixture containing an epoxy compound by an epoxidation reaction of an olefin compound using a tungsten peroxide compound as a catalyst and hydrogen peroxide as an oxidizing agent, and atmospheric distillation or A solvent removal step for removing the solvent from the reaction mixture by distillation under reduced pressure; a first thin film distillation step for separating the unreacted olefin compound by thin film distillation from the reaction mixture that has undergone the solvent removal step; It is related with the manufacturing method of an epoxy compound which has the 2nd thin film distillation process of isolate | separating the said epoxy compound from the said reaction mixture which passed through the 1st thin film distillation process by thin film distillation.

  According to the said manufacturing method, the epoxy compound produced | generated by the epoxidation reaction can be isolate | separated from a reaction mixture with high efficiency. Moreover, the said manufacturing method can be applied suitably for an industrial manufacturing process.

  In one embodiment, the present invention may further include a catalyst extraction step of extracting the catalyst by adding hydrogen peroxide to the reaction mixture that has undergone the second thin film distillation step. By having such a catalyst extraction step, the extracted catalyst can be used again, which is an industrially superior production method.

  In one embodiment of the present invention, the olefin compound may be an alicyclic olefin. The alicyclic olefin may be tetrahydroindene.

  In one embodiment of the present invention, the solvent removal step can be performed at 80 ° C. or lower. Moreover, the said solvent removal process can be performed at 10 kPa or less.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of an epoxy compound applicable suitably to an industrial manufacturing process is provided, using a tungsten peroxide compound for a catalyst.

It is a conceptual diagram which shows an example of the manufacturing apparatus for enforcing the manufacturing method which concerns on this invention. It is a conceptual diagram which shows the other example of the manufacturing apparatus for enforcing the manufacturing method which concerns on this invention.

  A preferred embodiment of the method for producing an epoxy compound of the present invention will be described below.

  The method for producing an epoxy compound according to the present embodiment includes an epoxidation step, a solvent removal step, a first thin film distillation step, and a second thin film distillation step, and optionally further includes a catalyst extraction step. . Each step will be described in detail below.

(Epoxidation process)
The epoxidation step is a step of obtaining a reaction mixture containing an epoxy compound by an epoxidation reaction of an olefin compound using a tungsten peroxide compound as a catalyst and hydrogen peroxide as an oxidizing agent.

  The olefin compound used in the epoxidation reaction is not particularly limited, but an alkene compound can be preferably used from the viewpoint of particularly remarkable effects of the present invention.

  The alkene compound can be used either acyclic or cyclic. Examples of the alkene compound include ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene and 1-tridecene. 1-tetradecene, 1-pentadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1,3-butadiene, isoprene, isobutene, diisobutylene, propylene trimer or tetramers, styrene, vinyltoluene, Terminal olefins such as divinylbenzene; intramolecular olefins such as 2-butene, 2-octene, 2-methyl-1-hexene and 2,3-dimethyl-2-butene; cyclopentene, cyclohexene, 1-phenyl-1-cyclohexene, 1-methyl-1-cyclohexene, cyclohept , Cyclooctene, cyclodecene, cyclopentadiene, cyclodecatriene, cyclooctadiene, dicyclopentadiene, methylenecyclopropane, methylenecyclopentane, methylenecyclohexane, vinylcyclohexane, norbornene, tetrahydroindene, indene, 4-vinyl-1-cyclo Examples include alicyclic olefins such as hecene; and terpenes such as limonene, α-pinene, β-pinene, and ferrandrene.

  The olefin compound may be a compound formed by substituting various functional groups for the alkene compound. Examples of the functional group include —CHO, —COOH, —CN, —COOR, and —OR (R represents an alkyl group, a cycloalkyl group, an aryl group, or an arylalkyl group). The olefin compound may have a functional group such as an aryl group, a halogen group, a nitro group, a sulfonic acid group, a carbonyl group, or a hydroxyl group.

  Since the catalyst A-1 described later can be suitably used for epoxidation of a cyclohexene ring, an alicyclic olefin compound can be preferably used as the olefin compound to be applied to this production method. As the olefin compound, tetrahydroindene can be particularly preferably applied.

  The olefin compound may be a compound having one olefin moiety in the compound or a compound having two or more.

  As the tungsten peroxide compound used as a catalyst for the epoxidation reaction, various tungsten peroxide compounds used as known epoxidation reaction catalysts can be used.

  Moreover, as a tungsten peroxide compound, the following tungsten peroxide compounds (henceforth "catalyst A-1") can be used suitably, for example.

[Tungsten Peroxide Compound (Catalyst A-1)]
Catalyst A-1 is a tungsten compound obtained by reacting tungstic acid with an ammonium hydroxide compound. The ammonium hydroxide compound is preferably a compound represented by (R ₁ R ₂ R ₃ R ₄ N) (OH).

R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, or a benzyl group, and these have a substituent. It may be.

R ₁ , R ₂ , R ₃ and R ₄ are specifically methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, Examples include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group and other alkyl groups, and these may be linear or branched. May be. Moreover, these alkyl groups may have a cyclic structure, and a part of hydrogen atoms may be substituted with a substituent. Examples of the substituent include a phenyl group, a benzyl group, and a hydroxyl group. Carbon number of an alkyl group becomes like this. Preferably it is 1-12, More preferably, it is 1-8.

  Examples of ammonium hydroxide compounds that can be used include tetraalkylammonium hydroxide and alkylpyridinium hydroxide.

  Examples of ammonium hydroxide compounds include benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, trimethyl-3-trifluoromethylphenylammonium hydroxide, water Tris (2-hydroxyethyl) methylammonium oxide or the like can also be used. Further, as the ammonium hydroxide compound, cetylpyridinium ammonium hydroxide or the like can be used.

R ₁ , R ₂ , R ₃ and R ₄ are a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group or a benzyl group, more preferably a linear or branched chain having 1 to 18 carbon atoms. It is an alkyl group. R ₁ , R ₂ , R ₃ and R ₄ are more preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and further preferably a linear alkyl group having 1 to 12 carbon atoms. A linear alkyl group having 1 to 8 carbon atoms is particularly preferable, and an n-butyl group is most preferable. R ₁ , R ₂ , R ₃ and R ₄ may be the same or different from each other, but it is more preferable that R ₁ , R ₂ , R ₃ and R ₄ are all the same alkyl group. That is, in the present embodiment, tetra-n-butylammonium hydroxide is particularly preferable as the ammonium hydroxide compound.

  Catalyst A-1 can be obtained, for example, by the following method. First, tungstic acid is added to aqueous hydrogen peroxide and stirred to obtain a solution in which tungstic acid is suspended or dissolved. Next, the reaction is carried out by adding an ammonium hydroxide compound.

  The concentration of the hydrogen peroxide solution used at this time is arbitrary, but 10% to 70% hydrogen peroxide solution is preferable from the viewpoint of safety and efficiency.

  The amount of tungstic acid can be appropriately set according to the concentration of the hydrogen peroxide solution. For example, when 30% hydrogen peroxide solution is used, the amount used is 30 ml of 30% hydrogen peroxide solution. In general, an amount of 5 to 50 g, preferably 10 to 30 g, is added. The stirring time is not particularly limited, but is a time sufficient for the tungstic acid to be sufficiently suspended or dissolved in the hydrogen peroxide solution, and is usually 10 minutes to 10 hours.

  The ratio of tungstic acid and ammonium hydroxide compound is not particularly limited, but the ion equivalent ratio (anion of tungstic acid) / (counter cation) is preferably in the range of 0.01 to 100, more preferably 0.1 to 10. It is a range.

  After the reaction, the insoluble matter is filtered, and the filtrate in which the reaction product is dissolved is added to a solvent (hereinafter referred to as precipitation solvent) to precipitate a tungsten peroxide compound insoluble in the precipitation solvent as a precipitate. Can be recovered.

  In addition, it is preferable from the viewpoint of efficiency that the filtrate is concentrated before being added to the precipitation solvent. Although the degree of concentration is arbitrary, it is preferable to concentrate it 2 to 10 times. The precipitation solvent is not particularly limited as long as it can precipitate the tungsten peroxide compound, but a mixed solution of diethyl ether and isopropyl alcohol is particularly preferably used.

  The precipitate obtained as described above is preferably subjected to a purification treatment. As the purification method, a lamination method using a good solvent and a poor solvent, or a vapor diffusion method is preferable. The lamination method using a good solvent and a poor solvent is a technique in which a poor solvent is added little by little to a solution in which a precipitate is dissolved in a good solvent, and crystals are grown using the difference in solubility. In the vapor diffusion method, a solution in which a precipitate is dissolved in a good solvent is put in a container with an open top, and the whole container is put in a container containing a poor solvent and sealed. After a while, both containers have the same solvent ratio due to the vapor pressure equilibrium of both solvents, and this is also a method of crystal growth utilizing the difference in solubility.

  The good solvent can be used without particular limitation as long as the tungsten peroxide compound is dissolved. For example, the first, second, and third carbon atoms having 1 to 6 carbon atoms such as methanol, ethanol, normal or isopropanol, and tertiary butanol. Grade monohydric alcohols; polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, diethylene glycol, and triethylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetyl acetone; methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate , Esters such as n-butyl acetate, iso-butyl acetate, sec-butyl acetate, tert-butyl acetate, methyl benzoate, etc .; ethylene carbonate, propylene carbonate, etc., dimethyl carbonate carbonate Preparative like; dimethylformamide, dimethylacetamide, nitromethane, acetonitrile, nitrogen compounds such as benzonitrile and the like. Among these, methanol, ethanol, normal or isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, dimethyl carbonate, dimethylformamide, dimethylacetamide, acetonitrile, and benzonitrile are preferably used. Acetone and acetonitrile are particularly preferred.

  The poor solvent is not particularly limited. For example, ethers such as diethyl ether, diisopropyl ether, dioxane, and tetrahydrofuran; halogenated hydrocarbons such as chloroform and dichloromethane; aliphatic hydrocarbons such as normal hexane and normal heptane; Examples include aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane and cyclopentane; norbornene compounds such as ethylidene norbornene, vinyl norbornene, and dicyclopentadiene. Among these, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, normal hexane, normal heptane, and normal octane are preferably used, and diethyl ether is particularly preferable.

  The use ratio of the good solvent and the poor solvent is arbitrary, and if the amount of the good solvent for dissolving the precipitate is too large, crystals do not precipitate. On the other hand, if there are too many poor solvents, sufficient crystal growth cannot be achieved, so an appropriate amount is required. Accordingly, the good solvent / poor solvent has a volume ratio of preferably 0.001 to 1000, and more preferably 0.01 to 100.

  In the conventionally known method, impurities are generated in addition to the tungsten peroxide compound, and sorting is necessary while observing the crystal form using a microscope or the like. Therefore, it is difficult to manufacture industrially and the yield is low. It was. In addition, since the raw material containing halogen is used in the conventional method, it has been an industrially limited catalyst that the epoxy compound contains halogen. According to the method described herein, a tungsten peroxide compound can be easily produced in a high yield, and the resulting tungsten peroxide compound does not contain a halogen. Therefore, by using it as an epoxidation catalyst, a low halogen product can be obtained. It can be manufactured easily.

By the above method, for example, a tungsten compound represented by (R ₁ R ₂ R ₃ R ₄ N) ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)] is produced as the catalyst A-1. Can do. In the chemical formula, μ represents a bridging atom. The catalyst A-1 is not limited to the tungsten compound of this chemical formula as long as it is produced by the above method.

  In the epoxidation step, hydrogen peroxide is used as an oxidant for the epoxidation reaction. As hydrogen peroxide, it is preferable to use 10% to 70% hydrogen peroxide water from the viewpoint of safety and efficiency.

  In the epoxidation reaction, the ratio of hydrogen peroxide to the olefin compound is arbitrary, but the ratio of the number of moles of hydrogen peroxide to the total number of moles of olefin of the olefin compound is preferably 0.1 to 10. In addition, hydrogen peroxide may be supplied to the reaction system in an amount necessary for the initial stage of the reaction, or may be sequentially added to the reaction system.

  The amount of the catalyst (tungsten compound) in the epoxidation reaction can be used in an arbitrary amount of 0.01 mol% to 1000 mol%, preferably 0.05 mol% to 100 mol%, relative to the olefin amount of the olefin compound. .

  The epoxidation reaction may be performed in a one-phase system using a water-soluble organic solvent, or may be performed in a two-phase system using a water-insoluble organic solvent. A mixed system may be used.

  Examples of usable organic solvents include primary, secondary, and tertiary monohydric alcohols having 1 to 6 carbon atoms such as methanol, ethanol, normal or isopropanol, and tertiary butanol; ethylene glycol, propylene glycol, glycerin, Polyhydric alcohols such as diethylene glycol and triethylene glycol; Ethers such as ethyl ether, isopropyl ether, dioxane and tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetyl acetone; Methyl acetate, ethyl acetate, propyl acetate and isopropyl acetate , Esters such as n-butyl acetate, iso-butyl acetate, sec-butyl acetate, tert-butyl acetate, methyl benzoate; ethylene carbonate, propylene carbonate, etc., dimethyl carbonate Carbonates; nitrogen compounds such as dimethylformamide, dimethylacetamide, nitromethane, acetonitrile and benzonitrile; phosphorus compounds such as phosphate esters such as triethyl phosphate and diethylhexyl phosphate; halogenated hydrocarbons such as chloroform and dichloromethane; Aliphatic hydrocarbons such as hexane and normal heptane; aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane and cyclopentane; norbornene compounds such as ethylidene norbornene, vinyl norbornene, and dicyclopentadiene .

  Among these solvents, alcohols having 1 to 4 carbon atoms, chloroform, dichloromethane, hexane, heptane, nonane, indane, indene, hydrindan, acetonitrile, benzonitrile, dimethyl sulfoxide, dimethylformamide, ethyl acetate, propyl acetate, isopropyl acetate It is preferable to use dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, dimethyl carbonate, ethylene carbonate, propylene carbonate, or a mixture thereof.

  The solvent is removed from the reaction mixture by atmospheric distillation or vacuum distillation in a solvent removal step described later. At this time, it is desirable that the solvent is removed at a temperature at which the target epoxy compound is not distilled off. For this reason, a solvent having a boiling point lower than that of the epoxy compound is preferably used as the solvent.

  It is also possible to use a phase transfer catalyst or a surfactant in the epoxidation reaction. Although these are arbitrary compounds, More preferably, cetylpyridinium chloride, cetylpyridinium bromide, methyltrioctyl hydrogen sulfate, etc. are mentioned.

  The reaction temperature of the epoxidation reaction is preferably 0 ° C. or higher and 100 ° C. or lower, more preferably 10 ° C. or higher and 80 ° C. or lower. The reaction time is preferably 1 minute or more and 400 hours or less. More preferably, it is 60 minutes or more and 300 hours or less. Moreover, although reaction pressure is arbitrary, 20 atmospheres or less are preferable, More preferably, it is 10 atmospheres or less, and it can also react under reduced pressure.

(Solvent removal step)
In the solvent removal step, the solvent is removed from the reaction mixture obtained in the epoxidation step by atmospheric distillation or vacuum distillation.

  The distillation conditions in the solvent removal step can be appropriately changed according to the solvent used in the epoxidation reaction, but it is preferably 100 ° C. or lower, more preferably 80 ° C. or lower. When a solvent whose removal temperature in atmospheric distillation is higher than these suitable temperatures is used, the solvent is removed under reduced pressure. The degree of reduced pressure can be appropriately adjusted according to the boiling point of the solvent, and can be, for example, 20 kPa or less, more preferably 10 kPa or less.

  In the solvent removal step, it is not always necessary to remove all the solvent in the reaction mixture, and the solvent may be removed to such an extent that the reaction mixture can be applied to thin film distillation. The solvent removed in the solvent removal step can be reused as a solvent for the epoxidation reaction.

(First thin film distillation process)
In the first thin film distillation step, an unreacted olefin compound (optionally further a reaction intermediate) is separated from the reaction mixture that has undergone the solvent removal step by thin film distillation.

  The conditions of the thin film distillation in the first thin film distillation step can be adjusted as appropriate according to the olefin compound used. For example, when tetrahydroindene (boiling point 160 ° C.) is used as the olefin compound, the temperature is 80 ° C. and the pressure is 1 kPa. The raw material (unreacted olefin compound) and the reaction intermediate can be separated. In addition, examples of the reaction intermediate to be removed include tetrahydroindene monoepoxide.

(Second thin film distillation process)
In the second thin film distillation step, the epoxy compound is separated from the reaction mixture that has undergone the first thin film distillation step by thin film distillation.

  The conditions of the thin film distillation in the second thin film distillation step can be adjusted as appropriate according to the epoxy compound of the target product. For example, when tetrahydroindene (boiling point 160 ° C.) is used as the olefin compound, the temperature is 80 ° C. and the pressure is 220 Pa. The target product tetrahydroindene diepoxide can be separated under certain conditions.

(Catalyst extraction process)
In the epoxidation step, when a tungsten compound is used as a homogeneous catalyst, the tungsten compound used in the epoxidation reaction remains in the reaction mixture (distillation residue) that has undergone the second thin film distillation step. For this reason, when a tungsten compound is used as a homogeneous catalyst, the manufacturing method according to the present embodiment adds a hydrogen peroxide to the reaction mixture that has undergone the second thin film distillation step to extract the catalyst. May further be included.

  In the catalyst extraction step, for example, 10 to 70% hydrogen peroxide solution can be added to the distillation residue to recover the catalyst eluted in the aqueous phase. The recovered catalyst can be reused as a catalyst for the epoxidation reaction.

  FIG. 1 is a conceptual diagram showing an example of a manufacturing apparatus for carrying out the manufacturing method according to the present embodiment. In the manufacturing apparatus 1 of FIG. 1, the manufacturing process using a homogeneous catalyst can be implemented suitably.

  1 includes an epoxidation reaction tank 12, a hydrogen peroxide decomposition tank 13, a distillation column 14, a first thin film distillation column 15, a second thin film distillation column 16, and a catalyst separation and regeneration building. 17.

  In the manufacturing apparatus 1 of FIG. 1, the raw material olefin compound is introduced from the raw material tank 11 into the epoxidation reaction tank 12, and the epoxidation reaction is performed in the epoxidation reaction tank 12. The reaction mixture after the epoxidation reaction is supplied from the epoxidation reaction tank 12 to the hydrogen peroxide decomposition tank 13, and the hydrogen peroxide in the reaction mixture is decomposed in the hydrogen peroxide decomposition tank 13.

  The reaction mixture that has passed through the hydrogen peroxide decomposition tank 13 is introduced into the distillation column 14, and the solvent (organic solvent and water) is removed from the reaction mixture at normal pressure or reduced pressure. The removed solvent is separated into an organic solvent and water, and the organic solvent is recovered in the solvent storage tank T1, and the water is recovered in the separated water storage tank T2. The organic solvent recovered in the solvent storage tank T1 is optionally sent to the epoxidation reaction tank 12 and reused.

  The reaction mixture from which the solvent has been removed in the distillation column 14 is introduced into the first thin film distillation column 15, and in the first thin film distillation column 15, unreacted raw materials (in some cases, further reaction intermediates are obtained from the reaction mixture by thin film distillation). ) Are separated. The raw material separated in the first thin film distillation column 15 is collected in the raw material storage tank T3. The recovered raw material is optionally sent to the epoxidation reaction tank 12 for reuse.

  The reaction mixture from which the raw material has been separated in the first thin film distillation column 15 is introduced into the second thin film distillation column 16, and the second thin film distillation column 16 performs an epoxy compound as a target product from the reaction mixture by thin film distillation. Are separated. The separated epoxy compound is collected in the product tank T 4, while the residue after the epoxy compound separation is sent to the catalyst separation / regeneration building 17.

  The residue sent to the catalyst separation / regeneration building 17 is mixed with the hydrogen peroxide solution introduced from the hydrogen peroxide solution storage tank T5 and separated into two layers, an oil layer and an aqueous layer. The catalyst contained in the residue is dissolved in hydrogen peroxide water and extracted into an aqueous layer.

  The water layer separated in the catalyst separation / regeneration building 17 is extracted from the bottom side of the catalyst separation / regeneration building 17 and collected in the separated catalyst storage tank T6. On the other hand, the oil layer is extracted from the catalyst separation and regeneration building 17 after the water layer is extracted, and is recovered in the heavy material storage tank T7. The water layer recovered in the separation catalyst storage tank T6 is removed from the water in some cases and then sent to the epoxidation reaction tank 12 for reuse.

  FIG. 2 is a conceptual diagram illustrating another example of a manufacturing apparatus for performing the manufacturing method according to the present embodiment. In the manufacturing apparatus 2 of FIG. 2, the manufacturing process using the immobilized catalyst can be suitably performed.

  2 includes a raw material uniform tank 22, an epoxidation reaction tank 23, a hydrogen peroxide decomposition tank 24, a distillation tower 25, a first thin film distillation tower 26, and a second thin film distillation tower 27. With.

  In the manufacturing apparatus 2 of FIG. 2, the raw material epoxy compound is introduced from the raw material tank 21 into the raw material uniform tank 22, and the reaction solution is uniformly mixed in the raw material uniform tank 22.

  The reaction solution uniformly mixed in the raw material uniform tank 22 is introduced into an epoxidation reaction tank 23 provided with an immobilized catalyst, and an epoxidation reaction is performed in the epoxidation reaction tank. The reaction mixture after the epoxidation reaction is supplied from the epoxidation reaction tank 23 to the hydrogen peroxide decomposition tank 24, and the hydrogen peroxide in the reaction mixture is decomposed in the hydrogen peroxide decomposition tank 24.

  The reaction mixture that has passed through the hydrogen peroxide decomposition tank 24 is introduced into the distillation column 25, and the solvent (organic solvent and water) is removed from the reaction mixture at normal pressure or reduced pressure. The removed solvent is separated into an organic solvent and water, and the organic solvent is recovered in the solvent storage tank T11 and the water is recovered in the separated water storage tank T12. The organic solvent recovered in the solvent storage tank T11 is optionally sent to the raw material uniform tank 22 and reused.

  The reaction mixture from which the solvent has been removed in the distillation column 25 is introduced into the first thin film distillation column 26, and in the first thin film distillation column 26, unreacted raw materials (in some cases, further reaction intermediates are obtained from the reaction mixture by thin film distillation). ) Are separated. The raw material separated in the first thin film distillation column 26 is recovered in the raw material storage tank T13. In some cases, the recovered raw material is sent to the raw material uniform tank 22 and reused.

  The reaction mixture from which the raw materials have been separated in the first thin film distillation column 26 is introduced into the second thin film distillation column 27, and the second thin film distillation column 27 performs the epoxy compound as the target product from the reaction mixture by thin film distillation. Are separated. The separated epoxy compound is collected in the product tank T14, while the residue after separation of the epoxy compound is sent to the heavy material storage tank T15.

[Confirmation test]
As confirmation test 1, an epoxidation reaction according to the production process by the production apparatus 1 of FIG. In addition, as confirmation test 2, an experiment simulating a manufacturing process in which thin film distillation is not performed was performed. The results of confirmation tests 1 and 2 are shown below.

(Confirmation test 1)
In a 20 L flask, 120.2 g (1.0 mol) of tetrahydroindene (hereinafter referred to as “THI”) and 5 L of acetonitrile are introduced and uniformly diffused, and 227.0 g (307.0% hydrogen peroxide) is added thereto. 2.0 mol), and _{[(n-C 4 H 9} ) 4 n] 2 [{WO (O 2) 2} 2 (μ-O)] was added 5 mol% as a catalyst.

_{Incidentally, [(n-C 4 H} 9) 4 N] 2 [{WO (O 2) 2} 2 (μ-O)] was prepared in the following manner. First, 1 g of tungstic acid was stirred in 10 ml of 30% hydrogen peroxide solution for 1.5 hours to obtain a white suspension (A). 4 ml of 1M aqueous solution of tetrabutylammonium hydroxide was added to this suspension solution (A) to obtain a light yellow suspension solution (B). Insoluble matter was filtered through membrane cellulose acetate, and the filtrate was concentrated to 2 ml. When this solution was added dropwise to a diethyl ether / isopropyl alcohol (150 ml / 20 ml) solution, a pale yellow powder (C) was produced. The powder (C) was separated by filtration and washed with diethyl ether to obtain 1.4 g of a white powder (D). After 0.5 g of white powder (D) was dissolved in acetone, this solution was put into a screw tube and diethyl ether was slowly laminated. When this was left still in the refrigerator for 1 day, 0.37 g of plate crystals (E) were obtained. The yield of (E) relative to (D) was 75%, and the overall yield was 52%. This crystal (E) was recovered and measured by IR to confirm that it was [(n-C ₄ H ₉ ) ₄ N] ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)].

  The reaction solution was reacted at room temperature for 24 hours with stirring. When the reaction solution after the reaction was measured using gas chromatography (GC), the THI conversion rate was 81.7%, the monoepoxide yield was 36.7%, and the diepoxide yield was 38.6%.

  After γ-alumina was added to the reaction solution after the reaction to decompose hydrogen peroxide, γ-alumina was removed. Thereafter, the solvent was distilled off by distillation under reduced pressure at 30 ° C. and 10 kPa. After the distillation, a viscous yellowish transparent liquid remained and its weight was 245.3 g.

  Thereafter, thin film distillation (first time) was performed under conditions of a temperature of 80 ° C. and a pressure of 1 kPa. The total amount of the solution after the distillation was 71 g, and the breakdown was 20.1 g of THI, 45.0 g of monoepoxide, and 6.0 g of diepoxide.

  The solution after the thin film distillation was subjected to the thin film distillation (second time) again under the conditions of a temperature of 80 ° C. and a pressure of 220 Pa. The total amount of the solution after the distillation was 36.0 g, and the breakdown was 0.5 g of monoepoxide and 35.5 g of diepoxide. The solution obtained after the second thin film distillation had a diepoxide purity of 98.6%, and it was possible to recover 60.4% of the diepoxide produced after the reaction.

  To the distillation residue remaining after the second thin film distillation, 227.0 g of 30% hydrogen peroxide was added and stirred. After removing the insoluble matter, the reaction was carried out by adding THI, confirming the formation of epoxide and confirming that the catalyst could be reused.

(Confirmation test 2)
The test was conducted in the same manner as in Confirmation Test 1 until the solvent was distilled off under reduced pressure. When the solvent was distilled off and vacuum distillation was performed at a pressure of 220 Pa, only a small amount of distillate was obtained. Further, when the temperature was raised to 140 ° C. in order to obtain a sufficient distillate amount, the distillate solution turned black, and a sufficiently purified diepoxide could not be obtained.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment. For example, one aspect of the present invention is a method for purifying a reaction mixture containing an epoxy compound, and another aspect of the present invention is an epoxy compound obtained by the above production method.

  The method for producing an epoxy compound according to the present invention can obtain an epoxy compound in a high yield using a tungsten peroxide compound as a catalyst, and can be suitably applied to an industrial production process.

DESCRIPTION OF SYMBOLS 1, ... Epoxy compound manufacturing apparatus, 11 ... Raw material tank, 12 ... Epoxidation reaction tank, 13 ... Hydrogen peroxide decomposition tank, 14 ... Distillation tower, 15 ... First thin film distillation tower, 16 ... Second thin film distillation Tower 17, catalyst separation / regeneration building, 21 raw material tank, 22 raw material uniform tank, 23 epoxidation reaction tank, 24 hydrogen peroxide decomposition tank, 25 distillation tower, 26 first film distillation tower, 27 ... second thin film distillation column.

Claims (6)

An epoxidation step of obtaining a reaction mixture containing an epoxy compound by an epoxidation reaction of an olefin compound using a tungsten peroxide compound as a catalyst and hydrogen peroxide as an oxidizing agent;
A solvent removal step of removing the solvent from the reaction mixture by atmospheric distillation or vacuum distillation;
A first thin film distillation step of separating the unreacted olefin compound by thin film distillation from the reaction mixture that has undergone the solvent removal step;
A second thin film distillation step of separating the epoxy compound by thin film distillation from the reaction mixture that has undergone the first thin film distillation step;
The manufacturing method of an epoxy compound which has these.   The method for producing an epoxy compound according to claim 1, further comprising a catalyst extraction step of extracting the catalyst by adding hydrogen peroxide to the reaction mixture that has undergone the second thin film distillation step.   The method for producing an epoxy compound according to claim 1 or 2, wherein the olefin compound is an alicyclic olefin.   The method for producing an epoxy compound according to claim 3, wherein the alicyclic olefin is tetrahydroindene.   The manufacturing method of the epoxy compound as described in any one of Claims 1-4 which performs the said solvent removal process at 80 degrees C or less.   The manufacturing method of the epoxy compound as described in any one of Claims 1-5 which performs the said solvent removal process at 10 kPa or less.

Images