JP2003012659A - Method for refining epoxidation reaction crude liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for refining an epoxidation reaction crude liquid obtained by epoxidation using an organic peracid comprising the step of selectively removing/separating minute metallic components such as sodium and water remaining in making a washing with water/neutralization treatment of the organic peracid or acidic matter left in the reaction crude liquid to effect the minute metallic components content to <=1 ppm and the minute water content to <=0.1 wt.% and enable product purity and thermosetting function to be kept stable under a wide range of operating conditions. SOLUTION: This method for refining an epoxidation reaction crude liquid synthesized by epoxidation using an organic peracid comprises the steps of making a washing with water/neutralization treatment of the crude liquid and then making a separation treatment of the residual water in the crude liquid using a coalescer to effect the residual minute metallic components content of the crude liquid to <=1 ppm.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for purifying a crude epoxidation reaction liquid obtained by epoxidizing a cyclohexene compound or the like using an organic peracid, and more specifically,
The present invention relates to a purification method for neutralizing and washing with water an organic peracid or the like remaining in the crude liquid for epoxidation reaction and then separating and reducing trace metals and trace moisture in the crude reaction liquid to be introduced into a specific treatment step.

[0002]

2. Description of the Related Art When an epoxidized derivative is produced from an unsaturated organic compound using an organic peracid, the component produced in the reaction step is a compound having a property of being extremely easily polymerized. Residual organic peracids and other acidic substances are factors that cause polymerization. For example, when an organic peracid or organic acid is present in the crude reaction liquid when purifying and distilling the crude epoxidation reaction liquid, polymerization or side reaction of the epoxy compound occurs at the bottom of the distillation column, and the desired epoxy compound is collected. The rate and quality are reduced. For this reason, conventionally
These residual organic peracids and organic acids were extracted, further neutralized and washed with water, and then removed by static separation with a decanter.

However, according to this method of static separation, not only the trace components as impurities and water cannot be stably separated and removed depending on the washing temperature and the mixed state of the liquid, but also trace components in the product fluctuate. Therefore, there is a problem that product performance is also affected. In particular, in the conventional method, it is extremely difficult to remove trace components in the reaction crude liquid to the order of 1 ppm or less in producing the epoxidized derivative, and a considerable amount of water remains in the reaction crude liquid. There is also a problem that the product purity is lowered and, for example, the thermosetting performance of the epoxidized derivative is lowered. Further, when the reaction crude liquid and water are mixed to a state close to that of an emulsion, it is extremely difficult to remove water and remove and separate trace components.

The object of the present invention is to purify an epoxidation reaction crude liquid obtained by epoxidizing an unsaturated organic compound such as a cyclohexene compound with an organic peracid, and to purify an organic peracid or other organic peroxides remaining in the reaction crude liquid. The acidic substance (simply referred to as "acidic substance") is neutralized and / or washed with water (in this specification, referred to as "neutralization / water washing" in any order) to be removed. Selectively removes and separates trace metal components such as sodium and trace moisture remaining in the product to reduce trace metal components to 1 ppm or less and trace moisture to 0.1 wt% or less. Product purity over a wide range of operating conditions Another object of the present invention is to provide a refining method capable of improving the hue of a product and keeping the heat curing, performance and hue of the obtained product stable.

[0005]

Means for Solving the Problems The present inventors have completely neutralized and washed with water an organic peracid and an acidic substance remaining in a reaction crude liquid obtained by epoxidation of a cyclohexene compound with an organic peracid, For the separation and removal of trace amounts of water that cannot be removed into water and trace metals that are substantially derived from neutralization, the order and number of times of neutralization and water washing, various removal and separation devices, concentration of residual components, application temperature, and product purity. , The hue, the thermosetting performance, etc. were earnestly studied. as a result,
Before distilling the reaction crude liquid, a trace amount of water remaining in the reaction crude liquid is aggregated, and alkali metals such as sodium remaining in the reaction crude liquid are aggregated together with a trace amount of water and separated and removed by a hydrophobic separator. Then, it was found that the trace component concentration can be maintained at a level of 1 ppm or less. By distilling the reaction crude liquid after removing the trace components, product purity is kept high, product hue is improved, product performance such as thermosetting property is dramatically improved, and stable manufacturing operation can be performed. The inventors have found that the above problems can be solved and completed the present invention.

That is, the first aspect of the present invention is to neutralize and wash the epoxidation reaction crude liquid obtained by epoxidation of an unsaturated organic compound with an organic peracid, and then to separate water by a coalescer. The present invention provides a method for purifying an epoxidation reaction crude liquid, characterized in that the metal content remaining in the reaction crude liquid is 1 ppm or less.
A second aspect of the present invention is to provide a method for purifying the first epoxidation reaction crude liquid of the present invention in which the unsaturated organic compound is a cyclohexene compound. The third aspect of the present invention is
The cyclohexene compound is a compound selected from 3-cyclohexenylmethyl-3-cyclohexenecarboxylate, 3-cyclohexenylmethyl (meth) acrylate, or a lactone adduct thereof, and the second invention is characterized in that A method for purifying a crude liquid of an epoxidation reaction is provided. A fourth aspect of the present invention is to provide a method for purifying an epoxidation reaction crude liquid according to the first to third aspects of the present invention, wherein the organic peracid is peracetic acid. Further, a fifth aspect of the present invention is a coalescer filter having a coalescer element for coagulating water in the crude liquid for epoxidation reaction and a hydrophobic filter element. The present invention provides a method for purifying a crude liquid of any epoxidation reaction. In a sixth aspect of the present invention, after extracting an organic peracid from the crude liquid for the epoxidation reaction, the residual organic peracid and the acidic substance are neutralized and washed with water, and then the neutralized and washed with water. The first aspect of the present invention is characterized in that residual water is aggregated by a coalescer element and selectively separated by a hydrophobic filter element so that a residual metal content is 1 ppm or less.
The method for purifying a crude liquid of an epoxidation reaction according to any one of 1 to 5 is provided. Further, a seventh aspect of the present invention provides a method for purifying an epoxidation reaction crude liquid according to any one of the first to sixth aspects of the present invention, which is characterized by further distilling after the separation treatment by a coalescer. The eighth aspect of the present invention is to provide an epoxidized cyclohexene compound having a water content of 0.02 wt% or less and a metal content of 0.5 ppm or less.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The reaction crude liquid used in the present invention is
It is a reaction crude liquid obtained by epoxidizing an unsaturated organic compound with an organic peracid. Examples of the unsaturated organic compound include unsaturated alicyclic compounds, aromatic compounds having an unsaturated group in the side chain, and the like, preferably cyclohexene compounds, (i) 3-cyclohexenyl methyl acrylate or the Lactone adduct, (b) 3-cyclohexenylmethyl methacrylate or a lactone adduct thereof,
(C) 3-cyclohexenylmethyl-3-cyclohexene carboxylate or a lactone adduct thereof, (D)
Examples thereof include vinylcyclohexene and (e) α-pinene compounds. Examples of the lactone include ε-caprolactone, trimethyl-ε-caprolactone, monomethyl-ε
-Caprolactone, γ-butyrolactone, δ-valerolactone and the like can be mentioned, and among them, ε-caprolactone is preferable in terms of versatility.

As a reaction crude liquid using these, 3,4-epoxycyclohexylmethyl acrylate or its ε-is obtained by epoxidizing the above (a) 3-cyclohexenylmethyl acrylate or its ε-caprolactone adduct with an organic peracid. A crude reaction liquid for producing a caprolactone adduct, (b) 3-cyclohexenylmethyl methacrylate or its ε-caprolactone adduct is epoxidized with an organic peracid to give 3,4-epoxycyclohexylmethyl methacrylate or its ε-caprolactone adduct. Crude liquid for producing a product, (c) 3-cyclohexenylmethyl-3-cyclohexenecarboxylate or its ε-
Epoxidation of a caprolactone adduct with an organic peracid gives 3,
A crude reaction liquid for producing 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or its ε-caprolactone adduct, (2) vinylcyclohexene is epoxidized with an organic peracid to produce vinylcyclohexene monoepoxide. Reaction crude liquid (e) in the case of producing an α-pinene oxide by epoxidizing α-pinene with an organic peracid, 1-methyl-
There is a crude reaction liquid in the case of producing dipentene diepoxide by epoxidizing 4-isopropenyl-1-cyclohexene (hereinafter abbreviated as “dipentene”) with an organic peracid. Further, a reaction crude solution in the case of producing styrene oxide by epoxidizing a styrene monomer with an organic peracid, a reaction crude solution in producing an epoxidized polybutadiene by epoxidizing a hydroxyl group-terminated polybutadiene with an organic peracid, and the like can be mentioned. In addition to the above, the purification method of the present invention can also be applied to a reaction crude liquid in the case of oxidizing pentylcyclohexanone with an organic peracid to produce 0-decalactone.

The cyclohexene compound will be described below as an example. Examples of the organic peracid used for epoxidizing the cyclohexene compound include performic acid, peracetic acid, perpropionic acid, m-chloroperbenzoic acid, trifluoroperacetic acid, and perbenzoic acid. For the epoxidation, an organic peracid and a catalyst may be used in combination. For example, an alkali such as sodium carbonate or an acid such as sulfuric acid may be used as a catalyst.

The molar ratio of the organic peracid to the double bond of the cyclohexenyl compound is theoretically 1/1, but usually 0.5 to 3.
It is preferable to use 0 times mol, particularly 1.0 to 1.5 times mol. Since cyclohexenyl compounds are more expensive than organic peracids, it often takes time to recycle raw materials, and organic peracids are decomposed in the reaction, albeit in small amounts, the theory of organic peracids It is preferable to use a little more than the amount.

The reaction may be performed in the presence of a solvent. The addition of a solvent has the effects of decreasing the viscosity of the reaction crude liquid, stabilizing the reaction by diluting the organic peracid, and further slowing the reaction rate between the organic acid and the epoxy group. Examples of usable solvents include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, isopropylbenzene, diethylbenzene, p-cymene, and aliphatic hydrocarbons such as cyclohexane, n-hexane, heptane, octane, nonane, decane, and decalin. Alicyclic hydrocarbons, cyclohexanol, hexanol, heptanol, octanol, nonanol, alcohols such as furfuryl alcohol, acetone,
Methyl ethyl ketone, ketones such as cyclohexanone, ethyl acetate, n-amyl acetate, cyclohexyl acetate, isoamyl propionate, esters such as methyl benzoate,
Polyhydric alcohols such as ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether, and their derivatives, chloroform, dimethyl. A halogen compound such as chloride, carbon tetrachloride and chlorobenzene, an ether compound such as 1,2-dimethoxyethane and the like can be used. The amount of the solvent used is usually 0.1 to 10 times the weight of the cyclohexene compound, and especially 0.1.
The weight is preferably 5 to 3.0 times. If it is less than 0.5 times the weight, the effect of stabilizing the reaction is small,
On the contrary, if the amount is more than 3 times the weight, the effect of stabilizing the reaction does not increase so much, and the recovery of the solvent requires a large amount of money, which is wasteful.

When carrying out the epoxidation reaction, a polymerization inhibitor may be added if necessary. As the polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, cresol, t-butylcatechol, 2,4-dimethyl-6-t-butylphenol, 2-t-butyl-4-methoxyphenol, 3-t.
-Butyl-4-methoxyphenol, 2,6-di-t-
Butyl-p-cresol, 2,5-dihydroxy-p-
Quinone, piperidine, ethanolamine, α-nitroso-β-naphthol, diphenylamine, phenothiazine, N-nitrosophenylhydroxylamine, N, N
-Diethylhydroxylamine and the like can be used. These may be used alone or in combination of two or more.

If necessary, ammonium hydrogenphosphate, potassium pyrophosphate, pyrophosphate-2-ethylhexyl ester, potassium pyrophosphate-2-ethylhexyl ester, sodium pyrophosphate-2-ethylhexyl are used as stabilizers for organic peracids, if necessary. Ester, tripolyphosphoric acid, potassium tripolyphosphate, sodium tripolyphosphate, tripolyphosphoric acid-2-ethylhexyl ester, tripolyphosphoric acid potassium-2-ethylhexyl ester,
Tetrapolyphosphoric acid, potassium tetrapolyphosphate, sodium tetrapolyphosphate, tetrapolyphosphoric acid-2-ethylhexyl ester, tetrapolyphosphoric acid potassium-2-ethylhexyl ester, sodium tetrapolyphosphate-
2-Ethylhexyl ester, potassium hexametaphosphate, sodium hexametaphosphate and the like can be used. These may be used alone or in combination of two or more.

The reaction temperature for the epoxidation is set to an upper limit value or lower so that the epoxidation reaction has priority over the decomposition reaction of the organic peracid. For example, when peracetic acid is used as the organic peracid, the temperature is preferably 0 to 70 ° C or lower. Reaction temperature is 0 ℃
If it is lower, it takes a long time to complete the reaction. Therefore, when peracetic acid is used, it is preferable to perform the reaction at 0 ° C. or higher. Further, in the case of an organic acid produced as a by-product of an organic peracid during the epoxidation reaction, when a side reaction in which the epoxy group is ring-opened occurs, the temperature at which the side reaction amount is reduced in advance is the temperature as described above. Select from the area and implement.

The reaction pressure is generally operated under normal pressure, but it can be carried out under pressure or under reduced pressure. Further, the reaction is carried out in a continuous system or a batch system, and in the case of the continuous system, a piston flow type is preferable. In the case of batch method,
The organic peracid is preferably a semi-batch system in which the organic peracid is charged sequentially. To sequentially charge the organic peracid in a semi-batch method, a cyclohexene compound and a reaction solvent to be used are charged in a predetermined amount in a reaction vessel, and a catalyst and a stabilizer of the organic peracid are dissolved therein, if necessary. The organic peracid is added dropwise to this. To confirm the end point of the reaction, the concentration of the remaining organic peracid is measured by a titration method or the like.

As a water washing method for washing the epoxidation reaction crude liquid obtained by epoxidizing the cyclohexene compound with an organic peracid as described above, a device such as a mixer-settler type or an extraction tower may be used. A centrifugal extractor may be used to shorten the contact time between the epoxy compound and the organic acid or water. The ratio of washing water and reaction crude liquid is
Washing water / reaction crude liquid = preferably in the range of 0.1 to 3, particularly preferably in the range of 1 to 2. It is necessary to perform the washing temperature within a range that maintains the difference in specific gravity required for liquid separation between the water layer and the organic layer, and if the liquid separation performance is poor even if the water washing temperature is adjusted, add a solvent to secure the specific gravity. To do.

The reaction crude liquid that has been washed with water is neutralized by adding an appropriate amount of an alkaline aqueous solution to an acidic substance in an alkaline neutralization tank or the like. As the alkaline aqueous solution, a 6 to 10 wt% aqueous solution of sodium hydroxide is usually used in about the same weight as the reaction crude liquid, but is not limited thereto. The reaction crude liquid that has been washed and neutralized is conventionally purified by distillation, but in the present invention, it is separated by the coalescer according to the present invention before the distillation of the reaction crude liquid. The order of the neutralization treatment and the water washing treatment may be either the water washing treatment or the neutralization treatment, depending on the respective concentrations of the residual substances in the epoxidation reaction crude liquid, or one of them may be used. Of course, the number of times of washing with water may be increased.

A step of extracting the organic peracid may be provided prior to the neutralization and washing with water. Examples of this extraction process include a centrifugal extractor, a mixer / settler extractor, a countercurrent differential type extraction column, and a stirred / non-stirred staged extraction column.

The coalescer according to the present invention is a reaction crude liquid which cannot be removed when the organic peracid and the acidic substance remaining in the epoxidation reaction crude liquid are washed with water as described above and further neutralized. It agglomerates trace metals and trace amounts of water and selectively separates them. The coalescer may be a multi-layer filter having a pore size of 1 to 50 microns and may be, for example, an ultrafine fiber layer, or a layered filter having a pore size varied in the thickness direction. In addition, a so-called filter bed coalescer, a tubular filtration unit composed of a lipophilic filter and a hydrophilic filter, a tubular coalescer filter composed of a hydrophilic filter and a hydrophobic filter, or a so-called outer and inner cylinder charged with an electric field. A charge aggregation coalescer or the like may be used. That is, it is called a coalescer filter or simply a coalescer.

Further, it may be an integrated coreless / separator in which a coreless element for coagulating a small amount of water and a hydrophobic separator element for separating coagulated water are vertically integrated. In this case, a liquid / liquid emulsion state, for example, a reaction crude liquid of water-containing oil flows from the inside to the outside in the coalescer element, and when the water droplet of a trace amount of water passes through the layer of the coalescer element, the water droplet and the water droplet are combined. Then grows large and aggregates. The hydrophobic separator element flows from the outside to the inside, and since the separator is a hydrophobic filter, most of the reaction crude liquid enters the inside because it is oily, but aggregated water droplets are discharged without entering and a high-quality reaction from the inside. On the other hand, the crude liquid is separated and discharged from the outside by the coagulated water containing trace metals. Of course, a plurality of these coalescers may be provided in parallel depending on the amount of the reaction crude liquid to be treated.

The trace metal content after the separation treatment with the coalescer is set to 1 ppm or less. When it exceeds 1 ppm, the product purity and thermosetting performance decrease, the insulating property of the electronic material product decreases, and the material hardness decreases. Because it does. Further, the lower the lower limit, the more preferable, but 0.001 ppm is practically used. This is because if it is less than 0.001 ppm, it takes too much time for production and is not practical. Moreover, the trace amount of water is set to 0.1 wt% or less. When it exceeds 0.1 wt%, the product purity and the thermosetting performance are lowered, the insulating property of the product for electronic materials is lowered, and the material hardness is lowered. Because. In addition, it is needless to say that the lower limit is lower, but practically, it is 0.001 wt%. 0.001w
This is because if it is less than t%, it takes too much time for production and is not practical. The product purity is preferably 94 wt% or more.

Further, the coalescer may be provided with a prefilter for removing solid components in advance as a pretreatment on the upstream side of the apparatus. With this, the life of the apparatus is extended, and the solid component and other components in the reaction crude liquid are separated to improve the quality of the reaction crude liquid.
It destroys the liquid / liquid emulsion state in the crude reaction liquid, facilitating water aggregation and its separation and removal.

[0023]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. (Example 1) FIG. 1 is a diagram showing a flow of a method for purifying a crude liquid of an epoxidation reaction according to the present invention. 11 is a reactor, 12 is a centrifugal extractor, 13 is an alkali neutralization tank, and 15 is a coalescer filter. Integrated coalescer / separator, 16
Is a distillation column consisting of a thin film evaporator. The reactor 11 is a jacketed SUS316 container having a stirrer 18 and has a volume of 15 m ³ . First, in the reactor 11, 2,000 kg of 3-cyclohexenyl methyl acrylate (hereinafter abbreviated as CHAA) which is a cyclohexene compound, 7,400 kg of ethyl acetate, 600 g of hydroquinone monomethyl ether as a polymerization inhibitor, and sodium tripolyphosphate as a stabilizer. 20% ethyl acetate (60% acetic acid
8.4 kg of a solution (containing wt%) was added and the temperature was raised to an internal temperature of 37 ° C. And 30 peracetic acid, which is an organic peracid
3,751 kg of a wt% ethyl acetate solution was added dropwise over 5 hours, followed by aging for 3 hours. The internal temperature was kept at 40 ° C. during the dropping and aging. Thus, the epoxy compound synthesized by the epoxidation method with an organic peracid is 3,
13,160 kg of an epoxidation reaction crude liquid containing 4-epoxycyclohexylmethyl acrylate (hereinafter abbreviated as CYM-A200) at a concentration of 18 wt% was obtained.

Next, the crude liquid for epoxidation reaction containing CYM-A200 is supplied from the light liquid inlet 12a of the centrifugal extractor 12, while the washing liquid is washed from the water injection port 12b = washing liquid / reaction crude liquid = 1.5. And then wash with water. As a result, 790 kg of reaction crude liquid which is light liquid from the light liquid outlet 12c
/ Hr, 1350 kg / hr of heavy liquid from the heavy liquid outlet 12d
Got The reaction crude liquid, which is a light liquid, contains 0.001 wt% and 0.25 wt% of peracetic acid and acetic acid, respectively.
Then, in order to neutralize the acidic substances remaining in the reaction crude liquid of the light liquid, the reaction crude liquid is fed to the injection port 13 of the alkali neutralization tank 13.
In addition, 10 wt% -alkali aqueous solution (sodium hydroxide aqueous solution) is injected into the alkali neutralization tank 13 at a ratio of alkali aqueous solution / crude reaction liquid = 0.57.
Inject from 3b to neutralize. Neutralized reaction crude liquid 676k
Water content is 3.5 wt% and sodium content is 10 in g / hr.
ppm is included.

The neutralized reaction crude liquid is taken out from the take-out port 13c, and is fed from the injection port 15a of a coalescer filter 15 (not shown in the figure) having a pre-filter which is a coalescer according to the present invention. Flow rate 676 kg
/ Hr, and trace amounts of water and trace metals were separated. As the coalescer filter 15, “Aquasep coalescer” manufactured by Nippon Pole Co., Ltd. was used.

The coalescer filter 15 is composed of a tubular coalescer element for aggregating water and a hydrophobic tubular separator element for separating agglomerated water, which are integrated vertically, and the reaction crude liquid is a tubular coalescer. The element passes from the inside to the outside, and the tubular separator element passes from the outside to the inside. At this time, the trace amount of water suspended in the reaction crude liquid dissolves trace metals, especially alkali metals such as sodium ions, and when passing through micron-class ultrafine pores of the coalescer element from inside to outside. , A trace amount of water emulsion is broken and aggregates to grow into large water droplets.

Then, when the water droplets containing trace metals pass through the hydrophobic separator element located below the coalescer element from the outside to the inside, they are blocked by the hydrophobic filter and descend outside the filter element. It is discharged to the outside through the lower discharge port 15b. On the other hand, the oily reaction crude liquid passes from the outside to the inside of the hydrophobic separator element to become a high-quality reaction crude liquid from which trace water and trace metals have been removed, and is discharged from the discharge port 15c, which is the thin film of the distillation column 16 in the next step. Injected into the evaporator. The reaction crude liquid treated with the coalescer filter 15 has a residual trace water content of 2.5.
The residual sodium concentration was wt% and the concentration was 0.1 ppm, and it was possible to greatly reduce these, especially the residual sodium, as compared with before using the coalescer filter 15. It is considered that the significant decrease in sodium content compared to water content is due to the filtering effect of the prefilter and coalescer.

Next, the reaction crude liquid taken out from the outlet 15c of the coalescer filter 15 is purified by a two-stage thin film evaporator which is the distillation column 15 at 770 kg / hr to remove low boiling components from the upper portion. Then, the purified product was continuously taken out from the lower part. Product color (APH
(A) was 60, which was excellent. The residual water content is 0.
Excellent results were obtained with the residual sodium concentration of not more than 02 wt% and 0.5 ppm. In addition, APHA was based on the standard oil and fat analysis test method (JIS K-1557). The smaller the numerical value, the better the hue level.

Also, 1 g of the product was added to 10 with normal heptane.
The diluted solution was dried under reduced pressure at 5 Torr and 50 ° C. for 1 hour, the weight of the filter paper was weighed, and the residue was calculated as the weight% in the sample (hereinafter referred to as heptane test).
It was stable at 0.02 wt% or less. Further, the distillation column 16 was continuously operated for 5 days, and the product purity was 97.
It was 7 wt% or more, APHA was in the range of 60 to 70, and was stable. In addition, the production of polymer in the thin film evaporator was small and stable operation was possible.

Comparative Example 1 In Comparative Example 1, in the method for purifying the crude liquid for epoxidation reaction in Example 1, coalescer filter 1 which is an integrated coalescer / separator is used.
This is the case where 5 is not used. That is, as shown in FIG.
The reaction crude liquid taken out from the reactor 11 is the centrifugal extractor 1.
After being washed with water 2 and then neutralized in the alkaline neutralization tank 13, the same procedure as in Example 1 was carried out except that the solution was directly injected into the distillation column 16 through the outlet 13c. In this case, a trace amount of water in the crude reaction liquid at the outlet 13c of the alkali neutralization tank 13,
Sodium concentration is 4.6wt% and 1.8ppm respectively
Met. In addition, the product after purification in the distillation column 16 APHA
Is 100 or more, sometimes fluctuates to about 150, residual water content is 0.04 wt%, residual sodium concentration is 8 to 15 ppm
Became. A further heptane test showed that it was 0.
It became 07 wt%. And CYM- which is extremely easy to polymerize
A200 could not be stably produced, and a large amount of a polymer was produced in the thin film evaporator during continuous operation for 2 days.

(Example 2) In Example 2, although the reaction crude liquid was different, in Example 1 shown in FIG. 1, the neutralization treatment was performed before the water washing treatment, and the capacity of the reactor was changed. Is 1 m ³ . First, as a cyclohexene compound, 119 kg of an adduct obtained by adding ε-caprolactone to 1 mol of 3-cyclohexenylmethyl-3-cyclohexenecarboxylate at a ratio of 1 mol.
Was charged into the reactor 11, and then ethyl acetate was diluted with 381 liters, and the temperature was kept constant at 40 ° C. for 30 w.
70% of 198 liters of ethyl acetate solution containing t% peracetic acid
The reaction was carried out by dropping at a rate of 1 / hr.

Then, 3-cyclohexenylmethyl-3
A cyclohexenecarboxylate ε-caprolactone adduct, a diepoxide (hereinafter abbreviated as CEL), of 25
A reaction crude liquid containing wt% was obtained. The resulting reaction crude liquid contained about 1.0 wt% peracetic acid and 6 wt% acetic acid.

Next, this reaction crude liquid was transferred to an alkali neutralization tank, neutralized with 213 liters of a 10 wt% sodium hydroxide aqueous solution at 40 ° C., and allowed to stand and separate. By neutralization, a reaction crude liquid containing 0.4 wt% of peracetic acid and 2.2 wt% of acetic acid was obtained.

The neutralized reaction crude liquid was transferred to a centrifugal extractor, washed with 236 liters of water, and then washed with ethyl acetate 1
00 liters were charged, washed with water at 40 ° C., and allowed to stand to separate a light liquid and a heavy liquid. Such washing with water was repeated three times to obtain a reaction crude liquid which was a light liquid and washed with water. The residual sodium concentration in the reaction crude liquid was 300 ppm, and the residual water content was 1.0 w.
It was t%.

Then, the reaction crude liquid washed with water has a flow rate of 7
A trace amount of water and trace metals were separated by an integrated coalescer / separator (the same as that used in Example 1) which is the coalescer filter 15 at 7.5 kg / hr. After passing through the integrated coalescer / separator 15, the residual sodium concentration is 0.5 ppm and the residual water content is 0.002 wt%.
Therefore, trace metals and residual water could be significantly reduced.

The reaction crude liquid that has passed through the coalescer filter 15 is fed to the thin film evaporator, which is the distillation column 16, at 55 liters / hour.
After charging with r and heating and concentrating at 150 ° C. under 9.3 KPa, purification was performed, and stable operation could be performed without generation of polymerization components. The residual sodium concentration in the purified product was 0.5 ppm and the water content was 0.01 wt%, and a stable product could be obtained. Aromatic sulfonium salt-based cationic polymerization catalyst (trade name "SAN-AID SI-60L", manufactured by Sanshin Chemical Industry Co., Ltd.) based on 100 parts by weight of the obtained product.
Was blended in an amount of 0.3 parts by weight and heat-cured in a dryer at 100 ° C. for 15 minutes. The Shore D hardness according to JIS K-7215 of the cured product was 50 or more.

(Comparative Example 2) In Comparative Example 2, in the method for purifying the crude liquid for epoxidation reaction in Example 2, the coalescer filter 1 which is an integrated coalescer / separator is used.
5 was not used, and the reaction crude liquid washed with water in Example 2 was treated in the same manner as in Example 2 except that it was directly injected into the distillation column 16 from the outlet. in this case,
The residual sodium concentration of the reaction crude liquid washed with water is 300p.
The pm and water content were 0.5 to 1.0 wt%. And
The residual sodium concentration in the product purified by the distillation column 16 without passing through the coalescer filter was around 3 to 15 ppm, and the sodium concentration was not constant and the operation was unstable. The obtained product was subjected to a thermosetting test in the same manner as in u Example 2. As a result, the Shore D hardness was 25, which was lower than that of Example 2 by 20 or more. In addition, white precipitates that were considered to be derived from sodium were confirmed on the surface of the cured resin.

[0038]

As described above, according to the present invention,
In the production of derivatives from organic peracids, trace metal components such as sodium and water remaining when the organic peracids or acidic substances remaining in the reaction crude liquid are washed and neutralized can be selectively removed and separated. The residual trace metal component can be 1 ppm or less, and the residual trace water content can be 0.1 wt% or less. Further, the product purity and the product hue can be significantly improved under a wide range of operating conditions, the thermosetting performance of the product can be stably maintained, and a stable refining operation can be performed.

[Brief description of drawings]

FIG. 1 is a diagram showing a flow of a first embodiment of the present invention.

FIG. 2 is a diagram showing a flow of Comparative Example 1.

[Explanation of symbols]

11 reactor 12 Centrifugal extractor 13 Alkaline neutralization tank 15 Coalescer filter 16 Distillation column consisting of thin film evaporator

Claims (8)

[Claims] 1. A crude epoxidation reaction liquid obtained by epoxidation of an unsaturated organic compound with an organic peracid is neutralized and washed with water, and then water is separated by a coalescer to remove the water in the reaction crude liquid. 1 pp of residual metal
A method for purifying a crude liquid of an epoxidation reaction, which is characterized in that 2. The method for purifying a crude epoxidation reaction liquid according to claim 1, wherein the unsaturated organic compound is a cyclohexene compound. 3. The cyclohexene compound is a compound selected from 3-cyclohexenylmethyl-3-cyclohexenecarboxylate, 3-cyclohexenylmethyl (meth) acrylate, or a lactone adduct thereof. Item 2. A method for purifying a crude liquid of an epoxidation reaction according to Item 2. 4. The method for purifying a crude epoxidation reaction liquid according to claim 1, wherein the organic peracid is peracetic acid. 5. The coalescer is a coalescer filter having a coalescer element that aggregates water in the crude liquid for epoxidation reaction and a hydrophobic filter element, and the coalescer is characterized in that: Purification method of crude liquid for epoxidation reaction. 6. The organic peracid is extracted from the crude liquid of the epoxidation reaction, if necessary, and then the residual organic peracid and the acidic substance are neutralized and washed with water, and then the water remaining after the neutralization and washing treatment. The residual metal content is reduced to 1 ppm or less by aggregating with a coalescer element and selectively separating with a hydrophobic filter element.
5. The method for purifying a crude liquid for epoxidation reaction according to any one of 5 above. 7. The method for purifying an epoxidation reaction crude liquid according to claim 1, further comprising distillation after the separation treatment with a coalescer. 8. An epoxidized cyclohexene compound having a water content of 0.02 wt% or less and a metal content of 0.5 ppm or less.