JPH1112209A - Separation and acquisition of cyclic alcohol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for separating a cyclic alcohol, capable of reducing the concentration of a cyclic olefin contained in the cyclic alcohol without lowering the yield of the cyclic alcohol. SOLUTION: This method for separating a cyclic alcohol comprises subjecting the oil layer of a cyclic olefin such as cyclohexene to a catalytic hydration reaction in the presence of a crystalline metallosilicate containing at least one kind of metal selected from aluminum, boron, gallium, titanium, chromium, iron, zinc, phosphorus, vanadium and copper as a catalyst in the coexistence of an aqueous phase and subsequently distilling the produced cyclic alcohol from the oil phase with a distillation tower. Therein, a basic substance such as an amine is added to the oil phase after the catalytic hydration reaction before or during the distillation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a process for the catalytic hydration of a cyclic olefin in the presence of an oil phase containing a cyclic olefin, an aqueous phase and the catalyst using a crystalline metallosilicate as a catalyst. And a method for separating and obtaining a cyclic alcohol which is a reaction product of the above.

[0002]

2. Description of the Related Art Conventionally, there are many literatures and patents on a method for producing a cyclic alcohol by using a crystalline metallosilicate as a solid catalyst in a hydration reaction of a cyclic olefin. For example, Japanese Patent Publication No. 2-31056 proposes a method for producing a cyclic alcohol by hydrating a cyclic olefin using a crystalline aluminosilicate having a primary particle diameter of 0.5 μm or less as a catalyst.

According to the description of the above publication, when a crystalline aluminosilicate having a primary particle diameter of 0.5 μm or less is used as a catalyst, the weight ratio of the cyclic olefin to water is 0.001 to 100. In the above, two phases, an oil phase and an aqueous phase, are formed in the reaction system, and the crystalline aluminosilicate is shown to be present in the aqueous phase. In addition, most of the cyclic alcohol produced by this reaction is present in the oil phase, and the mixture of the cyclic olefin and the cyclic alcohol obtained from the oil phase has a greatly different boiling point, so that it can be easily separated, and the cyclic alcohol can be separated. Indicates that it can be obtained. Furthermore, as a specific method, a part of the reaction solution consisting of two phases is continuously taken out, and the layers are separated by standing still. The oil phase is taken out from the upper layer, and the cyclic alcohol is removed from the oil phase by distillation or the like. The method of obtaining is given as a general example.

[0004] Further, the publication states that crystalline aluminosilicate does not exist in the oil phase, and does not mention a problem with the crystalline aluminosilicate entrained in the oil phase. In addition, Tokuhei 1-190644
In the publication, a method for producing a cyclic alcohol by hydrating a cyclic olefin using a crystalline aluminometallosilicate in which a part of the crystal lattice of the crystalline aluminosilicate is substituted with another metal element as a catalyst has been proposed. In addition, Japanese Patent Application Laid-Open No. 8-245454 discloses that a cyclic olefin is hydrated by using a crystalline metallosilicate in which all of the crystalline lattice of a crystalline aluminosilicate is substituted with another metal element as a catalyst. Although a method for producing alcohol has been proposed, it does not mention the problem with the catalyst entrained in the oil phase. No other literature or patent mentions this problem.

According to the knowledge of the present inventors, when the reaction solution consisting of two phases is allowed to stand after the reaction, the layers are continuously separated, and the oil phase is separated, the industrially used method is as follows. Entrainment of very small amounts of crystalline metallosilicate in the separated oil phase is inevitable. When an attempt is made to obtain a high-purity cyclic alcohol produced by a reaction from the oil phase containing the crystalline metallosilicate by a distillation separation method, in the course of distillation, the crystalline metallosilicate is mainly disadvantageously mainly composed of the cyclic alcohol. Concentrated in. At that time, the crystalline metallosilicate in the cyclic alcohol causes a dehydration reaction of the cyclic alcohol to produce a cyclic olefin, and the cyclic olefin in the cyclic alcohol is produced during the initial distillation purification and during the long-term storage of the purified product cyclic alcohol. There is a problem that the concentration is increased and the yield of the cyclic alcohol is reduced.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method capable of reducing the concentration of a cyclic olefin in a cyclic alcohol without reducing the yield of the cyclic alcohol.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above problems, and as a result, when obtaining a cyclic alcohol by distillation separation using a distillation column, after the catalytic hydration reaction, For the catalyst present in the oil phase,
The present inventors have found the surprising fact that a high-purity cyclic alcohol having a low cyclic olefin concentration and a low purity can be obtained only by adding a trace amount of a basic substance, and the present invention has been accomplished.

That is, the present invention is as follows. 1) As a catalyst, a crystalline metallosilicate containing at least one metal selected from aluminum, boron, gallium, titanium, chromium, iron, zinc, phosphorus, vanadium, and copper is used, and the following general formula (1) In the method of obtaining a cyclic olefin oil phase and a cyclic alcohol produced by a catalytic hydration reaction in the co-presence of an aqueous phase and the catalyst from the oil phase by distillation separation using a distillation column, A method for separating and obtaining a cyclic alcohol, wherein a basic substance is added to an oil phase after a hydration reaction before or during distillation.

C _s H _2s-2-t R _t (1) wherein R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a cyclohexyl group, and s is 5 to 12;
t is an integer of 1 to 4. 2) The method for separating and obtaining a cyclic alcohol according to 1 above, wherein the addition of the basic substance is 0.01 to 100 milligram equivalent / g with respect to the catalyst present in the oil phase.

3) The catalyst as described in 1 above, wherein the catalyst is a crystalline metallosilicate represented by the following general formula (2).
Or the method for separating and obtaining a cyclic alcohol according to 2. _{M 2 O n · xSiO 2 ·} yAl 2 O 3 · (1-y) Z 2 O w (2) ( wherein, M represents at least one cation of valence n,
O is oxygen, Si is silicon, Al is aluminum, Z is M
And metals other than aluminum, such as boron, gallium,
Represents at least one w-valent metal selected from titanium, chromium, iron, zinc, phosphorus, vanadium, and copper. Further, n is an integer of 1 to 6, w is an integer of 1 to 6, and 1 ≦ x ≦ 1
000, 0 ≦ y ≦ 1. 4) The crystalline metallosilicate has a primary particle size of 0.5 μm
4. The method for separating and obtaining a cyclic alcohol according to the above 1, 2 or 3, wherein the method is the following crystalline aluminosilicate.

(5) The method for separating and obtaining a cyclic alcohol according to (4) above, wherein the crystalline aluminosilicate is a crystalline aluminosilicate ZSM-5. 6) The method for separating and obtaining a cyclic alcohol according to any one of 1 to 5 above, wherein the basic substance is an amine. 7) The method for separating and obtaining a cyclic alcohol according to the above item 6, wherein the amine is an amine having a higher boiling point than the cyclic alcohol.

8) The method for separating and obtaining a cyclic alcohol according to any one of the above 1 to 7, wherein the cyclic alcohol is cyclohexanol. Hereinafter, the present invention will be described in detail. FIG. 1 is an example of a process flow sheet for carrying out the present invention, and will be described with reference to FIG. 1 as necessary.

The crystalline metallosilicate used in the present invention is a crystalline metallosilicate containing at least one metal selected from aluminum, boron, gallium, titanium, chromium, iron, zinc, phosphorus, vanadium and copper. Examples of the metallosilicate include, for example, those having a composition represented by the molar ratio of an oxide of an anhydride and represented by the general formula (2).

In the general formula (2), M is a cation in a crystalline metallosilicate, and is preferably a proton, IB, IIA, IIB, IIIA, I
Group IIB, IVB, VB, VIB, VIIB, VIII metal cations, more preferably protons. Z is a metal other than M and aluminum,
Boron, gallium, titanium, chromium, iron, zinc, phosphorus,
At least one metal selected from vanadium and copper, which are taken into the crystal during the hydrothermal synthesis of the crystalline metallosilicate and do not come out of the crystalline metallosilicate during the subsequent ion exchange operation It is metal. Particularly preferred among these metals are boron, gallium, titanium, chromium, and iron.

Specific examples of the catalyst include mordenite, faujasite, clinoptilolite, L-type zeolite,
Crystalline aluminosilicates, such as chabazite, erionite, ferrierite, and ZSM zeolite announced by Mobil, and elements other than aluminum, such as boron, gallium, titanium, chromium, iron, zinc, phosphorus, vanadium, and copper And metallosilicates such as gallosilicate and borosilicate substantially free of aluminum.

AZ-1 (Japanese Patent Application Laid-Open No. 59-12821)
0), TPZ-3 (JP-A-58-1104).
No. 19), Nu-3 (JP-A-57-3714).
No. 5), Nu-5 (JP-A-57-129820).
No. 6), Nu-6 (JP-A-57-123817).
No. 10), Nu-10 (JP-A-57-20021).
No. 8) is also effective.

The crystalline metallosilicate used in the present invention preferably has a primary particle size of 0.5 μm or less, more preferably 0.1 μm or less, and further preferably 0.05 μm or less. The lower limit of the particle size is defined by the term "crystallinity". A crystal is one in which atoms are regularly and regularly arranged according to a certain symmetry, and diffraction phenomena due to X-rays are recognized (Kyoritsu Shuppan Co., Ltd., Dictionary of Chemistry, 1963, 3rd edition)
Volume, page 349, "Crystal"). Therefore, in order for a certain period to occur and for the X-ray diffraction phenomenon to be recognized, there is a certain finite size based on the crystal structure. Therefore, the crystalline metallosilicate used in the present invention has X
Line diffraction phenomenon is observed, and the primary particle diameter is 0.5 μm
The following may be preferred.

Although there are various shapes of these primary particles, the primary particle diameter as referred to in the present invention is a value obtained by measuring the diameter of the narrowest part of the particle to be measured as seen with a scanning electron microscope,
Anything less than the measured value is at least 50
It means that it is more than the quantity%. In this case, as long as the primary particle diameter is 0.5 μm or less, it is effective even if the diameter of the secondary particles formed by their aggregation or the like is increased.

Further, depending on the type of particles, it is determined whether the surface of the large particles has irregularities or whether the primary particles are agglomerated.
In some cases, it cannot be determined from a scanning electron micrograph.
In this case, the fine particles are those in which the ratio of the outer surface acid sites to the total acid sites in the case of H-form is 0.03 or more, preferably 0.1%.
05 or more, more preferably 0.1 or more.

The method of measuring the ratio of the outer surface acid sites to the total acid sites is as follows. First, before measuring the acid point, it is necessary to make the crystalline metallosilicate used in the present invention H-type. There are various methods for converting the crystalline metallosilicate to the H-type, with or without the use of an organic substance in the synthesis system, and when using an organic substance, there are various methods depending on the type of the organic substance.
Type.

After the slurry used in the present invention is filtered, it is washed with 5 times the amount of water. When an organic substance is used in the synthesis system, the cake obtained is dried at 120 ° C. for 8 hours, and then dried.
After baking at 00 ° C. for 6 hours in a stream of air to remove organic substances, the mixture was added to 1N nitric acid to form a 10% by weight slurry, ion-exchanged at 60 ° C. for 4 hours, and the slurry was filtered. After washing with twice the volume of water,
Dry for 0 hours to obtain H-type crystalline metallosilicate.

When no organic matter is used in the synthesis system,
The cake obtained by filtration and washing is directly added to 1N nitric acid,
Hereinafter, an H type is formed in the same manner as described above. The acid point of the H-type crystalline metallosilicate obtained in this manner is measured by the following method (Reference: catalyst, vol. 25, p461).
(1983)). As an acid point measuring device, a gas chromatograph GC-7A manufactured by Shimadzu Corporation and a data processing device CR-1A were used. That is, inner diameter 4 mm, total length 80
A sample (0.2 to 1 g) is packed in a short column made of SUS (mm) and attached to a sample-side flow path in a thermostat of the gas chromatograph. 5 helium gas as carrier gas
Flow at a flow rate of 0 ml / min.
Set to 5 ° C.

Next, a fixed amount (0.2 to 2 ml) of the amine (pyridine, 4-methylquinoline) is supplied to the injection port of the sample-side channel for a predetermined period (2 to 5 minutes) using a microsyringe.
Continue to inject intermittently. The carrier gas that has passed through the packed column is analyzed using an FID type detector to obtain a chromatogram of a temporal change in amine concentration in which a peak appears periodically.

As the number of injections increases, the amount of amine adsorbed on the sample approaches saturation, and the amount of non-adsorbed amine increases by injection. Therefore, in the chromatograph, a peak area Si corresponding to the second injection of the amine was obtained.
Gradually approaches an area So corresponding to the amount of amine injected. Amount of amine adsorbed per unit weight of sample Ao (μmo
1 / g) can be determined by the following equation (a).

[0025]

(Equation 1)

In the present invention, Si / So ≧ 0.98
The injection was repeated until the k-th injection so that the amine adsorption amount A (μmol / g) was calculated by the following equation (b).

[0027]

(Equation 2)

In the present invention, the total acid point is represented by the amount of pyridine adsorbed when pyridine is used as the amine, and the outer surface acid point is the 4-acid quinoline measured when 4-methylquinoline is used as the amine. It is expressed by the amount of methylquinoline adsorbed. Therefore, the ratio of the outer surface acid sites to the total acid sites is 4
−Methylquinoline adsorption amount / pyridine adsorption amount. In the hydration reaction of a cyclic olefin, side reactions such as isomerization and polymerization occur. For example, in the hydration reaction of cyclohexene, by-products such as methylcyclopentenes, dicyclohexyl ether, and bicyclohexyl are generated. In order to suppress this side reaction and obtain a cyclic alcohol in good yield, for example, a crystalline aluminosilicate ZSM-5 as disclosed in Japanese Patent Publication No. 41131/1992 may be used.
It is also effective to use as a catalyst. Crystalline aluminosilicate ZSM-5 is a zeolite developed by Mobile Oil (see U.S. Pat. No. 3,702,886), in which the molar ratio of silica to alumina constituting the crystal is 20 or more, and the crystal structure Is a zeolite having three-dimensional pores having an inlet of a 10-membered oxygen ring.

On the other hand, in the present invention, the cyclic olefin used in the catalytic hydration reaction is a compound represented by the above general formula (1), for example, cyclopentene, cyclohexene, cyclooctene, cyclononene, cyclodecene, cycloun Decene, cyclododecene, methylcyclohexene, dimethylcyclohexene, trimethylcyclohexene, tetramethylcyclohexene, phenylcyclohexene, and the like, and mixtures thereof are also useful. These cyclic olefins are then hydrated to produce corresponding cyclic alcohols.

The reaction temperature is preferably low from the viewpoint of the problem of equilibrium in the hydration reaction of the olefin and the suppression of side reactions.
If the reaction temperature is too low, the reaction rate is too low to be economical. Therefore, the range of 50 ° C to 300 ° C is preferable. or,
The pressure of the reaction can be applied in a range from reduced pressure to increased pressure, but the reaction is carried out at such a pressure that both the cyclic olefin and water as the raw materials for the reaction can maintain a liquid phase.

The molar ratio of water, which is a reaction raw material, to the cyclic olefin can be set in a wide range, but if the cyclic olefin is excessive, the conversion of the cyclic olefin becomes low. On the other hand, if the amount of water is too large, the conversion of the cyclic olefin can be increased. Occurs. However, it is not advisable to increase the volume of the container unnecessarily due to problems in equipment production, maintenance and inspection, and operation.

Therefore, in the present invention, the molar ratio of the cyclic olefin to water is preferably in the range of 0.01 to 100. In a continuous reaction, the weight ratio of the cyclic olefin to the catalyst varies depending on conditions such as the reaction temperature, the reaction pressure, the molar ratio of the cyclic olefin to water, and the like. The weight of the catalyst is preferably in the range of 0.005 to 100 based on the weight of the cyclic olefin to be obtained.

In the present invention, the substance added and coexisted in the oil phase for distillation is a basic substance. The method for adding the basic substance is as follows: (A) adding the basic substance directly to the oil phase; A method of neutralizing the acid point of the catalyst, (B) a method of adding a strongly basic substance such as caustic soda directly to the oil phase and heating the oil phase to destroy the crystal structure of the metallosilicate, and the like. The method A) is simple in operation. Such addition of the basic substance is performed intermittently or continuously.

In the present invention, the liquid to be added is a cyclic alcohol, a cyclic olefin, and a small amount of crystalline metallosilicate obtained from the oil phase removed from the liquid-liquid separator after the above-mentioned catalytic hydration reaction. Containing liquid,
Alternatively, these are concentrated liquids, and the concentration of the cyclic alcohol in the oil phase taken out from the separator is about 12% by weight. In general, the cyclic alcohol is concentrated and purified to produce a product, while the unreacted cyclic olefin is recovered and recycled, and impurities having a high boiling point are separated and removed. Therefore, in order to prevent the added basic substance from being mixed into the recycled cyclic olefin and the product cyclic alcohol, and to effectively contribute to deactivation, the addition of the basic substance to the oil phase is performed by purifying the distillation column. It is preferable to target the inner liquid below the steam discharge pipe 11.

In the present invention, it is added to the oil phase for distillation.
As coexisting basic substances, inorganic substances include
General formula, M^IOH, M^II(OH)_Two, M^III(OH)
_Three[Where M^I, M^II, M^IIIAre monovalent, 2
OH is a hydroxyl group.
You. ] Represented by an alkali metal hydroxide, and
General formula, M^I _TwoOH_TwoO, M^IIOH_TwoO, M^III _Two
O_Three・ 3H_TwoO [where M^I, M ^II, M^IIIEach
Is a monovalent, divalent or trivalent alkali metal;_TwoO
Water and O are oxygen. An alkali metal acid represented by
Hydrates, and ammonia, and the like.
Mixtures of are also useful.

Among the basic substances, organic substances include those represented by the following general formulas: R1NH ₂ , R1R2NH, R1R2R3
N [wherein R1, R2, and R3 are an alkyl group having 1 to 16 carbon atoms, a phenyl group or a cyclohexyl group, and a substituent containing nitrogen such as an amino group or an imino group. And the like, and typically include amines.

When the basic substance is added to the oil phase,
It is preferable to reduce the catalytic action of the mixed catalyst, and it is particularly preferable to use amines because the operation is simple. The amines are compounds represented by the above general formula and the like. In order to prevent the added amines from being mixed into the product, it is preferable to select a high-boiling or low-boiling substance having an appropriate boiling point difference from the cyclic alcohol to be the product, preferably a high-boiling substance.

For example, when cyclohexanol in oil-phase cyclohexene is obtained by distillation, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, cetylamine, Diamylamine, tributylamine, triamylamine, aniline, methylaniline, dimethylaniline, ethylaniline, diethylaniline, methylquinoline, toluidine,
Benzylamine, dibenzylamine, tribenzylamine, diphenylamine, triphenylamine, naphthylamine, tripelenamine, diaminomethylaminooctane, triethanolamine, triethylenetetramine, etc., it is preferable to use amines having a higher boiling point than cyclohexanol, Even more preferred is triethylenetetramine.

The amount of the basic substance to be coexisted varies depending on the acid amount of the catalyst used in the catalytic hydration reaction, the use condition, the degree of deterioration, etc., but is usually 0 to the amount of the catalyst in the oil phase for distillation. .01 to 100 milligram equivalent / g
Is preferred.

[0040]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. The content of the crystalline metallosilicate in the cyclic alcohol and the cyclic olefin liquid was determined by filtering the liquid, washing the residue after filtration, drying at 120 ° C. for 1 hour, and further calcining at 500 ° C. for 4 hours. It was calculated from the weight of the obtained solid.

[0041]

Example 1 In the hydration reaction, as a crystalline aluminosilicate serving as a catalyst, ZSM-5 fine particles which are crystalline aluminosilicate described in JP-A-3-193622 were used. The primary particle size of this crystalline aluminosilicate was 0.1 μm. The crystalline aluminosilicate was mixed with water at a weight ratio of twice to obtain a slurry catalyst, the reaction temperature was 125 ° C., and the reaction pressure was 6 kg / cm ² G.
The gaseous phase is pressurized with nitrogen gas so that the rotation speed of the stirrer is 530 rpm and cyclohexene is added to 1 part by weight of the catalyst.
Water was supplied at a rate of 1 part by weight per hour, and water corresponding to the amount of water consumed by the reaction was supplied through the raw material supply pipe 5.

The amount of the slurry-like catalyst returned to the reactor 1 via the return pipe 7 was adjusted so that the oil-water interface level of the separator 2 was located below the discharge pipe 8. The liquid supplied to the distillation column 3 via the discharge pipe 8 is composed of 11.8% by weight of cyclohexanol, crystalline aluminosilicate 1
It was a cyclohexene mixture containing 8 ppm by weight. 100 parts by weight of this product liquid is supplied to the distillation column 3 via the discharge pipe 8. 0.5 parts by weight of the catalyst and cyclohexanol are extracted from the bottom of the distillation column 3 via the discharge pipe 12 to the outside of the system. 88.5 parts by weight of a distillate is withdrawn from the top of the distillation column 3 via a discharge pipe 10. This distillate is recycled to the reactor 1. Its composition is 99.7% by weight of cyclohexene and 0.3% by weight of cyclohexanol.
Crystalline aluminosilicate is below the detection limit (1
Weight ppm or less).

0.0005 of cyclohexanol containing 10% by weight of deutilized triethylenetetramine was supplied from the supply pipe 9.
When parts by weight were supplied (corresponding to 0.5 milligram equivalent / g as triethylenetetramine relative to the supplied crystalline aluminosilicate), above the supply pipe 9 and below the connection between the discharge pipe 8 and the distillation column 3 As a vapor from the purified vapor discharge pipe 11 provided, cyclohexene 2 weight p
11.0 parts by weight of cyclohexanol containing pm were obtained. The concentration of triethylenetetramine in the cyclohexanol was below the detection limit (1 ppm by weight or less). At this time, the crystalline aluminosilicate as a catalyst at the bottom of the distillation column was 0.36% by weight.

Further, the bottom liquid of the distillation column to which triethylenetetramine was added and withdrawn was taken out from the discharge pipe 12 and stored at 25 ° C. for one year. As a result, the concentration of cyclohexene in cyclohexanol did not increase, and the yield of cyclohexanol did not increase. No decrease in the rate was observed, and no other compounds were formed.

[0045]

Example 2 A hydration reaction was carried out in the same manner as in Example 1 except that the crystalline gallosilicate described in Example 1 of JP-A-8-245454 was used as the crystalline metallosilicate serving as a catalyst. went. Distillation tower 3 via discharge pipe 8
8.4% by weight of cyclohexanol,
It was a cyclohexene mixed solution containing 25 ppm by weight of crystalline gallosilicate. 100 parts by weight of this product liquid is supplied to the distillation column 3 via the discharge pipe 8. 0.5 parts by weight of the catalyst and cyclohexanol are extracted from the bottom of the distillation column 3 via the discharge pipe 12 to the outside of the system. 91.8 parts by weight of a distillate is withdrawn from the top of the distillation column 3 via the discharge pipe 10. This distillate is recycled to the reactor 1. The composition was 99.8% by weight of cyclohexene and 0.2% by weight of cyclohexanol, and the crystalline gallosilicate was below the detection limit (1% by weight or less).

0.0004 of cyclohexanol containing 10% by weight of recycled triethylenetetramine from the supply pipe 9
When parts by weight were supplied (corresponding to 0.5 mg equivalent / g as triethylenetetramine relative to the supplied crystalline gallosilicate), above the supply pipe 9 and below the connection between the discharge pipe 8 and the distillation column 3 Cyclohexene 3 wt ppm as steam from the purified steam discharge pipe 11 provided
Was obtained in an amount of 7.7 parts by weight.
The concentration of triethylenetetramine in the cyclohexanol was below the detection limit (1 ppm by weight or less).
At this time, the crystalline gallosilicate as a catalyst at the bottom of the distillation column was 0.50% by weight.

Further, the bottom liquid of the distillation column to which triethylenetetramine was added and supplied was withdrawn from the discharge pipe 12 and stored at 25 ° C. for one year. As a result, the cyclohexene concentration in cyclohexanol did not increase, and the yield of cyclohexanol did not increase. No decrease in the rate was observed, and no other compounds were formed.

[0048]

COMPARATIVE EXAMPLE 1 The same operation as in Example 1 was performed except that triethylenetetramine was not supplied.
10.9 parts by weight of cyclohexanol containing ppm by weight were obtained. At this time, the crystalline aluminosilicate at the bottom of the distillation column was 0.36% by weight.

When the bottom of the distillation column was withdrawn from the discharge pipe 12 and stored at 25 ° C. for one year, the concentration of cyclohexene in cyclohexanol increased to 5215 ppm by weight, and the yield of cyclohexanol decreased. It was confirmed that 1135 ppm by weight of 1-methylcyclopentene was produced as another impurity.

[0050]

Comparative Example 2 The same operation as in Example 2 was carried out except that triethylenetetramine was not supplied. As a result, 7.6 parts by weight of cyclohexanol containing 985 ppm by weight of cyclohexene was obtained as steam from the purified steam discharge pipe 11. Obtained. At this time, the crystalline aluminosilicate at the bottom of the distillation column was 0.50% by weight.

When the bottom liquid of the distillation column was withdrawn from the discharge pipe 12 and stored at 25 ° C. for one year, the concentration of cyclohexene in cyclohexanol increased to 4011 ppm by weight, and the yield of cyclohexanol decreased. Further, it was confirmed that 1-methylcyclopentene was produced as much as 934 ppm by weight as another impurity.

[0052]

According to the method of the present invention, the operation of reducing the concentration of the cyclic olefin in the cyclic alcohol and not reducing the yield of the cyclic alcohol can be simultaneously performed by the distillation separation method.

[Brief description of the drawings]

FIG. 1 is an example of a process flow sheet for implementing the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Reactor 2 Separator 3 Distillation tower 4 Raw material supply pipe 5 Raw material supply pipe 6 Drain pipe 7 Return pipe 8 Drain pipe 9 Supply pipe 10 Drain pipe 11 Purified steam discharge pipe 12 Drain pipe

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07C 35/02 C07C 35/02 // C07B 61/00 300 C07B 61/00 300

Claims (8)

[Claims] 1. A crystalline metallosilicate containing at least one metal selected from the group consisting of aluminum, boron, gallium, titanium, chromium, iron, zinc, phosphorus, vanadium and copper is used as a catalyst. (1) A method for obtaining a cyclic olefin oil phase, a cyclic alcohol produced by a catalytic hydration reaction in the co-presence of an aqueous phase and the catalyst, and a cyclic alcohol from the oil phase by distillation separation using a distillation column. A method for separating and obtaining a cyclic alcohol, wherein a basic substance is added to the oil phase after the contact hydration reaction before or during distillation. C _s in _{H 2s-2-t R t} (1) ( wherein, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a cyclohexyl group, s is 5-12,
t is an integer of 1 to 4. ) 2. The method for separating and obtaining a cyclic alcohol according to claim 1, wherein the addition of the basic substance is 0.01 to 100 milligram equivalent / g with respect to the catalyst present in the oil phase. 3. The catalyst according to claim 1, wherein the catalyst is a crystalline metallosilicate represented by the following general formula (2).
Or the method for separating and obtaining a cyclic alcohol according to 2. _{M 2 O n · xSiO 2 ·} yAl 2 O 3 · (1-y) Z 2 O w (2) ( wherein, M represents at least one cation of valence n,
O is oxygen, Si is silicon, Al is aluminum, Z is M
And metals other than aluminum, such as boron, gallium,
Represents at least one w-valent metal selected from titanium, chromium, iron, zinc, phosphorus, vanadium, and copper. Further, n is an integer of 1 to 6, w is an integer of 1 to 6, and 1 ≦ x ≦ 1
000, 0 ≦ y ≦ 1. ) 4. The method for separating and obtaining a cyclic alcohol according to claim 1, wherein the crystalline metallosilicate is a crystalline aluminosilicate having a primary particle size of 0.5 μm or less. 5. The method for separating and obtaining a cyclic alcohol according to claim 4, wherein the crystalline aluminosilicate is a crystalline aluminosilicate ZSM-5. 6. The method for separating and obtaining a cyclic alcohol according to claim 1, wherein the basic substance is an amine. 7. The method for separating and acquiring a cyclic alcohol according to claim 6, wherein the amine is an amine having a boiling point higher than that of the cyclic alcohol. 8. The method for separating and obtaining a cyclic alcohol according to claim 1, wherein the cyclic alcohol is cyclohexanol.