JP3088875B2 - Hydration of cyclic olefins - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a cyclic alcohol by reacting a cyclic olefin with water. More specifically, a method for hydrating a cyclic olefin to produce a cyclic alcohol by reacting a cyclic olefin with water includes a continuous aqueous phase obtained by suspending a crystalline aluminosilicate in water and an oil phase containing the cyclic olefin. The present invention relates to a method for hydrating a cyclic olefin, which comprises reacting a cyclic olefin using a reaction system that performs a reaction by dispersing an oil phase as a droplet having a specific droplet diameter in a continuous aqueous phase. According to the method of the present invention, not only can the cyclic alcohol be produced with high selectivity and high yield, but also the catalyst activity can be stably maintained at a high level for a long time, and the generated cyclic alcohol can be easily separated. can do.

[0002]

2. Description of the Related Art Conventionally, as a hydration reaction method for producing a cyclic alcohol by reacting a cyclic olefin with water, an indirect or direct hydration reaction using a mineral acid, particularly sulfuric acid, is known. A method using aromatic sulfonic acid as another homogeneous catalyst (Japanese Patent Publication No. 43-16125) has been proposed. According to Example 2 in that specification,
Oil phase 2 of a mixture of cyclohexane and cyclohexene is added to 160 g of an aqueous phase containing paratoluenesulfonic acid.
00g is reacted at 90 ° C for 12 hours. After the completion of the reaction, oil-water separation is performed, 200 g of water is further added to the aqueous phase, and steam distillation is performed under heating to distill and recover cyclohexanol. However, these systems are reactants,
In particular, there is a drawback that separation and recovery from the aqueous solution phase become complicated, and a large amount of energy is consumed. As a method of improving these disadvantages, a method using a solid catalyst, for example,
A method using an ion exchange resin has been proposed (Japanese Patent Publication No. 38-15819, Japanese Patent Publication No. 44-26656). However, these ion exchange resins have problems such as pulverization of the resin due to mechanical disintegration, reduction in catalytic activity due to insufficient heat resistance, and the like, and cannot maintain stable activity for a long time. There is.

Further, as a method of using a solid catalyst,
A method using a crystalline aluminosilicate has been proposed. Crystalline aluminosilicate is insoluble in water,
It has excellent mechanical strength and heat resistance, and is expected to be used as an industrial catalyst. JP-A-60-104028 describes an example in which finely divided crystalline aluminosilicate is used as a catalyst. According to this, water, a catalyst and cyclohexene as a cyclic olefin were charged into an autoclave equipped with a stirrer, and the reaction temperature was 50 to 25.
This is a method of reacting at 0 ° C. for a reaction time of 15 minutes to 4 hours to obtain cyclohexanol as a cyclic alcohol from the oil phase.

[0004]

The present reaction field is composed of three phases: an oil phase mainly containing cyclic olefins, an aqueous phase mainly containing water, and a solid phase of a catalyst suspended in the aqueous phase. It is homogeneous. In such a reaction field, if the mixing of oil and water is insufficient, there is a phenomenon that the reaction yield is remarkably reduced and the original performance of the catalyst cannot be sufficiently exhibited. After the reaction is completed, the reaction product is allowed to stand and oil-water separated to obtain a cyclic alcohol from the oil phase.If the oil-water mixture is too strong in the reaction field, the oil-water separation time This would be significantly longer and would require an excessive resting part. Particularly, depending on the physical properties of the catalyst and impurities in the raw materials, in extreme cases, the emulsion is formed and oil-water separation becomes difficult, the catalyst leaks into the reaction product, and a stable reaction cannot be maintained continuously. In order to destroy the emulsion once generated, a method of constantly treating the reaction product containing the catalyst with a centrifuge may be considered. There was a problem that the catalyst was broken and the catalyst separation became insufficient, and thus it was not practically usable. Further, when the emulsified catalyst is reused after the emulsion is destroyed, there is also a problem that the activity is remarkably reduced as compared with a usual catalyst which is separated by standing.
Thus, a reaction method that does not emulsify has been desired.

As described above, in the conventionally known method,
Maintaining a long-term stable reaction yield in producing a cyclic alcohol from a cyclic olefin has not yet been fully satisfactory. It wasn't.

[0006]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, surprisingly, the purpose of the present invention is to provide a continuous aqueous phase obtained by suspending crystalline aluminosilicate in water. Using a reaction system that includes an oil phase and a hydrophobic phase containing a cyclic olefin or an oil phase, and performing a reaction by dispersing the oil phase as a droplet having a specific droplet diameter in a continuous aqueous phase. I learned that I can do it. The present invention has been completed based on the above findings. That is, the present invention can advantageously produce a cyclic alcohol on an industrial scale, and can not only produce a high selectivity and a high yield, but also can stably maintain the catalyst activity at a high level for a long time,
An object of the present invention is to provide a hydration reaction of a cyclic olefin that can easily separate a generated cyclic alcohol. The above and other objects, features and advantages of the present invention will become apparent from the following detailed description and the appended claims, taken in conjunction with the accompanying drawings.

That is, according to the present invention, the primary particle diameter is
The cyclic olefin in the presence of a crystalline aluminosilicate catalyst is 0.5μm or less have your hydration reaction method of the cyclic olefin to produce a cyclic alcohol is reacted with water,
A reaction system including a continuous aqueous phase in which the crystalline aluminosilicate is suspended in water and an oil phase containing a cyclic olefin is used, and the oil phase is formed into a droplet having an average droplet diameter of 0.05 to 30 mm. A method for hydrating a cyclic olefin is provided, wherein the reaction is carried out by dispersing in a phase.

First, the mechanism of this reaction will be described in the case where cyclohexene is used as a cyclic olefin. Cyclohexene in an oil phase is diffused and dissolved in an aqueous phase through an oil-water interface in a reaction field. The dissolved cyclohexene reaches the active site on the catalyst and is adsorbed, and simultaneously reacts with the adsorbed water to produce cyclohexanol. The cyclohexanol is separated from the catalyst and dissolves and diffuses in the aqueous phase. The cyclohexanol in this water phase moves to the oil phase through the oil-water interface. From this oil phase, for example, cyclohexanol is obtained by distillation. in this way,
The reaction system of the method of the present invention is a reaction system including a mass transfer process.

Here, the oil phase comprises a cyclic olefin as a main component, a cyclic alcohol, dissolved water and the like. The aqueous phase is a suspension of a crystalline aluminosilicate catalyst in water, and is composed of dissolved cyclic olefin, cyclic alcohol, and the like. By the way, the hydration reaction of a cyclic olefin such as cyclohexene is a thermodynamic equilibrium reaction, and at a normal reaction temperature of 50 to 250 ° C.,
This reaction proceeds according to the following formula (1).

[0010]

(Equation 1) Kp: thermodynamic equilibrium constant C ₁ : molar concentration of cyclohexanol C ₂ : molar concentration of cyclohexene C ₃ : molar concentration of water

Here, the thermodynamic equilibrium value Kp is on the order of 10 ^{-3. When} a small amount of cyclohexene is reacted in a two-phase system of water and a catalyst without an oil phase, the amount of cyclohexanol produced is very small. It is. However, in the reaction system used in the present invention, by the presence of an oil phase, for example,
The concentration of cyclohexanol in the aqueous phase of a normal reaction solution is 0.1.
The liquid-liquid distribution equilibrium of cyclohexanol between the oil phase and the aqueous phase is significantly higher than that of the oil phase, as the concentration of cyclohexanol in the oil phase is 1 to 30% by weight with respect to 1 to 5% by weight. Therefore, the concentration of cyclohexanol in the oil phase is increased, so that cyclohexanol can be obtained at a higher yield than in the oil phase. That is, it is considered that the presence of the oil phase is an essential condition. In such a heterogeneous reaction, a mass transfer process such as diffusion of a reactant or product to a phase interface or diffusion through a phase interface affects the reaction rate. The reaction rate is determined by the product of the overall reaction rate constant and the concentration of the reactant, and the overall reaction rate constant consists of the mass transfer rate constant and the reaction rate constant on the catalyst.

The present inventors analyzed the experimental data of the autoclave equipped with a stirrer for the reaction rate. As a result, although the reaction rate on the catalyst was relatively high, the dissolution rate of cyclohexene from the oil phase to the aqueous phase was high. It has been found that the mass transfer rate such as the extraction rate of cyclohexanol from the aqueous phase to the oil phase and the generated cyclohexanol may be lower than the reaction rate on the catalyst depending on the conditions of the reaction system, which may reduce the overall reaction rate. . In particular, in the case of weak mixing, a phenomenon occurs in which the oil phase separates from the aqueous phase to form two layers. In this case, the interfacial area between the oil phase and the aqueous phase is insufficient, and mass transfer is limited,
The overall reaction rate will be very slow. Incidentally, the overall mass transfer rate at the interface between the oil phase and the aqueous phase is represented by the product KLa of the film mass transfer coefficient KL and the interfacial area a per unit volume.
It is represented by The film mass transfer coefficient depends on the physical properties (diffusion coefficient, viscosity, density) of the oil phase and the aqueous phase, the relative velocity of the droplet and the continuous phase, the droplet diameter, and the like. On the other hand, the boundary area a is the product of the number of droplets and the specific surface area of each droplet. By providing a large number of fine droplets, an interface area necessary for mass transfer can be created. As described above, it is preferable that the diameter of the droplet is small. However, if the diameter is too small, it takes a long time for the droplets to coalesce when the oil and water are allowed to stand still after the reaction is completed. become. In addition, when a small amount of impurities or the like acting as a surfactant is present in the raw material cyclic olefin, if the droplet diameter is too small, it is difficult to unite, and the oil-water separation becomes difficult due to emulsification.

The oil / water separation speed in the stationary region can be measured as follows. A predetermined reaction liquid is charged in a 4 liter stainless steel autoclave with a viewing window attached, and after stirring and mixing, the stirring is stopped. When the stirring is stopped, the oil droplets rise in the aqueous phase and reach the upper part of the tank. The oil droplets coalesce to form a continuous oil phase. The lower interface of this continuous oil phase descends until there is no dispersed droplet layer between the continuous water phases, and finally stops as a bicontinuous oil-water interface. The time from the stop of the stirring to the stop of the lowering of the continuous oil phase lower interface is defined as the oil-water separation time. In the method of the present invention, usually,
When the reactor volume is 4 liters, two layers are separated in 2 to 30 seconds. The larger the reactor, the longer the rise time of the oil droplets and the longer the separation time. The descending speed V _{0 at the} continuous oil phase interface is an important factor in designing a stationary tank. The superficial velocity V _e of the oil phase supplied to the reactor needs to be smaller than V ₀ . In general, when the coalescence of droplets is not rate-limiting by oil-water separation, the relationship between the droplet size and the interface descent speed is determined by the terminal velocity U _{m of the} droplet in the region of Stokes' law according to equation (2). From the relational expression (3) with the volume ratio ε of the oil droplet to the aqueous phase, the descending speed of the interface can be obtained.

[0014]

(Equation 2) U _m : rising speed of droplet g: gravitational acceleration ρ _c : continuous phase density ρ _d : density of droplet d _p : droplet diameter μ: viscosity

[0015]

V ₀ = ε · U _m V ₀ : velocity of descent at the continuous oil phase interface ε: drop-up hold-up rate U _m : as defined by [Equation 2]

As can be seen from these equations, the oil-water separation time can be shortened not only by increasing the diameter of the droplets but also by increasing the temperature of the reaction solution to increase the rising speed of the droplets. On the other hand, when an emulsion is formed, coalescence of the droplets floating on the upper part of the tank is hindered, and it is difficult to form a continuous oil phase, which cannot be expressed by the equations (2) and (3).

It is necessary to make the oil-water contact in an appropriately fine droplet state without forming such fine droplets. The volume average droplet diameter (hereinafter simply referred to as the average droplet diameter) is preferably 0.05 to 30 mm. A more preferable average droplet diameter is 0.1 to 10 mm.

As a method for measuring the diameter of the droplets dispersed in the aqueous phase, there are a light transmission method, a photographing method and the like. However, the present inventors have determined that the reaction system contains an opaque aqueous phase. Adopted the photography method. As a method of sampling the mixed solution from the reaction tank, the pressure is slightly lower than that of the reaction tank (for example, 0.1.
350 ml of water containing 0.2% by weight of a surfactant is put in a 1000 ml pressure-resistant transparent container having a pressure difference of 0.5 to 0.2 kg / cm ² ), and the pressure is transparent through a sampling nozzle from the stirred reaction tank. In a container, about 10 ml of a slurry liquid containing oil phase droplets is collected. The collected slurry is diluted with the water in the container, and a photograph is taken of the oil droplets floating on the upper layer. The photograph was magnified 2 to 100 times, and the diameter of 150 to 350 droplets was measured using a normal ruler, and the volume average droplet diameter was determined. When the droplet diameter was large, the sampling device was enlarged to avoid coalescence of droplets during sampling. It can also be achieved simply by taking a picture through a glass viewing window directly attached to the reactor.

The present inventors have studied which of the oil phase and the aqueous phase is to be the continuous phase.
When the oil phase was used as the dispersed phase, the results showed that the decrease in the activity of the catalyst over time was extremely small as compared with the opposite case. This is presumed to be because if the catalyst comes into contact with a large amount of cyclohexene in a state where the water adsorption amount is small, the cyclohexene itself is polymerized and poisoned at the active site of the catalyst. It is also conceivable that the catalyst activity decreases when the reaction solution forms an emulsion, possibly because the oil phase increases in the emulsion portion and poisons the catalytically active sites. For this reason, the aqueous phase needs to be a continuous phase, and for the above-mentioned reason, it is not preferable to unnecessarily increase the number of dispersed droplets of the oil phase. In this way, the cyclic olefin in the oil state is dissolved in the dispersed oil phase in the continuous aqueous phase, adsorbed on the catalyst, and is prevented from coming into direct contact with the catalyst from the oil phase, so that the catalyst can be stabilized for a long time. It is possible to maintain a state where there is no decrease in activity.

For example, when cyclohexanol is produced using cyclohexene as a cyclic olefin, there is isomerization to methylcyclopentenes such as 1-methylcyclopentene, 3-methylcyclopentene and 4-methylcyclopentene, These isomerized methylcyclopentenes are further converted to methylcyclopentanol, which is a by-product, by a hydration reaction. Furthermore, the desired cyclohexanol may react with cyclohexene to produce another by-product, such as dicyclohexyl ether.

These by-products not only reduce the reaction yield to cyclohexanol, but also have a boiling point close to each other when the reaction product is separated by distillation to obtain the desired cyclohexanol with high purity. Requires a large amount of energy for separation (for example, the boiling points of cyclohexanol, 1-methylcyclopentanol and 3-methylcyclopentanol are 161 ° C. and 154 ° C., respectively).
° C, 163 ° C). Furthermore, it is difficult to recover cyclohexene from the isomers because the boiling points are close to each other (for example, the boiling points of cyclohexene, 1-methylcyclopentene, and 3-methylcyclopentene are:
83.0 ° C, 75.8 ° C, 65.0 ° C respectively).

The present inventors have analyzed the formation rates of these by-products. The main reaction rate from cyclohexene to cyclohexanol is linear with the cyclohexene concentration, while the formation rate of methylcyclopentenes is high. The rate and the rate of formation into dicyclohexyl ether are zero order with respect to the cyclohexene concentration. In addition, it was found that the reaction rate of methylcyclopentene to methylcyclopentanol is primary in the concentration of methylcyclopentene. Here, when the mass transfer rate of cyclohexene at the interface between the oil phase and the aqueous phase is low, the production of the main reaction cyclohexanol is greatly suppressed, whereas the reaction of methylcyclopentene and dicyclohexyl ether is quantitatively small. However, since it proceeds reliably, the selectivity of cyclohexanol is reduced. This is due to the dispersed state of the oil droplets in the continuous aqueous phase and is important. For that purpose, the ratio of the oil phase to the aqueous phase in the reaction system is preferably 0.001 to 1.0 by volume, more preferably 0.01 / 0.8.

Further, it is preferable to use a cyclic olefin having a low cyclic alcohol concentration as a raw material because productivity per catalyst becomes higher. However, in an industrial-scale continuous reaction process, after the reaction, the oil phase in the stationary region is taken out, applied to a distillation separation column, the cyclic alcohol is taken out from the bottom of the column to produce a product, and the cyclic olefin is distilled out from the top of the column. The recovered cyclic olefin is then mixed with the raw material cyclic olefin and re-supplied to the reactor. For this reason, in order to make the cyclic alcohol in the recovered cyclic olefin substantially zero, a relatively large amount of energy is required. Therefore, a small amount (for example, about 1 to 2% by weight) of the cyclic alcohol is left to be recycled. It is also conceivable to reduce the distillation energy as much as possible.

As described above, this reaction is an equilibrium reaction, and the lower the reaction temperature, the less the generation of by-products, and the higher the cyclic alcohol equilibrium concentration, but the lower the reaction speed. For this reason, it is not advisable to lower the reaction temperature and use a large amount of catalyst to carry out the reaction in an attempt to forcibly increase the cyclic alcohol concentration. Usually the reaction is 50-
It is carried out at 250C, preferably 70-200C, most preferably 80-150C. In the present invention, the pressure in the reaction tank is not particularly limited, but it is preferable to perform the reaction under a pressure at which both water and the cyclic olefin can maintain a liquid state. In a normal reaction, 30 to 80% of the cyclic alcohol equilibrium concentration
It is operated at a cyclic alcohol concentration of For this reason, there is a limit to the cyclic alcohol concentration in the reactor. Therefore, the droplets preferably contain 50 to 100% by weight and 0 to 50% by weight, more preferably 60 to 99.9% by weight and 0.1 to 40% by weight, respectively, of the cyclic olefin and the cyclic alcohol.
It is preferable to configure the ratio.

The cyclic olefin used in the present invention includes cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cyclooctene, cyclododecene and the like. In the present invention, another organic solvent may coexist. In this case, the organic solvents are halogenated hydrocarbons, alcohols, ethers, ketones, and phenols. Halogenated hydrocarbons are methylene chloride, chloroform, tetrachloromethane, trichloroethane, tetrachloroethane and the corresponding bromides, iodides, fluorides. Examples of the alcohols include C _{1 to} C ₁₀ such as methanol, ethanol, isopropanol, n-propanol, isobutanol, and n-butanol.
Alcohols.

As ethers, dioxane, tetrahydrofuran, diethyl ether, diisopropyl ether, diisopropyl ether, diamyl ether, dimethyl ether of ethylene glycol, diethylene glycol or sulfone, for example, dipropyl sulfone, sulfolane, sulfoxide, for example, monoether such as dimethyl sulfoxide and the like; And double ethers. Ketones include acetone, methyl ethyl ketone and the like. Phenols include phenol and cresol. Any of the above organic solvents may be a mixture of two or more, and is contained in the oil phase, the aqueous phase, or both depending on the characteristics of the solvent used.

The raw material composition is desirably high in cyclic olefin purity, but hydrocarbon compounds such as aromatics such as benzene and toluene, naphthenes such as cyclohexane and cyclopentane, and pentane and hexane. It may contain paraffins. The concentration of these impurities is preferably 30% by weight or less. Further, the inorganic substance may include, for example, water, nitrogen, argon, carbon dioxide, carbon monoxide and the like. However, oxygen may cause a decrease in the activity of the catalyst, and it is preferable that oxygen does not coexist as much as possible.

The crystalline aluminosilicate used in the present invention has a primary particle diameter of 0.5 μm or less, preferably 0.1 μm or less. The effect of the present invention becomes clearer as the particle size becomes finer, but the lower limit is defined by the term “crystallinity”. Crystallinity means that atoms are regularly and regularly arranged in accordance with a certain symmetry, and diffraction phenomena due to X-rays are recognized (Kyoritsu Shuppan Co., Ltd., Dictionary of Chemistry, 1963, 3rd edition).
Vol., P. 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 limit size based on the crystal structure. Therefore, the crystalline aluminosilicate used in the present invention is:
X-ray diffraction phenomenon was observed, and the primary particle diameter was 0.5 μm.
m or less. In addition, the measurement of the primary particle diameter was performed using a scanning electron microscope photograph (magnification: 2000 to 100).
000 times).

The primary particle diameter used in the present invention is 0.5 μm
The following crystalline aluminosilicate does not particularly limit the molar ratio of silica to alumina, but those having a molar ratio of silica and alumina of 10 or more, particularly those having a molar ratio of silica and alumina of 20 or more. preferable. When the molar ratio of silica to alumina is as high as 10 or more, the acid strength of the acid site, which is the active site of the hydration reaction, increases, but the amount of the acid site decreases significantly. When using a cyclic olefin as a raw material,
Due to its properties, reactivity, etc., it does not necessarily improve the activity and selectivity of the hydration reaction as it is. The practical meaning is significant.

By the way, if the particle size of the primary particles is small,
It is effective even if the diameter of the secondary particles formed by such aggregation is increased. The secondary particle diameter is preferably 50 μm or less. Above this, mass transfer of the cyclic olefin or cyclic alcohol in the macropores of the catalyst particles is suppressed, and the reaction rate is reduced. The particle size referred to herein means a particle having a value less than the indicated value is at least 50% by weight or more.

The crystalline aluminosilicate used in the present invention includes, for example, mordenite, boshasite, clinoptilolite, L-type zeolite, and ZSM zeolite (ZSM-5, ZSM-11) published by Mobil.
Etc.), chabazite, erionite and the like. Mixtures of these are also useful. Examples of the crystalline aluminosilicate containing a metal element include those containing a thorium element (JP-A-60-248632), those containing copper and / or silver (JP-A-60-248633),
One containing at least one of chromium, molybdenum and tungsten (JP-A-60-248634), titanium,
It may contain at least one of zirconium and hafnium (JP-A-60-248635). In addition, a urea compound is used as a synthesis method (Japanese Patent Application Laid-Open No. 61-6831).
9), (JP-A-61-180735), in the presence of a cyanoalkene (JP-A-62-36017), (JP-A-63-1)
54633), (JP-A-63-315512) and (JP-A-61-221141). Synthesized only with inorganic substances (JP-A-1-180835);
(JP-A-1-190644) and synthesis in the presence of an amine (JP-A-1-192717). In particular, finely divided crystalline aluminosilicate is effective.

When the amount of the catalyst in the aqueous phase in the reaction solution is small, the reaction rate is slow and the reactor becomes large, and it is difficult to industrially work. The diffusion rate of the cyclic olefin in the phase is inhibited and the reaction rate is reduced. Therefore, the weight ratio of the catalyst to water is preferably in the range of 0.01 to 2.0, and more preferably in the range of 0.1 to 1.0. The reaction temperature is usually in the range of 50 to 250 ° C., preferably 7 to 250 ° C.
The range of 0 to 200 ° C, particularly 80 to 150 ° C, is preferred.
The reaction pressure is not particularly limited, but is preferably a pressure at which both water and the cyclic olefin can maintain a liquid state.

In the present invention, the oil phase has an average droplet diameter of 0.0
It must be dispersed in the continuous aqueous phase as droplets of 5 to 30 mm. By the way, as a method of dispersing fine droplets of the oil phase in the continuous phase of water, a method of ejecting the oil phase from a disperser having many holes, and a method of mechanically dispersing the fluid by applying a shear force to the fluid with a stirrer etc. There is a way to make it happen. In this case, in order to form fine droplets, it is necessary to apply an external force sufficient to overcome the interfacial pressure and viscous stress to the droplets for a certain period of time or more to break up the droplets. Therefore, when a disperser is used, it can be achieved by reducing the hole diameter or increasing the ejection speed. In addition, when a stirrer is used, the shearing rate may be increased, and generally, the stirring power supplied to the fluid may be increased.

The embodiments of the method for hydrating a cyclic olefin of the present invention will be described below with reference to FIGS. 1 to 9, but the present invention is not limited to these embodiments. FIG. 1 is a schematic diagram showing an internal cross section of a reaction vessel for performing one embodiment (first embodiment) of the method of the present invention. The reaction tank 4 has a disperser 6 connected to the raw material supply pipe 3 in the lower part of the tank, and further has a thermometer sheath pipe (both not shown) containing a thermometer and a pressure gauge (not shown) attached thereto. is there. An oil phase outlet connected to an extraction pipe 5 for an oil phase containing the generated cyclic alcohol and unreacted cyclic olefin is provided at the upper part of the reaction tank 4. The above-mentioned pipe 3 is connected to the cyclic olefin supply pipe 1 and the water supply pipe 2, and is also connected to the circulation pipe branched from the oil phase extraction pipe 5, and a part of the extracted oil phase is pumped. 8 is used to recycle to the reaction phase 4 and eject it from the disperser 6. Further, an electric heater (not shown) is attached to the outer surface of the reaction tank 4,
Flow meters (not shown) for all of the above pipes
With. On the side wall of the reaction tank 4, a glass viewing window (not shown) for observing the separation state of the continuous aqueous phase and the oil phase in which the oil droplets are dispersed and for observing the oil-water interface is attached. That is, according to the first aspect of the present invention, at least one disperser connected to the raw material supply pipe and having a large number of pores is provided in the lower part of the reaction tank, and the generated cyclic alcohol and the unreacted cyclic alcohol are provided in the upper part of the reaction tank. The reaction is carried out in a reaction vessel having an oil phase outlet connected to a withdrawing means for extracting the oil phase obtained by the reaction containing the cyclic olefin, and the oil phase is supplied through a raw material supply pipe to pass through the pores of the disperser. A method for hydrating a cyclic olefin is provided, wherein the oil phase is dispersed and circulated as a droplet having an average droplet diameter of 0.05 to 30 mm in a continuous aqueous phase by jetting the oil phase into a reaction system. . The continuous phase of the oil phase formed at the upper part in the reaction tank by coalescence of the oil droplets obtained by the reaction is extracted from the outlet and the extraction means, and a part thereof is branched from the extraction means and connected to the raw material supply pipe by a conduit. The oil is circulated to the reaction tank, and the circulated oil layer is ejected from the pores of the disperser. The shape of the reaction tank is not particularly limited, and may be a vertical type, a horizontal type, a square type, a cylindrical type, or the like. desirable.

In the case of the present invention, when the raw material cyclic olefin oil phase is allowed to flow without circulation, the overall reaction rate tends to be mass transfer-controlled because the volume ratio of oil droplets to the aqueous phase is not sufficient. Therefore, in order to increase the oil phase droplet hold-up, a part of the unreacted cyclic olefin and a part of the cyclic alcohol product, that is, the unreacted cyclic olefin and the cyclic alcohol product are combined at the upper part of the reactor, for example, by using a pump or the like. Circulate using
By spouting through a disperser arranged at the bottom of the reaction tank, the ratio of the oil phase containing mainly cyclic olefin to the aqueous phase at the reaction site can be increased, and mass transfer rate-limiting can be avoided. The circulation flow rate is more effective as the circulation flow rate increases, but in the present invention, the aqueous phase is a continuous phase as described above. Usually, the reaction product circulation flow rate to the feed flow rate of the raw material cyclic olefin is preferably 1 to 150 weight ratio.

As the disperser for dispersing the cyclic olefin in the reaction solution, a disperser having a large number of holes having an inner diameter of 0.3 to 10.0 mm is used. If the cyclic olefin used is one that allows oil droplets to coalesce quickly, the above disperser is sufficiently effective.
In the case of a reaction solution that easily forms an emulsion, the diameter of the hole should be 2 to 5 in order to prevent the formation of fine droplets.
It is more preferable to use a disperser having a pipe with a double inner diameter and a length of 10 to 200 mm. In addition, uniform dispersion can be achieved by increasing the number of disperser pipes depending on the size of the reaction tank cross-sectional area.

According to another embodiment (second embodiment) of the present invention, the reaction is carried out in at least one reaction vessel having a stirrer having a plurality of stirring blades, and the whole reaction system is stirred to generate a shear force. By operating the stirrer to prevent the sedimentation of the catalyst suspended in the continuous aqueous phase, the oil droplets that have coalesced away from the stirring blades are redispersed to remove the oil phase in the continuous aqueous phase. A method is provided for maintaining a droplet. FIG. 2 is a schematic view of a second embodiment of the method of the present invention in which a stirrer is installed in a reaction vessel. In the above-described first embodiment of the present invention, the reaction tank 4 is connected to the disperser 6 connected to the raw material supply pipe 3 and the reaction product extraction pipe 5 containing the cyclic alcohol obtained by the reaction and the unreacted cyclic olefin. It has a product outlet, and the raw material supply pipe 3 is connected to the cyclic olefin supply pipe 1 and the water supply pipe 2. In the second embodiment, unlike the reaction tank 4 used in the first embodiment, the reaction tank 4 has a stirrer having a plurality of stirring blades 9 and generates a shear force by stirring the entire reaction system. By operating the stirrer such that the catalyst suspended in the continuous aqueous phase is prevented from settling, the oil droplets that have coalesced at a distance from the stirring blade 9 are redispersed to remove the oil phase in the continuous aqueous phase. Can be maintained in the form of droplets. In addition, the reaction tank 4 has an outlet for a reaction product that is an oil phase at an upper portion,
Since the weir 7 is disposed near the outlet of the reaction product and the stationary region is provided, the obtained reaction mixture is easily converted into an oil phase as an upper layer containing a cyclic alcohol and an aqueous phase as a lower layer containing a catalyst. Can be separated.

The type of the stirring blade 9 is preferably a blade structure such as a turbine, a propeller, or a paddle. In particular, the propeller blades are preferable because they can generate up-and-down circulating flows with small power and do not produce unnecessarily fine droplets. The shaft of the stirrer does not need to be at the center of the reaction vessel, and the number of the stirrers does not need to be one. Further, the blade attached to the stirrer may have one or more stages and a multi-stage blade structure. Further, the blade type of each stage of the multi-stage blade may be different.

In the method of the present invention, it is preferred that the oil phase containing the cyclic olefin is circulated as a mixture with the aqueous phase by using a stirrer with a downward fluid component. Specifically, to mix the oil phase, which is lighter than the specific gravity of the aqueous phase, with the aqueous phase,
It is preferred that there be a downward flowing component that entrains the raised oil phase. The direction of the flow may be either downward at the center as shown in FIG. 2 or downward at the outside.

The disperser for ejecting the raw material cyclic olefin is:
The pipe having a large number of holes used in the first embodiment may be used, but a small turbine blade having a large number of blades is attached to the stirring shaft, and a raw material supply pipe is arranged above or below the blade. With the structure, moderately coarse droplets can be created and agitated flow can be applied, so that as soon as the raw material is supplied, the raw material is prevented from forming a large oil phase lump and short-passing to the stationary area Can be. When this method is used, the material supply port can be enlarged, so that scaling or clogging due to the catalyst can be avoided.

The reaction tank shown in FIG. 3 further enhances the effect of stirring, and is obtained by adding a hollow cylinder 10 to the apparatus shown in FIG. Specifically, a hollow cylinder 10 having inner and outer walls and open at the upper and lower ends is arranged in the reaction vessel so as to surround the stirrer. A first space is provided therebetween, and a second space is provided between the outer wall of the hollow cylinder 10 and the inner wall of the reaction tank 4, and the hollow cylinder 10 is provided with a reaction system sufficient for the first and second spaces. It has a cross-sectional area that circulates through and functions as a draft tube. The hollow cylinder 10 is usually arranged so as to surround the stirrer. However, even if the stirring blade 9 slightly protrudes outside, the effect is not significantly impaired. The hollow cylinder 10 is usually fixed to the inner wall of the reaction vessel, or the fixing method is not particularly limited as long as the fixing means withstands the pressure generated by the circulation of the reaction system and the circulation flow of the reaction system is smooth. As a fixing means, for example, a metal plate can be used. By circulating the aqueous phase containing droplets of the cyclic olefin oil phase by arranging the hollow cylinder, the downward circulating flow can be strengthened, and the oil phase and the aqueous phase can be stirred and mixed even with weak stirring power. Therefore, a sufficient reaction rate can be obtained. Further, since no strong stirring is performed, fine droplets are not generated, and the separation of oil and water in the stationary region after the reaction becomes very easy. Also, strong stirring may cause catalyst damage,
There were problems such as catalyst loss when extracting from the reactor and filtering during regeneration of the catalyst, or clogging when using a filter, but the problem was that sufficient mixing for the reaction was possible with weak stirring. Solving the problem is one of the effects.

[0042] The stirring power of the reactor equipped with a hollow cylinder is such that the same reaction yield can be obtained at 1/5 to 1/10 as compared with the case without it. In the case of a stirring type reaction tank, it is more effective to add a baffle plate. That is, the reaction vessel has at least one vertically extending baffle plate projecting from the inner wall of the reaction vessel substantially toward the center toward the inner wall, and the baffle plate is disposed above and below the reaction system in the reaction system. The baffle plate has a longer length, and the longer the baffle plate is, the stronger the vertical circulating flow is and the more effective the baffle plate is. In addition, the baffle plate is generally fixed to the inner wall of the reaction tank, but the method of fixing is not particularly limited as long as the baffle plate is perpendicular to the inner wall of the reaction tank.

The number of baffle plates is generally determined by the size of the reactor stirring area, and it is effective to increase the number of baffle plates according to the size of the stirring area. The baffle plate is a hollow cylinder 10 shown in FIG.
When used in combination with, the effect of strengthening the downward circulating flow is enhanced, which is preferable. However, the effect can be achieved only with the baffle plate.

In order to take out only the oil phase containing the cyclic alcohol generated by oil-water separation, as shown in FIGS. 2 and 3, the reaction product outlet (connected to the reaction product discharge pipe 5) This can be achieved by disposing a weir 7 at the bottom to provide a stationary area to facilitate phase separation. That is, the oil droplets in the reaction mixture rise in the stationary region, and a continuous oil phase is formed in the upper layer,
A continuous aqueous phase is formed in the lower layer. The continuous oil phase is withdrawn from the reaction product withdrawing tube 5, whereby the cyclic alcohol is isolated. On the other hand, since the specific gravity of the continuous oil phase is higher than that of the reaction mixture, the continuous oil phase descends and replaces the reaction mixture. Oil-water separation of the reaction mixture is performed as described above.

FIG. 4 shows another embodiment in which oil-water separation is performed in the method of the present invention. A reaction mixture containing an oil phase and an aqueous phase obtained by the reaction is passed through a pipe 12 to the outside of the reaction tank. It is introduced into the provided oil / water separation tank 11 and is separated into an oil phase as an upper layer containing the generated cyclic alcohol and an aqueous phase as a lower layer containing the catalyst. The oil phase is extracted from the pipe 5 and a part of the oil phase is circulated to the reaction tank 4 as in the first embodiment of the method of the present invention, and the aqueous phase is circulated to the reaction tank 4 by the pipe 13 by the pump 8. The movement of the reaction mixture from the reaction tank 4 to the oil / water separation tank 11 through the pipe 12 and the movement from the oil / water separation tank 11 to the reaction tank 4 through the pipe 13 are performed by gravity or by a pump as described above. Compared with a reaction tank having a stationary area, in the reaction tank 4 for performing oil / water separation in the oil / water separation tank 11 as described above, an oil droplet having an appropriate droplet diameter is more likely to be generated, and therefore, oil / water separation can be performed effectively. it can.

Oil-water separation of a large amount of the reaction mixture can also be achieved by installing a baffle plate in the reaction tank instead of using the oil-water separation tank 11 described above, and the stationary area can be made compact. it can. As shown in FIG. 5, the reaction tank 4 is partitioned using baffle plates 7A, thereby providing a stirring area as a lower area in the tank and a stationary area 5A as an upper area in the tank, and the reaction system in the stirring area. By generating a shearing force by stirring, the oil phase becomes droplets and disperses in the continuous aqueous phase, and the oil droplets move from the stirring region to the stationary region 5A through the baffle plate 7A, and stand still. The oil droplets unite in the region 5A to form a continuous oil phase. As a baffle plate, a perforated disk (directly attached to the inner wall of the reaction vessel at its outer periphery); a non-perforated disk (a gap is provided between the inner wall of the reaction vessel and fixed to the inner wall of the reaction vessel by a support) ;
Grid deck (peripherally attached directly to the inner wall of the reactor); flat donut plate (peripherally attached directly to the inner wall of the reactor); truncated hollow cone with a vertex pointing downwards Donut plate (directly attached to the inner wall of the reaction vessel at the outer periphery of the bottom surface of the open cone); a donut plate in which the tip of a hollow cone whose apex faces upward is cut off (a gap is provided between the inner wall of the reaction vessel and Is fixed directly to the inner wall of the reactor at the outer periphery of the bottom surface of the open cone); and for a hollow cone having a downward apex and a hollow cone having an apex upward,
A donut plate formed by cutting off the respective tips and joining them at the cut-out portion (the open conical bottom faces upward and downward, respectively, and is directly attached to the inner wall of the reaction vessel at the outer periphery of each conical bottom surface) ) Can be used.

For example, in the reaction tank 4 shown in FIG. 6, a donut plate 7A-1 is disposed in a tank, and a stationary area 5A-1 as an upper area in the tank and a stirring area as a lower area in the tank are provided. Provided. The donut plate 7A-1 is a combination of a hollow cone having a downwardly directed apex and a hollow cone having an upwardly directed apex, which are obtained by cutting off the respective tips and joining the cut portions. Each cone is directly attached to the inner wall of the reaction tank at the outer periphery of the bottom surface of each cone so as to face upward and downward. FIG.
In the reaction tank 4 shown in Fig. 5, a porous disk 7A-2 is arranged in the tank, and a stationary area 5A-2 as an upper area in the tank and a stirring area as a lower area in the tank are provided.

Further, as the baffle plate, an obstacle as shown in FIGS.

According to still another embodiment (third embodiment) of the present invention, the reaction is carried out using a plurality of serially connected reaction tanks each comprising a first reaction tank and at least one supplementary reaction tank. The reaction mixture containing the cyclic alcohol and the unreacted cyclic olefin obtained in the first reaction vessel or the supplementary reaction vessel preceding the at least one supplementary reaction vessel is supplied to the next supplementary reaction vessel of each preceding reaction vessel. A method is provided for feeding and hydrating unreacted cyclic olefins there.

FIG. 8 is a schematic view showing the internal cross section of two reaction vessels connected in series for carrying out still another embodiment (third embodiment) of the method of the present invention. First reaction tank 4-1
A stirrer having stirring blades 9, a raw material supply pipe 3 connected to a supply pipe 1 and a water supply pipe 2 for an oil phase containing a cyclic olefin, a weir 7 for providing a stationary area, and an inlet 14 and an outlet. A steam flow coil having 15 is installed. First
The oil phase separated in the stationary region of the reaction tank 4-1 is extracted from the pipe 5-1 and supplied to the lower part of the supplementary reaction tank 4-2. The supplementary reactor 4-2 has substantially the same structure as the first reactor 4-1 except that a steam or cooling water flowing coil having an inlet 16 and an outlet 17 is attached instead of the steam flowing coil. After the hydration reaction, the oil phase supplied to the supplementary reaction tank 4-2 is separated in the stationary region, extracted from the pipe 5-2, and all the extracted oil phase is distilled to isolate the generated cyclic alcohol. I do. The first reaction tank 4-1 and the supplementary reaction tank 4-2 are connected through a pressure equalizing pipe 18, and by supplying an inert gas from the pressure equalizing pipe 18 to an inert gas supply pipe 19, a gas phase in each tank is supplied. The pressure is adjusted so that the pressures are uniform. In the third embodiment of the method of the present invention as shown in FIG. 8, as shown in FIG. 1 and FIG.
-2, a circulation pipe is branched from each of the oil phase extraction pipes 5-1 and 5-2, and a part of the extracted oil phase is recycled to each reaction tank by a pump, and dispersed together with the raw materials. It may be spouted from.

As mentioned previously, the equilibrium conversion of cyclic olefins to cyclic alcohols increases with lower temperature. On the other hand, the reaction rate increases as the temperature increases.
Therefore, in order to increase the reaction yield per cyclic alcohol single stream from a cyclic olefin, it is necessary to contact the catalyst at a low temperature for a long time. However, since the temperature is low, the reaction rate is low, a large amount of catalyst is required, and the productivity is poor, as described above, because the reaction tank becomes large.

The present inventors have carefully studied the mechanism of the present reaction in order to solve the above-mentioned problems. As a result, as shown in FIG. 8, the temperatures of a plurality of reaction vessels connected in series are successively changed according to the flow direction of the reaction system. By controlling the reaction yield to be as low as possible, a condition was found which further increased the reaction yield per single stream of the cyclic alcohol as compared with the above-mentioned method.

Further, in the third embodiment of the method of the present invention, the flow of the reaction system approaches the piston flow in the plurality of reaction tanks connected in series, so that the cyclic alcohol concentration in the oil phase is equal to the equilibrium concentration. It approaches a certain 10 to 40% by weight, and the reaction yield per single stream can be increased.

The effect of the third embodiment of the method of the present invention described above is as shown in FIG. 9, in which a plurality of small chambers are partitioned by obstacles, and each chamber has at least one stirring blade set. Can also be achieved. That is, according to still another embodiment (third embodiment) of the present invention, as shown in FIG. 9, the reaction tank 4 has a stirrer provided with a plurality of stirring blades 9, and the plurality of stirring blades 9 The reaction vessel 4 is divided into a plurality of small chambers arranged in a multi-stage manner by an obstacle 20, and each chamber includes at least one stirring blade set. Providing a stirring area for the system, operating the stirrer to stir the entire reaction system in each chamber to disperse the oil phase in the continuous aqueous phase, and to prevent the sedimentation of the catalyst suspended in the continuous aqueous phase, In each chamber, the coalesced oil droplets are re-dispersed at a distance from the stirring blade 9, and between the two adjacent chambers separated by the obstacle 20, from the first chamber to the second chamber in a predetermined direction. That the reaction system flows toward the cell At the same time, a method is provided that prevents the reaction system from backflowing in the above direction, thereby preventing the reaction system in the second compartment from backmixing with the reaction system in the second compartment. . In this way, each of the compartments formed by the obstacles 20 functions as an individual reaction tank having a stirrer.

Further, in the reaction tank shown in FIG. 9, a stirring area as an area below the obstacle and a stationary area as an area above the obstacle are provided by the uppermost obstacle, and the reaction system is stirred in the stirring area. As a result, the oil phase is dispersed as droplets in the continuous aqueous phase by causing a shear force, and the oil droplets move from the stirring region to the stationary region through the obstacles, and are moved in the stationary region. The oil droplets coalesce to form a continuous oil phase.

The obstacle 20 is not particularly limited, and may be, for example, a perforated plate, a wire mesh, a donut plate, a meniscus, a grid deck, a conical angle deck, or a disk fixed to the inner wall of a reaction tank with a support (the outer periphery and the reaction tube). There is a gap between the inner wall of the tank and the like), and these may be used in combination.

FIGS. 10 to 12 show three types of obstacles. FIG. 10 shows a perforated plate 20A as an example of an obstacle; FIG. 11 shows a disc 20B as another example of an obstacle; FIG. 12 shows a flat donut plate 20C as another example of an obstacle (reaction at the outer periphery thereof). Directly attached to the inner wall of the tank). FIG.
0, 13 to 15 further show examples of the donut plate of FIG. FIG. 13 shows still another example of a donut plate as an obstacle. A donut plate 20C-1 in which the tip of a hollow cone whose top is downward is cut off is directly attached to the inner wall of the reaction vessel at the outer periphery of the bottom surface of the cone. FIG. 14 shows another example of a donut plate as an obstacle, a donut plate 20C-2 in which the tip of a hollow cone with an apex pointing upward is cut off (a gap is formed between the donut plate 20C-2 and the inner wall of the reaction tank). Provided and fixed directly to the inner wall of the reaction vessel at the outer periphery of the bottom of the above-mentioned cone); and FIG. 15 shows another example of a donut plate as an obstacle, a hollow cone having a downward apex and an upward cone. Donut plate 20C-3 (open cone bottom faces upward and downward, respectively) in the form of a hollow cone that is obtained by cutting off the respective ends and joining the cut-out portions. Ensure a mounted directly to the reaction vessel inner wall at the outer periphery of each conical bottom)
Is shown. In the above-mentioned reaction tank, the reaction system flows in the direction of the arrow shown in each figure.

The ratio of the height of each small chamber (that is, the stirring area) to the inner diameter of the reaction vessel is preferably 0.2 to 2. The shape of the stirring blade 9 may be the same or different for each stirring region, and the position of the stirring blade set in each stirring region is not particularly limited as long as sufficient stirring is performed.

Referring back to FIG. 9, a heating steam jacket 21 and a cooling water jacket 22 are attached to the outer surface of the reaction tank 4 to adjust the temperature of the reaction system.

In such a multi-stage reaction tank, the concentration of cyclohexanol in the oil phase is low in the reaction system near the outlet of the raw material supply pipe, and the equilibrium concentration has not been reached. Therefore, the reaction temperature is raised to convert cyclohexene to cyclohexanol. By increasing the reaction rate of, the productivity per catalyst can be increased. On the other hand, the concentration of cyclohexanol increases in the later stages and approaches the equilibrium concentration, so by lowering the reaction temperature, the equilibrium value is increased even if the reaction rate is slightly reduced, and the final single-flow reaction The yield is improved. Therefore, when dividing the reaction tank into a plurality of small chambers by obstacles, the temperature of the plurality of small chambers is
It is preferable to control the temperature to decrease gradually according to the flow direction of the reaction system.

However, this reaction is an exothermic reaction, and if a multi-stage reaction is carried out adiabatically, the temperature of the reaction system will increase as going to the subsequent stage, and conversely the single-stream reaction yield will decrease, so that Generally, the reaction system in the lowermost chamber is heated and the subsequent reaction zones in each stage are appropriately cooled.
As a specific reaction temperature, the initial reaction zone is 110 to 170
° C and lower the reaction temperature as you go to the next stage.
It is preferable to lower the temperature of the final stage by 1 to 30 ° C. from the initial reaction temperature. Further, as the temperature control means for the reaction zone, a pipe for flowing cooling water or steam may be arranged in a coil shape in a vessel, or the vessel itself may have a jacket structure for flowing cooling water or steam. It is preferable that the amount of cooling water or steam in each stage can be controlled independently for each mixer settler.

In order to obtain the reaction product, the uppermost chamber among the small chambers has a reaction product outlet, and a weir is provided near the reaction product outlet to provide a stationary area. It is preferable to facilitate separation into an oil phase as the upper layer containing the cyclic olefin that has produced the reaction mixture and a continuous aqueous phase as the lower layer containing the catalyst. Or, as shown in FIG.
The obtained reaction mixture is introduced into an oil / water separation tank provided outside the reaction tank, and separated into an oil phase as an upper layer containing the generated cyclic alcohol and an aqueous phase as a lower layer containing the catalyst, and then the oil phase is extracted. A part thereof may be circulated to the reaction tank, and the aqueous phase may be circulated to the reaction tank.

In the fourth embodiment of the method of the present invention, the flow of the reaction system approaches the piston flow in a plurality of small chambers arranged in a multistage manner. Cyclic alcohol concentration of 10 to 40 is the equilibrium concentration
% By weight, and the reaction yield per single stream can be increased.

Further, in the fourth embodiment of the method of the present invention, similarly to the above-described third embodiment, the reaction yield can be further increased by connecting a plurality of reaction vessels in series.

[0065]

EXAMPLES The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. (Example 1) An average primary particle diameter of 0.04 μm and SiO ₂
The hydration reaction of cyclohexene was performed under the following conditions using an H-type ZSM-5 catalyst having a / Al ₂ O ₃ ratio of 28. As a cyclohexene hydration reactor, as shown in FIG. 1, a thermometer and sheath pipe (not shown), a raw material supply pipe 3 and an oil phase extraction pipe are provided inside a 24-liter stainless steel pressure-resistant reactor 4. Reaction product connected to 5 (oil phase)
An outlet / pressure gauge (not shown) was attached, and a disperser 6 composed of a pipe having many pores was connected to the raw material supply pipe 3 in the lower part of the reaction tank 4. Further, an electric heater for temperature control (not shown) is attached to the outer surface of the reaction tank 4, branched from the oil phase extraction pipe 5, connected to the raw material supply pipe 3 via the circulation pump 8,
Oil circulation piping was provided. Further, a cyclohexene supply pipe 1 and a water supply pipe 2 were connected to the raw material supply pipe 3. A flow meter (not shown) was attached to each pipe. The reaction product outlet was provided above the reaction tank 4. In order to observe the oil-water separation state and measure the interface position, a glass viewing window (not shown) was provided directly on a part of the side surface of the reaction tank 4.

In the hydration reaction, first, the inside of the reaction tank was purged with nitrogen, and then 19.7 of a water slurry having a catalyst concentration of 30% by weight was used.
kg into the reactor, pipes 1 and 3 and disperser 6
, A cyclohexene solution was immediately introduced to fill the inside of the reaction tank, the circulation pump and the piping. The circulation pump 8 was started, the circulation flow rate was adjusted to be constant at 600 liter / hr, and cyclohexene oil droplets were dispersed in the reaction tank. The temperature was raised by an electric heater, and the temperature inside the reaction tank was controlled to be constant at 120 ° C. Reaction tank internal pressure is 6
It was constantly pressurized with nitrogen gas so that kg / cm ² gauge was constant. About 6.1 kg of raw material cyclohexene liquid at steady state
/ Hr (: kg / hour: the same applies hereinafter), and feed the water in an amount corresponding to the water consumption so that the oil-water interface level in the reaction tank is located slightly below the reaction product outlet. Feeded through tube. The reaction product withdrawal amount was controlled so that the gas-liquid interface was located above the reaction product outlet. After stabilization of the entire system, the concentration of cyclohexanol in the reaction product discharged from the reactor was 11.0% by weight, and the selectivity to cyclohexanol was 99.5%. This value is a reaction result in the reaction-limited state, and is a satisfactory value. The average droplet diameter of the oil phase in the reaction tank was 2 mm. The extracted reaction product had no catalyst at all and was in a good oil-water separation state. Subsequently, in order to evaluate the oil-water separation time, the feed and circulation were temporarily stopped at the same time. A continuous oil phase was formed at the upper part and a continuous water phase was formed at the lower part 26 seconds after the supply of the raw material and the circulation were stopped, and the oil droplets existing between the two phases were completely disappeared. The hold-up rate of the droplets during stirring was 10.5% by volume.

(Examples 2 to 4) Using the hydration reactor of Example 1, the reaction conditions were the same as in Example 1, and only the circulation flow rate was changed as shown in Table 1, and the reaction results were examined. The results were as shown in Table 1. The extracted reaction product had no catalyst at all and was in a good oil-water separation state.

(Comparative Example 1) Using the hydration reactor of Example 1, the reaction conditions were the same as in Example 1, except that the disperser 6 was removed and the material was directly ejected from the raw material supply pipe 3.
The reaction was carried out at a circulation rate of 200 l / hr. As a result, the concentration of cyclohexanol in the reaction product withdrawn from the reactor was 1 to 3%, and the concentration also fluctuated. The selectivity to cyclohexanol was 98.5%. At this time, the average droplet diameter of the oil phase in the reaction tank was 40 mm.
Table 1 shows the results of Comparative Example 1 together with the results of Examples 1 to 4.

[0069]

[Table 1]

Example 5 As shown in FIG. 2, an autoclave 4 with a stainless steel stirrer of 4 liters having a glass observation window (not shown) was attached so that the internal state could be observed. A thermometer, a sheath pipe (not shown), a reaction product (oil phase) outlet and a pressure gauge (not shown) connected to a raw material supply pipe 3 and an oil phase extraction pipe 5 are attached, and the stirrer 9 is stirred. As a blade of a propeller blade, a disperser 6 similar to that of the first embodiment was provided immediately below the blade, connected to the raw material supply pipe 3, and a weir 7 penetrating the gas-liquid interface near the outlet of the reaction product.
To provide a stationary area for oil-water separation. Further, an electric heater for temperature control (not shown) was attached to the outer surface of the autoclave, and the raw material supply tube 3 was connected to the cyclohexene supply tube 1 and the water supply tube 2. A flow meter (not shown) was attached to each pipe. The reaction product outlet was provided above the autoclave. Four baffle plates (not shown) projecting from the inner wall surface of the stirring section toward the center and near the inner wall were mounted.

In the hydration reaction, first, after purging the inside of the hydration reaction tank 4 with nitrogen, 2.68 kg of a water slurry having a catalyst concentration of 30% by weight with the same new catalyst as in Example 1 was charged into the reaction tank. Then, the stirrer was rotated at 530 rpm, and the temperature in the reaction tank was controlled to be constant at 120 ° C. by heating with an electric heater. The raw material cyclohexene solution is gradually supplied,
The constant value was about 0.85 kg / hr. Reaction tank internal pressure is 6k
The pressure was constantly increased with nitrogen so that the g / cm ² gauge was constant. Water corresponding to the consumed water amount was supplied through the raw material supply pipe 3 so that the oil-water interface level in the stationary region in the reaction tank was located below the reaction product outlet connected to the pipe 5. The gas-liquid interface was kept constant by making the oil phase extraction pipe 5 an overflow type. After the entire system was stabilized, the concentration of cyclohexanol in the reaction product discharged from the reactor was 11.1% by weight, and the selectivity to cyclohexanol was 99.5.
%Met. This value is the reaction result in the reaction limited state,
This is a satisfactory value. The stirring power at this time is about 0.5
Kw / m ³ (volume is the volume of the whole reaction system). The average droplet diameter of the oil phase in the reaction tank was 0.22 mm. The extracted reaction product had no catalyst at all and was in a good oil-water separation state.

Subsequently, the stirring and the raw material supply were temporarily stopped at the same time, and the oil / water separation time was evaluated in batches. As a result, a continuous oil phase was formed on the upper part and a continuous aqueous phase was formed on the lower part 12 seconds after the suspension of the stirring and the supply of the raw material, and the dispersed phase of the intermediate oil droplets was completely disappeared. The droplet hold-up rate at this time was 30% by volume. After operating for 50 hours under the above reaction conditions, the cyclohexanol concentration in the reaction product was 10.8% by weight, and the selectivity to cyclohexanol was 9%.
It was 9.5%. There was almost no decrease in the activity of the catalyst, and no catalyst was mixed in the extracted reaction product. The state of separation of the oil and water after 50 hours was evaluated by the same method as that at the start of the reaction. As a result, the dispersed phase of the droplets was completely disappeared 13 seconds after the stirring and the supply of the raw material were stopped. Thus, it was found that a long-term stable reaction could be maintained.

(Examples 6 to 8) Using the hydration reaction apparatus of Example 5, the reaction conditions were the same as in Example 5, and only the rotation speed of stirring was changed as shown in Table 2, and the reaction results were examined. . The results are as shown in Table 2. The extracted reaction product contained no catalyst at all and was in a good oil-water separation state.

(Comparative Example 2) The reaction conditions were the same as in Example 5 using the hydration reactor of Example 5, but the reaction was carried out at 310 rpm with a stirrer rotation speed. The cyclohexanol concentration is 1-2%,
The selectivity to cyclohexanol was 98.0%.
The stirring state was such that an oil continuous phase was present in the upper part of the reactor, separated into two layers, and almost no oil dispersed phase was observed. Table 2 shows the results of Comparative Example 2 together with the results of Examples 5 to 8.
Shown in

[0075]

[Table 2]

(Example 9) A hollow cylinder 10 (draft tube) was placed inside the reaction vessel 4 of Example 5 so as to surround the stirring blade 9 and slightly away from the bottom of the reaction vessel.
All other equipment such as the stirring blade 9 was the same as in Example 5. The position of the reaction product outlet was set slightly higher than in Example 5. The catalyst used was the same as the new catalyst in Example 1. The reaction conditions were the same as in Example 5. After the whole system was stabilized, the concentration of cyclohexanol in the reaction product discharged from the reaction vessel was 11.2% by weight, and the selectivity of cyclohexene was 99.5%. The extracted reaction product had no catalyst at all and was in a good oil-water separation state. The oil-water separation time was measured in batches in the same manner as in Example 5. The oil-water separation time was 11 seconds after the stirring and the supply of the raw materials were stopped. The oil droplet hold-up rate at this time was 40% by volume.

(Examples 10 to 12) Using the reactor of Example 9, the reaction conditions were all the same as in Example 9 except that the number of revolutions was changed as shown in Table 3. Table 3 shows the results. The extracted reaction product had no catalyst at all and was in a good oil-water separation state. It can be seen that the concentration of cyclohexanol in the reaction product from the reaction tank was kept high even though the stirring rotation speed was lowered by attaching the draft tube.

(Comparative Example 3) Using the reactor of Example 9,
All reaction conditions were the same except that the number of revolutions was reduced to 50 rpm. The cyclohexanol concentration in the reaction product is 1-2% by weight, and the selectivity of cyclohexene is 9%.
It was 7.8%. The stirring state was such that an oil continuous phase was present in the upper part of the reactor, separated into two layers, and almost no oil dispersed phase was observed. The results of Comparative Example 3 were compared with Examples 9-1.
The results are shown in Table 3 together with the results of Example 2.

[0079]

[Table 3]

Example 13 As shown in FIG. 4, in the reactor of Example 9, the weir 7 in the reaction tank was removed to separate oil and water from the draft tube. A liter container is provided with a reaction solution introduction tube 12, a reaction product extraction tube 5, and a water slurry extraction tube 13, and the reaction solution introduction tube 12 and the water slurry extraction tube 13 are attached to side surfaces of an autoclave with a stirrer, respectively. I have. Also,
A glass viewing window is attached directly to the oil-water separation tank 11,
It was made possible to measure the oil-water interface. Withdrawal of the reaction product from the oil / water separation tank 11 was adjusted so that the gas-liquid interface between the reaction tank 4 and the oil / water separation tank 11 was kept substantially the same and constant.

A part of the reaction product (oil phase) from the oil / water separation tank 11 was circulated to the raw material supply pipe 3 via the circulation pump 8. The circulation flow rate was 20 l / hr. The rotation speed of the stirrer is 100 rpm, and the input stirring power is 0.0
It was 1 Kw / m ³ . The hydration reaction was carried out in the same manner as in Example 9. As a result, the cyclohexanol concentration in the reaction product discharged from the reactor after stabilization of the entire system was 11.2% by weight, and the selectivity was 99.5%. And the same result as in Example 9.
The extracted reaction product had no catalyst at all and was in a good oil-water separation state. Subsequently, the supply of the raw material, the stirring and the circulation by the pump were temporarily stopped simultaneously, and the oil-water separation time in the batch was measured. As a result, the oil-water separation time was 4 seconds.

(Example 14) Using the hydration reactor of Example 5, the reaction conditions were the same as in Example 5, and the reaction results were examined by changing the starting material to cyclopentene. The cyclopentanol concentration in the resulting reaction product was 7.1% by weight, and the selectivity for cyclopentanol was 9%.
A good reaction result of 9.5% was obtained. The extracted reaction product had no catalyst at all and was in a good oil-water separation state.
Subsequently, the raw material supply and stirring were stopped in the same manner as in Example 5, and the oil-water separation time was measured. As a result, the oil-water separation time was 13 seconds.

(Example 15) Inside the reaction vessel of Example 5,
As shown in FIG. 5, a baffle plate 7A for separating the stirring area from the stationary area was provided, and all other equipment such as stirring blades were the same as in Example 5. The catalyst used was the same as the new catalyst in Example 1. The reaction conditions were the same as in Example 5. After the reaction was stabilized, the concentration of cyclohexanol in the reaction product discharged from the reactor was 11.0% by weight, and the selectivity of cyclohexene was 9%.
It was 9.5%. The extracted reaction product had no catalyst at all and was in a good oil-water separation state. The oil-water separation time was measured in batches in the same manner as in Example 5. The oil-water separation time was 11 seconds after stopping the stirrer.

(Comparative Example 4) Using the hydration reaction apparatus of Example 5, the reaction conditions were the same as in Example 5, but when the reaction was performed at 1000 rpm with the rotation speed of the stirrer, the reaction product extracted from the reaction tank was produced. A part of the catalyst was mixed in the product, and the separation of oil and water was insufficient. At this time, the cyclohexanol concentration in the reaction product was 10.9% by weight, and the cyclohexanol selectivity was 99.5%. At this time, the average droplet diameter of the oil phase in the reaction tank was 0.03 mm.

Subsequently, the stirring and the raw material supply were temporarily stopped at the same time, and the oil-water separation time was evaluated in batches. As a result, a part of the emulsion layer remained even 74 seconds after the stirring was stopped. As a result of operating continuously for 50 hours under the above reaction conditions, the cyclohexanol concentration in the reaction product was reduced to 8.5% by weight. In addition, the catalyst which flowed out of the reaction tank 4 was subjected to oil-water separation treatment with a centrifugal separator and collected. The recovered catalyst was charged into the reaction tank 4 from a preliminary nozzle (not shown) so that the amount of the catalyst in the reaction tank 4 was equal to the initial charge amount. Table 4 shows the results of Comparative Example 4 together with the results of Examples 13 to 15.

[0086]

[Table 4]

Example 16 As a cyclohexene hydration reaction tank, the 4-liter stainless steel pressure-resistant autoclave 4 with a stirrer of Example 5 as shown in FIG. 8 was used by connecting two tanks in series. The second-stage reaction tank 4-2 is installed at a position lower than the first-stage reaction tank 4-1.
The reaction liquid extraction pipe 5-1 of the first was connected to the raw material supply pipe 3 of the second-stage reaction tank 4-2. The gas phase portions of the first-stage reaction tank 4-1 and the second-stage reaction tank 4-2 are provided with a pressure equalizing tube 12 so as to have the same pressure. This pressure equalizing pipe has an inert gas supply pipe 13 for pressurization.
Are connected. The first-stage reactor 4-1 incorporates a steam flow coil having an inlet 14 and an outlet 15, and the second-stage reactor 4-2 incorporates a steam or cooling water flow coil having an inlet 16 and an outlet 17. , Temperature control. In the hydration reaction, first, after purging each device with nitrogen, 5.36 kg of a water slurry having a catalyst concentration of 30% by weight was charged into each reactor.
The stirrer was rotated at 530 rpm, steam was introduced into each of the above-described coils, and the temperatures in the first-stage reaction tank 4-1 and the second-stage reaction tank 4-2 were increased to 120 ° C.
It was fixed. Fresh cyclohexene solution was gradually supplied to a steady state of about 1.7 kg / hr. The pressure inside the reactor was constantly increased with nitrogen so as to be constant at 7 kg / cm ² gauge. Water corresponding to the amount of water consumed was supplied to each reaction tank through the raw material introduction pipe so that the oil-water interface level in the stationary area in each reaction tank was located below the reaction product (oil phase) extraction pipe. . The gas-liquid interface was kept constant by making each of the reaction product (oil phase) extraction pipes an overflow type. In addition, the second-stage reaction tank 4-
With respect to the coil having the inlet 16 and the outlet 17 incorporated in No. 2, the temperature in the second-stage reaction tank 4-2 was controlled to be constant at 120 ° C. by switching from steam to cooling water. After stabilization of the whole system, the concentration of cyclohexanol in the product discharged from the reaction vessel should be 1
2.2% by weight, and the selectivity to cyclohexanol was 99.5%. The stirring power at this time was about 0.5 Kw / m ³ (the volume is the volume of the reaction system). Although the amount of cyclohexene supplied per catalyst amount is the same as in Example 5, the concentration of cyclohexanol is about 10% as compared with the concentration of cyclohexanol obtained in Example 5.
You can see that it has become higher. The extracted reaction product had no catalyst at all and was in a good oil-water separation state.

(Examples 17 and 18) Using the hydration reactor of Example 16, the reaction conditions were the same as in Example 16, and only the reaction temperature was changed as shown in Table 5, and the reaction results were examined.
The results are as shown in Table 5.

Comparative Example 5 Using the hydration reaction apparatus of Example 16, the reaction conditions were the same as in Example 16, except that the temperature of the first-stage reaction tank was set to 120 ° C., and the second-stage reaction was performed. When the reaction was performed at a tank temperature of 130 ° C., the cyclohexanol concentration in the reaction product (oil phase) extracted from the reaction tank 4-2 was 9.2%, and the selectivity of cyclohexanol was 9%.
It was 9.3%. That is, the concentration of cyclohexanol in the reaction product extracted from the reaction vessel was about 25% lower than that in Example 16 in which the reaction was performed at a constant temperature of 120 ° C. Table 5 shows the results of Comparative Example 5 together with the results of Examples 13 to 15.

[0090]

[Table 5]

Example 19 As a cyclohexene hydration reactor, a thermometer and a sheath tube (not shown) were placed inside a 32 liter stainless steel pressure-resistant reactor 4 with a stirrer as shown in FIG. , A raw material supply pipe 3, a reaction product extraction pipe 5, and a gas-liquid level gauge / liquid-liquid interface gauge / pressure gauge (these are not shown). Disperser 6 was connected to raw material supply pipe 3. The stirring blade 9 was provided with a plurality of small chambers by partitioning the inside of the reaction tank as 10 stages of disk turbine blades, and the disperser 6 was disposed immediately below the lowest stage blade. A perforated plate (same thing as 20A in FIG. 10) having a porosity of 14% was provided as an obstacle 20 between each stirring blade 9. The reaction product extraction pipe 5 was provided above the uppermost stirring blade, and was a stationary area for separating the liquid phase near the reaction product extraction pipe 5 from oil and water. Further, a steam jacket 21 capable of controlling the temperature is provided around the lowermost chamber.
Was attached. In addition, from the second chamber from the bottom to the 10th
A cooling jacket 22 was provided around the small chamber of the stage and used for temperature adjustment. The cooling jacket was provided with a valve capable of controlling the amount of cooling water. The raw material supply pipe 3 was connected to a cyclohexene supply pipe 1 and a water supply pipe 2. All pipes were fitted with flow meters. The hydration reaction was carried out by first purging the inside of the reaction vessel with nitrogen, and then using the same new catalyst as in Example 1 and a water slurry having a catalyst concentration of 30% by weight of 19.7 k.
g was charged into the reaction tank, and the stirrer was rotated at 350 rpm. The water vapor is circulated through the jacket 21 to raise the temperature so that the temperature inside the reaction vessel becomes constant at 120 ° C., and the pressure inside the reaction vessel becomes 7 k
It was constantly pressurized with nitrogen gas so that g / cm ² gauge was constant. Fresh cyclohexene solution at steady state about 6.1
The supply was started at a rate of kg / hr, and cooling water was circulated through the jacket 22 and cooled to a constant temperature of 120 ° C. Water corresponding to the amount of water consumed was supplied through the raw material supply pipe 3 so that the level of the oil-water interface in the reaction tank was located slightly below the reaction product outlet. The reaction liquid withdrawal amount was controlled so that the gas-liquid interface was located above the reaction product discharge outlet. After stabilization of the entire system, the concentration of cyclohexanol in the reaction product in the reaction vessel was 13.0% by weight, and the selectivity to cyclohexanol was 99.5%. From the above results, it can be seen that the cyclohexene supply amount per catalyst amount is the same as in Example 5, but the concentration of cyclohexanol in the reaction product is improved by increasing the number of stages. The extracted reaction product had no catalyst at all and was in a good oil-water separation state.

Example 20 Using the hydration reactor of Example 19, the reaction conditions were the same as in Example 19, and only the reaction temperature was changed as shown in Table 6, and the reaction results were examined. The temperature in the reaction tank is set so that the temperature of the reaction system in the lowermost chamber is kept constant at 120 ° C., and the temperature of the reaction system in the upper chamber is made constant at 105 ° C., and the temperature distribution during that period changes almost linearly. Was controlled by the flow rate of the cooling water. After stabilization of the whole system, the cyclohexanol concentration in the reaction product discharged from the reaction vessel was 15.
1% by weight and the selectivity to cyclohexanol is 9
It was 9.6%. This revealed that the concentration of cyclohexanol in the reaction product was higher than that of Example 19 at a constant temperature. Table 6 shows the results of Examples 19 and 20.

[0093]

[Table 6]

[0094]

According to the present invention, in the reaction system, the aqueous phase is a continuous phase, the catalyst is suspended in the aqueous phase, and the cyclic olefin oil phase is reacted with water as fine droplets. And a cyclic alcohol can be obtained with a substantially high yield. Further, the decrease in the dropping activity of the catalyst with time is remarkably suppressed, and as a result, high activity and high selectivity can be maintained for a long time. In addition, after the completion of the reaction, oil-water separation was very easy, the stationary area could be made compact, and there was no leak catalyst in the reaction product, and a long-term stable reaction could be maintained. In addition, when a reaction vessel with a draft tube was used, it was possible to further reduce damage to the catalyst and to reduce the energy for stirring.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of an internal cross section of a reaction vessel having a disperser connected to a raw material supply pipe for performing a first embodiment of the method of the present invention.

FIG. 2 is a schematic view of an internal cross section of a reaction tank provided with a weir having a stirrer for performing the second embodiment of the method of the present invention.

FIG. 3 is a schematic diagram of an internal cross section of a reaction tank further provided with a hollow cylinder (draft tube) in the second embodiment of the method of the present invention.

FIG. 4 is a schematic diagram of an internal cross section of a reactor in which a weir is removed and an oil / water separation tank is provided outside the reactor in place of the second embodiment of the method of the present invention.

FIG. 5 is a schematic view of an internal cross section of a reaction vessel in which a baffle plate is arranged instead of a weir as shown in FIG. 2 in the second embodiment of the method of the present invention.

FIG. 6 is a perspective view of a reaction tank in which a donut plate is arranged as a baffle plate.

FIG. 7 is a perspective view of a reaction tank in which a perforated disk is arranged as a baffle plate.

FIG. 8 for implementing a third aspect of the method of the invention;
It is the schematic of the internal cross section of two reaction tanks connected in series.

FIG. 9 for performing a fourth aspect of the method of the present invention;
It is the schematic of the internal cross section of a multistage stirring tank.

FIG. 10 is a perspective view showing an example of the obstacle in FIG. 9 and showing a lower part of a reaction tank using a perforated disk.

11 is a perspective view showing an example of the obstacle in FIG. 9 and showing a lower portion of a reaction tank using a disk.

12 is a perspective view showing an example of the obstacle in FIG. 9 and showing a lower part of a reaction tank using a donut plate. FIG.

FIG. 13 is a perspective view of the lower part of the reaction tank using another donut plate in FIG.

FIG. 14 is a perspective view of a lower portion of a reaction tank using still another donut plate in FIG.

FIG. 15 is a perspective view of the lower part of the reaction tank using a donut plate different from the above in FIG.

[Description of Signs] 1 Cyclohexene supply pipe 2 Water supply pipe 3 Raw material supply pipe 4 Hydration reaction tank 5 Reaction product extraction pipe 5A Continuous oil phase 6 Disperser 7 Oil / water separation weir 8 Circulation pump 9 Stirrer blade 10 Hollow cylinder ( (Draft tube) 11 oil / water separation tank 12 reaction liquid introduction pipe 13 water slurry return pipe 14 steam inlet 15 steam drain outlet 16 cooling water inlet 17 cooling water outlet 18 equalizing pipe 19 inert gas supply pipe 20 obstacle 21 steam jacket 22 cooling water Jacket 23 Obstacle fixed love

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-97736 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 29/04 C07C 35/02 C07C 35 / 08 C07B 61/00 300

Claims (24)

(57) [Claims] 1. A method for hydrating a cyclic olefin, which comprises producing a cyclic alcohol by reacting a cyclic olefin with water in the presence of a crystalline aluminosilicate catalyst having a primary particle size of 0.5 μm or less . Using a reaction system including a continuous aqueous phase in which an aluminosilicate is suspended and an oil phase containing a cyclic olefin, and dispersing the oil phase in the continuous aqueous phase as droplets having an average droplet diameter of 0.05 to 30 mm. A method for hydrating a cyclic olefin, wherein the reaction is carried out. 2. The volume ratio of the oil phase to the continuous water phase is 0.0
2. The method according to claim 1, wherein the number is from 01 to 1.0. 3. The weight ratio of the catalyst to water is from 0.01 to 3.
The method according to claim 1 or 2 , wherein the method is 2.0. Wherein 50 to 100 wt% oil phase of the cyclic olefin, and claims 1, characterized in that it a cyclic alcohol corresponding to the cyclic olefin containing 0-50 wt% according to any one of 3 the method of. 5. A reaction, at 50 to 250 ° C., the method according to any one of claims 1 to 4 both water and cycloolefin is characterized in that under pressures which can keep the liquid. 6. The reaction is carried out in at least one reaction tank. The reaction tank has at least one disperser connected to a raw material supply pipe at a lower portion thereof and having a large number of pores. through by ejected from the pores of supplying disperser in the reaction system, according to claim 1, <br/> to 5, characterized in that dispersing and distribution oil phase in a continuous aqueous phase as droplets The method according to any of the above. 7. An oil phase outlet connected to a withdrawing means for withdrawing an oil phase obtained by a reaction containing a formed cyclic alcohol and an unreacted cyclic olefin in an upper portion of the reaction vessel, A continuous layer of the oil phase formed in the upper part of the reaction tank by the coalescence of the obtained oil droplets is withdrawn from the outlet and withdrawal means, and a part thereof is branched from the withdrawal means and connected to the raw material supply pipe by a conduit connected to the raw material supply pipe to the reaction vessel. The method according to claim 6 , wherein the oil is circulated and the circulated oil layer is ejected from pores of the disperser. 8. The method according to claim 7 , wherein the flow rate of the circulating oil phase relative to the feed flow rate of the raw material cyclic olefin is 1 to 150 by weight. 9. A reaction is carried out in at least one reaction tank having a stirrer having a plurality of stirring blades, and the stirrer is operated so as to stir the entire reaction system to generate a shear force. 2. The method according to claim 1, further comprising: preventing sedimentation of the catalyst suspended in the oil, and redispersing the oil droplets at a distance from the stirring blade to maintain the oil phase in the continuous aqueous phase in the form of droplets. 6. The method according to any one of claims 1 to 5 . 10. The reaction vessel has a stirrer having a plurality of stirring blades, and the suspension is suspended in a continuous aqueous phase by operating the stirrer so as to stir the entire reaction system to generate a shearing force. 7. The method according to claim 6 , wherein the settling of the catalyst is prevented, and the oil droplets united away from the stirring blade are redispersed to maintain the oil phase in the continuous aqueous phase in the form of droplets. Method. 11. A reaction is carried out using a plurality of serially connected reaction tanks comprising a first reaction tank and at least one supplementary reaction tank, and a first reaction tank preceding each of the at least one supplementary reaction tank. Supplying the reaction mixture containing the cyclic alcohol and the unreacted cyclic olefin obtained in the reaction tank or the supplementary reaction tank to the next supplementary reaction tank of each preceding reaction tank, where the unreacted cyclic olefin is hydrated. Claims characterized by the following:
The method according to 6, 9 or 10 . 12. The reaction vessel has an outlet for a reaction product which is an oil phase at an upper portion thereof, a weir is disposed near the reaction product outlet to provide a stationary area, and the obtained reaction mixture is annularly formed. The method according to any of claims 9 to 11 , wherein the separation is facilitated into an oil phase as an upper layer containing an alcohol and an aqueous phase as a lower layer containing a catalyst. 13. A reaction chamber is partitioned by using a baffle plate to provide a stirring area as a lower area in the tank and a stationary area as an upper area in the tank, and agitating the reaction system in the stirring area to reduce a shearing force. This causes the oil phase to be dispersed as droplets in the continuous aqueous phase, and the oil droplets move from the stirring region to the stationary region through the baffle plate, where the oil droplets coalesce in the stationary region. the method according to any one of claims 9 to 11, characterized in that so as to form a continuous oil phase Te. 14. The method of claim 13 , wherein the baffle is selected from the group consisting of a perforated disk, a non-perforated disk, a donut plate, and a grid deck. 15. A hollow cylinder having an inner wall and an outer wall and having an open upper end and a lower end is disposed in a reaction vessel so as to surround the stirrer. In the reaction vessel, a first cylinder is provided between the stirrer in the reaction system and the inner wall of the cylinder.
Is provided with a second space between the outer wall of the cylinder and the inner wall of the reaction tank, and the cylinder has a cross-sectional area such that the reaction system sufficiently circulates through the first and second spaces. , to 9 claims, characterized in that it functions as a draft tube 14
The method according to any of the above. 16. The reactor has at least one vertically extending baffle plate projecting from the inner wall of the reactor substantially toward the center and near the inner wall, and the baffle plate is disposed above and below the baffle plate. 10. A system according to claim 9, wherein the space is left in the system.
16. The method according to any one of claims 15 to 15 . 17. A plurality of agitating blades are composed of a plurality of agitating blade sets arranged in a multistage manner, and a reaction tank is divided into a plurality of small chambers arranged in a multistage manner by obstacles, and each chamber is provided with at least one agitating blade. A stirrer is provided for each reaction system so as to include the set, and the above stirrer is operated to stir the entire reaction system in each chamber to disperse the oil phase in the continuous aqueous phase and suspend the oil phase in the continuous aqueous phase. In order to prevent sedimentation of the catalyst and to re-disperse the coalesced oil droplets away from the agitating blades in each chamber, a first direction is defined according to a predetermined direction between two adjacent small chambers separated by obstacles. At the same time as allowing the reaction system to flow from the second chamber toward the second chamber, and preventing the reaction system from flowing back in the above-described direction, thereby allowing the reaction system in the second chamber to react in the second chamber. Backmixing with the system The method according to any one of claims 9 to 11 and 15 to 16, characterized in that the Guyo. 18. A stirrer area as a lower area of the obstacle and a stationary area as an upper area of the obstacle are provided by an uppermost obstacle, and the reaction system is agitated in the agitation area to generate a shearing force. As a result, the oil phase becomes droplets and is dispersed in the continuous aqueous phase, and the oil droplets move from the stirring area to the stationary area through the obstacles, where the oil droplets coalesce in the stationary area to form a continuous oil. The method of claim 17 , wherein a phase is formed. 19. The uppermost chamber of the small chambers has a reaction product outlet, and a weir is arranged near the reaction product outlet to provide a stationary area, and an annular ring in which an obtained reaction mixture is generated. 19. The method according to claim 17 or 18 , wherein the separation is facilitated into an oil phase as the upper layer containing the olefin and a continuous aqueous phase as the lower layer containing the catalyst. 20. A reaction mixture containing an oil phase and an aqueous phase obtained by the reaction is introduced into an oil / water separation tank provided outside the reaction tank,
After separating the oil phase as the upper layer containing the generated cyclic alcohol and the aqueous phase as the lower layer containing the catalyst, withdrawing the oil phase and circulating a part of the oil phase to the reaction tank, and circulating the aqueous phase to the reaction tank The method according to claim 1 or 6 , wherein: 21. A reaction mixture containing an oil phase and an aqueous phase obtained by the reaction is introduced into an oil / water separation tank provided outside the reaction tank,
After separating the oil phase as the upper layer containing the generated cyclic alcohol and the aqueous phase as the lower layer containing the catalyst, withdrawing the oil phase and circulating a part of the oil phase to the reaction tank, and circulating the aqueous phase to the reaction tank the method according to any one of claims 9 to 11, characterized in. 22. A reaction mixture containing an oil phase and an aqueous phase obtained by the reaction is introduced into an oil / water separation tank provided outside the reaction tank,
After separating the oil phase as the upper layer containing the generated cyclic alcohol and the aqueous phase as the lower layer containing the catalyst, withdrawing the oil phase and circulating a part of the oil phase to the reaction tank, and circulating the aqueous phase to the reaction tank The method according to claim 17 , characterized in that: 23. The method according to claim 11 , wherein the temperatures of the plurality of reaction vessels are controlled so as to decrease sequentially according to the flow direction of the reaction system. 24. The method according to claim 17 , wherein the temperature of the plurality of small chambers is controlled so as to gradually decrease in accordance with the flow direction of the reaction system.