JPH10273457A - Production of cyclic alcohol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To react a cyclic olefin with water in a suspended state of a zeolite catalyst in the liquid phase and industrially and advantageously produce the subject alcohol by preventing the zeolite catalyst from sticking to a liquid contact part in a reactor. SOLUTION: The amount of a zeolite catalyst sticking to a liquid contact part (a metal having <=50 μm Ry surface roughness measured by JIS B 0601) is regulated to <=3 wt.% based on the zeolite used expressed in terms of dry weight and a washing liquid is preferably made to flow to the liquid contact part on the upper side of a gas-liquid interface during the reaction in a method for continuously feeding preferably a 3-10C cyclic olefin to a reactor holding water and the zeolite (ZSM-5s, etc.), continuously taking out the reactional product from the reactional system, separating an oil from water of the taken out reactional product, distilling and separating the oily phase containing the cyclic olefin and a cyclic alcohol and providing the cyclic alcohol from the column bottom. Thereby, the objective alcohol is efficiently obtained.

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 in a liquid phase using a zeolite catalyst as a suspension bed.

[0002]

2. Description of the Related Art Conventionally, as a method for producing an alcohol by hydrating an olefin in a liquid phase, a homogeneous catalyst such as a mineral acid, an aromatic sulfonic acid and a heteropoly acid, a strongly acidic ion exchange resin, a crystalline aluminosilicate Many methods using solid acid catalysts such as zeolites such as JP-B-47-45323 and JP-B-53-15485 are known.
JP-A-57-70828, JP-A-58-1247
No. 23, JP-A-58-194828, JP-A-60-1
No. 04028, JP-A-61-180735, JP-B-6-180735
No. 3-47695). In particular, in the olefin hydration reaction using a solid acid catalyst, the reaction is usually performed in a three-phase system of a catalyst, an aqueous phase, and an oil phase. Since the solid acid as a catalyst is distributed only to the aqueous phase, the produced alcohol is By separating the contained oil phase from the aqueous phase, the separation of the produced alcohol from the catalyst is also achieved, which is an industrially preferable method.

[0003]

However, when this method is carried out industrially, the reaction results do not change stably.
There was a problem that the catalyst activity was greatly reduced.

[0004]

Means for Solving the Problems The present inventors have studied in detail that the reaction results are unstable for each operation and the cause of the decrease in activity. I found to do. That is, the present invention relates to a method for synthesizing a cyclic alcohol by reacting a cyclic olefin with water in a liquid phase while suspending the zeolite catalyst, to prevent the adhesion of the zeolite catalyst to a liquid contact portion of the reactor. The present invention relates to a method for producing a cyclic alcohol.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The zeolite catalyst targeted in the present invention is a zeolite catalyst which is known to be effective for a hydration reaction of a cyclic olefin. Zeolite catalysts
It is an acidic solid substance. The form in which the zeolite catalyst is used is not particularly limited, but is usually used in the form of powder or granules. The primary particle size of this zeolite is usually 0.1.
5 μm or less, preferably 0.1 μm or less, more preferably 0.05 μm or less. The lower limit is usually 0.01 μm or more. Further, alumina, silica, titania or the like may be used as a carrier or a binder. The zeolite catalyst used in the present invention is not particularly limited. For example, its skeleton structure includes mordenite type, erionite type, shabazite type, faujasite type, clinoptilolite type, ferrierite type, L type, beta type. ZSM series announced by Mobile Oil Co .; for example, ZSM-5 type, ZSM-4 type,
ZSM-11, ZSM-12, ZSM-20, Z
SM-40 type, ZSM-35 type, ZSM-48 type, MC
M-22 type and those having the SSZ series announced by Chevron Co., Ltd. are exemplified. Preferably, mordenite type, faujasite type, ferrierite type, beta type, ZSM
Zeolite having a structure such as -5 type, ZSM-11 type, and MCM-22 type. Particularly preferred are pentasil-type zeolites such as beta-type, ZSM-5-type and ZSM-11-type, and most preferred are those having a ZSM-5-type structure. Further, as the zeolite catalyst, in addition to the aluminosilicate having these structures, part or all of the aluminum atoms may be gallium,
Those replaced with boron, iron, etc. can also be preferably used,
For example, zeolites containing different elements such as borosilicate, gallosilicate, ferroaluminosilicate, galloaluminosilicate, and boroaluminosilicate can be exemplified. Z
The SM-5 type is characterized in that the X-ray diffraction pattern has at least a peak of an inter-plane distance shown in Table 1 below.

[0006]

[Table 1] Distance between planes d Å 11.1 ± 0.2 10.1 ± 0.2 3.85 ± 0.07 3.74 ± 0.05 3.72 ± 0.05 What is ZSM-5 type? Is a synthetic zeolite (see U.S. Pat. No. 3,702,886) developed by Mobile Oil Co., Ltd. In recent years, ZSM-5 analogs have been reported due to slight differences in X-ray diffraction patterns. . In the present invention, these are collectively referred to as ZSM-5s. Similarly, ZSM-11s also exist. For the ZSM-5s, the characteristic diffraction peaks in Table 1 above are included in any of them. These ZSM-5s are exemplified below.

Table 2 ZSM-5 Class ZSM-5 (U.S. Pat. No. 3,702,886) ZSM-8 (German Patent No. 2,049,755) ZETA-1 (German Patent No. 2,548) ZETA-3 (British Patent No. 1,553,209) NU-4 (German Patent No. 3,268,503) NU-5 (German Patent No. 3,169,606) TZ-01 (U.S. Pat. No. 4,581,216) Crystaline aluminosilicate (U.S. Pat. No. 4,954,954)
326) TRS (German Patent No. 2,924,870) MB-28 (European Patent No. 21445) TSZ (JP-A-58-45111) AZ-1 (European Patent No. 113) in 116 Pat) and these zeolite catalysts, preferred composition the molar ratio of SiO ₂ / Al ₂ O ₃ is of 20 to 100. The zeolite catalyst used in the present invention is preferably (1) ZSM-5, (2) ZSM-11, (3) at least a part of the aluminum atom of ZSM-5 or ZSM-11 is a boron atom, At least one selected from zeolites substituted with at least one selected from the group consisting of gallium atoms and iron atoms is selected,
Particularly preferably, ZSM-5s or those in which at least a part of aluminum atoms are at least one selected from zeolites substituted with at least one selected from the group consisting of boron atoms, gallium atoms and iron atoms. Can be These zeolites are usually of the proton exchange type (H type), and some of them are Na, K, Li
May be exchanged with a cation species selected from ions such as an alkali metal element such as Mg, Ca, and Sr, an alkaline earth metal element such as Mg, Ca, and Sr, and a Group 8 element such as Fe, Co, Ni, Ru, and Pd.

In the present invention, a cyclic olefin is hydrated in a liquid phase in the presence of a zeolite catalyst as described above. The cyclic olefin has 3 to 10 carbon atoms.
Cyclic olefins, for example, cyclopentene, methylcyclopentenes, cyclohexene, methylcyclohexenes, cyclooctene, cyclododecene and the like can be exemplified, and a cycloolefin having a 5- to 8-membered ring is preferred, and cyclohexene is particularly preferred. These cyclic olefins may contain various substances as impurities. For example, when cyclohexene is produced by partial hydrogenation of benzene, it may contain trace amounts of cyclohexane and benzene. During the storage, the content of cyclohexane oxide such as epoxycyclohexane, 2-cyclohexen-1-one, and cyclohexene hydroperoxide may increase. In the reaction of the present invention, when cyclohexene is the raw material, the amount of cyclohexane oxide is preferably as small as possible in the reaction system, and the total amount is preferably 100 ppm or less, more preferably 50 ppm or less. Further, another organic substance may be allowed to coexist in the reaction system as a solvent or an additive. Examples of the organic substance include oxygen-containing organic compounds such as benzoic acids, carboxylic acids, phenols, salicylic acids, alcohols, fluoroalcohols, ethers, esters, and ketones, and amide compounds. , Nitriles and other nitrogen-containing organic compounds, thio-
, Sulfur-containing organic compounds such as sulfonic acid, halogen-containing organic compounds such as halogenated carbon, aliphatic hydrocarbons,
And aromatic hydrocarbons.

The hydration reaction is preferably carried out continuously. In this case, the hydration reaction is carried out by continuously supplying the cyclic olefin to the aqueous phase of the catalyst slurry composed of the zeolite catalyst and water. A method in which a cyclic alcohol is produced, the aqueous phase is separated from the reaction solution into an oil phase containing the produced cyclic alcohol, and the oil phase is continuously collected. The reaction is usually performed by mixing an aqueous phase and an oil phase containing a cyclic olefin by stirring or the like, thereby dispersing the oil phase in a suspended state, for example, a continuous aqueous phase in a droplet state. The reaction solution normally separates into an aqueous phase and an oil phase when the mixing is weakened or stopped, and the volume ratio of the oil phase to the aqueous phase is usually 0.001 to 10, preferably 0.1 to 1.0. 01 to 1. If one of the oil phase and the aqueous phase is excessively large compared to the other, it is not preferable because the phase separation of the two phases becomes poor and the reaction rate decreases.

The weight ratio of the catalyst to the cyclic olefin is usually 0.001 to 50, preferably 0.01 to 2
0, more preferably 0.05-5, most preferably 0.1-3. When the amount of the catalyst is too small, the reaction rate becomes low, and when the amount is too large, the cost of the catalyst increases, which is not preferable. In the reaction system, the aqueous phase mainly contains the zeolite catalyst, and the oil phase mainly contains the cyclic olefin as the raw material and the generated cyclic alcohol.
After at least a part of the aqueous phase containing the catalyst is separated from the oily phase, the aqueous phase can be recycled to the reactor as a catalyst slurry and reused. Further, the generated cyclic alcohol can be easily purified and recovered from the separated oil phase by a known method such as distillation. The residual liquid of the oil phase containing the starting olefin after separating the cyclic alcohol can be reused as the starting material for the hydration reaction.

Regarding the conditions of the hydration reaction, the reaction temperature varies depending on the starting cyclic olefin used, but the optimal temperature range is usually 50 to 300 ° C., preferably 70 to 200 ° C.
More preferably 80-160 ° C, most preferably 100
~ 140 ° C. The reaction pressure is not particularly limited, but is preferably a pressure that can keep the cyclic olefin and water in a liquid phase, and is usually 5 MPa or less, preferably 0.2 to 2 MPa.
a, more preferably in the range of 0.3 to 1 MPa. The reaction time or residence time in the reactor is usually 1 minute to 10 minutes.
Time, preferably in the range of 5 minutes to 5 hours. In addition, the reaction system is preferably maintained in an atmosphere of an inert gas such as nitrogen, helium, hydrogen, argon, and carbon dioxide. In this case, the content of oxygen in the inert gas is preferably small, and the oxygen content is usually 100 ppm or less, preferably 2 ppm.
Those having 0 ppm or less are used. Range.

FIG. 2 is a schematic view of a continuous hydration reaction apparatus that can be used in the present invention. Raw material cyclic olefin is supplied to the hydration reactor 13 from the raw material supply pipe 11, and water is supplied to the hydration reactor 13 from the water supply pipe 12. The reactor 13 is provided with a stirrer 20, and the reaction proceeds in a suspension state of an aqueous phase containing a zeolite catalyst and an oil phase containing a starting material, a cyclic olefin and a generated cyclic alcohol. Part of the contents of the reactor is withdrawn from the pipe 15 and separated into oil and water by the oil and water separator 14. The separated oil phase is withdrawn from the tube 16 and sent to the next step such as distillation for obtaining a cyclic alcohol. On the other hand, the oily water separated aqueous phase is withdrawn from the bottom through a pipe 17, a part of which is returned to the reactor 13 from a pipe 18, and the remainder is sent to a regeneration step through a pipe 19. In this case, the ratio of the aqueous phase separated into oil and water to be returned to the reactor and sent to the regeneration step is appropriately determined according to the load of the regeneration step, the amount of catalyst, and the like. Further, the extraction into these tubes may be performed intermittently. FIG. 3 is a schematic diagram of another continuous hydration reaction apparatus that can be used in the present invention. In this figure, the numerals are common to those in FIG. The operation in FIG. 3 is basically the same as that in FIG. The difference is that an oil / water separation weir 21 is provided inside the reactor 13. The oil phase separated by the oil-water separation weir 21 is withdrawn from the pipe 22 and separated by the oil-water separator 14 with the oil phase extracted with the pipe 16 in the same manner as in FIG. Sent to the process. FIG. 4 is a schematic view of still another continuous hydration reaction apparatus that can be used in the present invention. In this figure, the numerals are common to those in FIG. The configuration of FIG. 4 is basically the same as that of FIG.
The difference is that a pipe 15 connected to the oil / water separator 14 is provided on the oil / water separation weir 21 side provided in the reactor 13. As described above, since oil / water separation is performed in the oil / water separation weir, the one extracted from the pipe 15 without the oil / water separator 14 contains a relatively large amount of aqueous phase. However, since an oil phase is also contained at the same time, the oil / water separation is performed again by the oil / water separator 14. The method of FIG. 4 is different from that of FIG. 3 in that most of the contents supplied to the oil-water separator 14 are in the water phase, so that the separator 14 can be downsized and the standing time in the oil-water separator 14 can be reduced. There is an effect that can be done. FIG.
In any of the cases (1) to (4), the connection position of the tube to the reactor or the like is not particularly limited, and is appropriately determined by those skilled in the art. Even when the hydration reaction of a cyclic olefin is performed using a zeolite catalyst as described above, the reactor is often industrially shut down for periodic inspection and repair. In such a case, it is economically essential to reuse the zeolite catalyst used in the reaction when the reaction is restarted. However, if the catalyst subjected to the hydration reaction is subjected to the hydration reaction again after the termination of the reaction, the activity before the interruption is not obtained, and the reaction results are not stable. As described above, even when performing a hydration reaction of a cyclic olefin using a zeolite catalyst, the reaction results do not change stably, such as the reaction results are unstable at each operation, and a large decrease in catalyst activity does not occur. This is a big problem in industry. Particularly, when a corresponding cyclic alcohol is obtained by hydration of a cyclic olefin in a liquid phase using a zeolite catalyst, the yield of the obtained alcohol is reduced due to the fact that this reaction is an equilibrium reaction and the catalytic activity is low. There is a problem that the amount is low and the amount of catalyst used is large. In order to solve this problem, it is necessary to increase the amount of the catalyst used. However, since the unit price of the catalyst is generally high, it is extremely important to reduce the decrease in the catalyst activity. However, according to the studies so far, the activity was extremely reduced by the ordinary reaction method, and the change in the reaction results with the lapse of time during the reaction fluctuated, so that stable operation could not be performed.

In order to solve such a problem, the present invention has found that it is extremely effective to carry out the reaction under the condition that the zeolite catalyst does not adhere to the liquid contact portion of the reactor. Although the reason for this is not clear, it can be considered as follows. That is, once the catalyst starts to adhere in the reactor,
On top of that, there is a swelling property, which results in large clumps if adhesion is significant. When the adhesion progresses and the mass becomes large, it is detached and attached by its own weight and falls. Therefore, the catalyst concentration in the catalyst slurry changes, and the reaction result becomes unstable. In addition, the above-mentioned lump generally occurs near the gas-liquid or liquid-liquid interface in the upper part of the reactor even in the liquid contact part, and gradually accumulates upward away from the reaction liquid to form a lump. It has been found that the catalyst used in the present invention has a large decrease in catalytic activity particularly when not immersed in water. Therefore, the activity of the agglomerated catalyst is reduced, and the activity of the entire catalyst is also greatly reduced.

Therefore, by performing the reaction under the condition that the zeolite catalyst of the catalyst does not adhere to the liquid contact portion in the reactor, no lumps of the catalyst are generated, and as a result, the change over time in the reaction results during the reaction is stabilized, It is considered that a stable operation can be performed, and a decrease in catalyst activity can be prevented. In the present invention, the reaction is specified by preventing the zeolite catalyst from adhering to the liquid contact portion of the reactor. The ratio of the catalyst is 3% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less, based on the amount of the zeolite catalyst used during the operation, in terms of the dry weight of the attached catalyst. It is a condition to make it. The amount of the catalyst adhered to the reactor may be determined by accurately measuring the concentration of the catalyst in the reactor, and using this value and the amount of the supplied catalyst. The dry weight of the zeolite catalyst refers to a catalyst in which raw materials, products, and solvents present in the reaction system have been removed from the catalyst slurry after the reaction by washing, drying, and the like. The amount of the zeolite catalyst used during the operation is the average weight of the amount of the catalyst held in the reactor during the reaction, and is usually equal to the amount used at the start of the reaction.

However, the suspension bed reactor used for carrying out the reaction while the zeolite catalyst is suspended has a complicated apparatus structure, so that the operation is usually carried out without attaching the zeolite catalyst to the reactor. It is impossible to do. Therefore, it is necessary to take some method to prevent the zeolite catalyst from adhering to the liquid contact part of the reactor. As this method, for example, the following method can be used.

That is, the (dry) adhered to the operating reactor.
Preventing the zeolite catalyst from adhering to the liquid contact portion in the reactor in advance so that the ratio of the zeolite catalyst does not exceed 3% by weight can be mentioned. Here, the `` liquid contact part '' of the reactor means not only a part that can come into contact with the reaction liquid on the inner wall of the reactor during the reaction, but also a stirring blade, a stirring shaft, etc. installed inside the reactor. Also refers to equipment. Specific examples of such means include smooth processing, lining, and coating of the inner surface of the reactor or the liquid contact portion. The degree of this smoothness is based on JIS B
0601 can be represented by the surface roughness Ry. The surface roughness Ry can be measured by a commercially available device, and examples thereof include Tarisurf type 4 manufactured by Rank Taylor Bobson of a stylus type surface roughness measuring device, and Surfcom 103B manufactured by Tokyo Seimitsu Co., Ltd. The measurement method is JIS B 0
651 can be used. The degree of surface roughness is usually 50 μmRy or less, preferably 40 μmRy.
It is at most mRy, more preferably at most 30 μmRy, particularly preferably at most 20 μmRy. On the other hand, when smoothing by lining or coating, glass lining, PTFE, PFA, FEP, PVDF, ETF
Lining or coating with a fluororesin such as E, PCTFE or ECTFE can be performed. Preferably, the fluororesin is Teflon (registered trademark). When the surface is made of metal, it can be made smooth by a cutting process, a polishing process, etc. in the manufacturing process. Specifically, forging, casting, die casting, hot rolling, cold rolling, drawing, extrusion, tumbling, sanding, rolling, milling, planing, shaping, precision boring, filing, rounding, Boring, drilling, broaching, reaming, shaving, grinding, horn finishing, super finishing, buff finishing, paper finishing, lap finishing, liquid honing, burnishing finishing, roller finishing,
Chemical polishing, electrolytic polishing, and the like can be given, but are not limited to these methods. In addition, the reaction solution may gradually become smoother during the reaction. In the present invention, it is not necessary to perform such a treatment for preventing the catalyst from adhering to the entire liquid-contacting portion of the reactor, and a portion of the liquid-contacting portion may be treated. It is also effective to flow the cleaning liquid to the liquid contact portion above the gas-liquid interface of the reactor during the reaction. For example, it is possible to flow a washing liquid along the vessel wall from above the reactor to below. The attachment of the zeolite catalyst is likely to occur particularly immediately above the gas-liquid interface. This is considered to be because the catalyst slurry containing the zeolite catalyst easily adheres to the droplets while drying easily. Therefore, if the portion immediately above is moistened with the cleaning liquid, the strong adhesion of the zeolite catalyst can be suppressed. The washing liquid may flow along the inner wall of the reactor, or may flow through a shaft of a stirring blade. In the case of a reactor having an oil-water separation weir inside, the washing liquid may flow through the oil-water separation weir. Various washing liquids can be used as long as they do not adversely affect the reaction. In the present invention, the presence of water in the reaction system is essential, and in the case of a continuous reaction, it is necessary to supply a portion corresponding to the water consumed in the reaction. Is most preferred. Although the inside of the suspension bed reactor is complicated as described above, it is also effective to change the structure so as to minimize the adhesion of the catalyst.

[0016]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. Comparative Example 1 (Continuous Flow Hydration of Cyclohexene) A hydration reaction of cyclohexene was performed using a continuous flow reactor having an oil / water separation tank outside the reactor as shown in FIG. That is, 100 g of H-type gallosilicate (SiO ₂ / Ga ₂ O ₃ = 50) as a zeolite catalyst and 25 ml of water were placed in a stainless steel autoclave reactor 3 having a stirrer of 2000 ml in internal volume.
After charging 0 g, the inside of the system was replaced with nitrogen gas. Rotation speed 500
After the temperature was raised to 120 ° C. while stirring at rpm, cyclohexene was supplied from the supply pipe 1 at a rate of 120 g / hr. The reaction solution was taken out from the tube 4 and was combined with an oil phase in an oil / water separation tank 5 having an internal volume of 30 ml and installed outside the reactor.
After separation into the aqueous phase containing the catalyst, the aqueous phase was returned to reactor 3 via tube 7 while the oil phase was drained from tube 6. In addition, the supply pipe 2 supplies the total amount of water consumed in the hydration reaction and the water flowing out of the pipe 4 as a dissolved component to the oil phase, thereby keeping the water volume in the reactor 3 constant. Kept. After 5 hours from the start of feeding the raw material cyclohexene, the concentration of cyclohexanol in the oil phase effluent from the tube 6 was 12.0% by weight,
11.8% by weight after 10 hours, 11.5% by weight after 30 hours, 11.4% by weight after 80 hours, 9%
11.2% by weight after 0 hours, 1 after 200 hours
0.7% by weight. As described above, the variation in the concentration of cyclohexanol with respect to the course of operation was large, and it was not possible to operate with stable results. Also, the catalyst activity was significantly reduced.

Furthermore, the slurry concentration after 200 hours has passed is 27.5% by weight, and the amount of adhesion to the inner surface of the reactor determined from the change in slurry concentration is 5.2 for the charged catalyst.
%, Which is 5.2 g. The surface roughness of the inner surface of the reactor (Ry: measured by a stylus-type surface roughness measuring device, measured in the same manner hereinafter) was 61 μmRy.

Example 1 In Comparative Example 1, the inner surface of a stainless steel autoclave was polished to # 400 (# 1).
20, # 180, # 230, # 320, # 400, etc.), except that the reaction was carried out using a reactor having a surface roughness of 0.4 μmRy. It carried out like Example 1. In the continuous flow hydration reaction of cyclohexene, the concentration of cyclohexanol in the effluent oil phase after 1 hour from the start of the supply of the raw material cyclohexene is 1%.
Although it was 2.0% by weight, the concentration of cyclohexanol in the oil spill after 200 hours was 11.8% by weight. Thus, there was almost no change in the concentration of cyclohexanol in the oil spill over time. In addition, it was confirmed that the catalyst activity was very small and decreased at a constant rate. The slurry concentration after 200 hours has passed is 28.
The amount of the catalyst deposited on the inner surface of the reactor determined from the change in the slurry concentration was 0.84 g, which was 0.84% by weight of the charged catalyst.

Example 2 The procedure of Comparative Example 1 was repeated except that the inner surface of the stainless steel autoclave was coated with Teflon (registered trademark). In the continuous flow hydration reaction of cyclohexene, the concentration of cyclohexanol in the effluent oil phase after 5 hours from the start of supply of the raw material cyclohexene was 12.0% by weight, and the concentration of cyclohexanol in the effluent oil phase after 200 hours passed was 11%. 0.8% by weight. It was confirmed that there was almost no change in the concentration of cyclohexanol in the spilled oil phase with time, and that the catalyst activity was extremely reduced, and that it was reduced at a constant rate. Also,
After the elapse of 200 hours, the slurry concentration was 28.5% by weight, and the amount of adhesion to the inner surface of the reactor determined from the change in slurry concentration was 0.35% by weight of the charged catalyst.
It was 35 g.

[0020]

According to the method of the present invention, that is, a method of synthesizing a cyclic alcohol by reacting a cyclic olefin with water in a liquid phase while suspending the zeolite catalyst, the zeolite catalyst is introduced into the liquid contact part of the reactor. By preventing adhesion,
The reaction results are stable, and the catalyst activity is small, which is extremely advantageous for industrial production.

[Brief description of the drawings]

FIG. 1 is a schematic view of a continuous flow reactor used in Examples and Comparative Examples.

FIG. 2 shows a schematic diagram of an example of a continuous flow reactor that can be used in the present invention.

FIG. 3 shows a schematic view of an example of a continuous flow reactor that can be used in the present invention.

FIG. 4 shows a schematic view of an example of a continuous flow reactor that can be used in the present invention.

[Explanation of symbols]

 1: Cyclohexene supply pipe 2: Water supply pipe 3: Reactor 4: Reaction liquid extraction pipe 5: Oil / water separation tank 6: Oil phase extraction pipe 7: Water phase return pipe 8: Catalyst slurry extraction pipe 11: Raw material supply pipe 12: Water supply pipe 13: Hydration reactor 14: Oil / water separator 15-19: Pipe 20: Stirrer 21: Oil / water separation weir 22: Pipe

Claims (16)

[Claims] In a method for producing a cyclic alcohol by reacting a cyclic olefin with water in a liquid phase while suspending the zeolite catalyst, it is desirable to prevent the adhesion of the zeolite catalyst to a liquid contact portion in a reactor. A method for producing a cyclic alcohol. 2. The method according to claim 1, wherein the amount of the zeolite catalyst attached to the liquid-contacting part of the reactor is 3% by weight or less based on the zeolite catalyst used during the operation in terms of dry weight. A method for producing a cyclic alcohol. 3. The material of the liquid contact part of the reactor is JIS B
The surface roughness (Ry) of the liquid contact part measured at 0601 is 50
3. The method for producing a cyclic alcohol according to claim 1, wherein the metal is a metal having a value of μmRy or less. 4. The method for producing a cyclic alcohol according to claim 1, wherein the material of the liquid contact portion of the reactor is a fluororesin. 5. The method for producing a cyclic alcohol according to claim 1, wherein during the reaction, a cleaning liquid is caused to flow into a liquid contact portion above the gas-liquid interface of the reactor. 6. The method for producing a cyclic alcohol according to claim 5, wherein the washing liquid is water. 7. The method for producing a cyclic alcohol according to claim 1, wherein the cyclic olefin is a cyclic olefin having 3 to 10 carbon atoms. 8. The method according to claim 1, wherein the cyclic olefin is cyclohexene. 9. The method for producing a cyclic alcohol according to claim 1, wherein the zeolite catalyst has a pentasil type structure. 10. The zeolite catalyst comprises the following (1):
The method for producing a cyclic alcohol according to any one of claims 1 to 9, wherein the method is at least one selected from the group consisting of (2) and (3). (1) ZSM-5, (2) ZSM-11 (3) at least a part of the aluminum atom of ZSM-5 or ZSM-11 selected from the group consisting of boron, gallium and iron Zeolite substituted with a kind 11. The zeolite catalyst is at least one selected from zeolites in which at least a portion of ZSM-5s or aluminum atoms therein are substituted with at least one selected from the group consisting of boron, gallium and iron atoms. The method for producing a cyclic alcohol according to any one of claims 1 to 10, wherein 12. A step of continuously supplying a cyclic olefin to a reactor holding water and zeolite, a step of continuously taking out a reaction product from a reaction system, and separating the taken out reaction product into oil-water to obtain a cyclic olefin and a cyclic olefin. The cyclic alcohol according to any one of claims 1 to 11, further comprising a step of separating the cyclic alcohol-containing oil phase and an aqueous phase containing water and zeolite, and a step of returning at least a part of the aqueous phase to the reactor. Production method. 13. A process for continuously supplying a cyclic olefin to a reactor holding water and zeolite and having an oil-water separation function, and an oil phase containing a cyclic olefin and a cyclic alcohol separated from the water and oil in the reactor. 12. The method for producing a cyclic alcohol according to claim 1, further comprising a step of continuously extracting the alcohol. 14. The method according to claim 12, wherein the extracted oil phase is separated by distillation, a cyclic olefin is removed from the top of the column, a cyclic alcohol is removed from the bottom of the column, and the removed cyclic olefin is returned to the reactor. A method for producing a cyclic alcohol. 15. The method for producing a cyclic alcohol according to claim 1, wherein the reaction temperature is 50 to 300 ° C. 16. The method for producing a cyclic alcohol according to claim 1, wherein the reaction pressure is 5 MPa or less.