JPH0995463A - Production of cycloalkanone - Google Patents

Abstract

PROBLEM TO BE SOLVED: To raise the selectivity of a cycloalkanol prepared by hydrating a cycloalkene for dehydrogenating reaction, reduce by-products and produce a cycloalkanone useful as an intermediate for raw materials for nylon by adding a specific compound into a reactional system. SOLUTION: A cycloalkanone or a compound having a cycloalkyl group or both obtained by dehydrogenating reaction in an amount of 0.0001-20wt.% are previously added into the reactional system when dehydrogenating a cycloalkanol prepared by hydrating a cycloalkene. Furthermore, the cycloalkyl group is preferably cyclohexyl group and the cycloalkene is preferably cyclohexene in the reaction.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing cycloalkanone. More specifically, it relates to a method for producing cycloalkanone by dehydrogenating a cycloalkanol obtained by hydrating a cycloalkene. Such cycloalkanones such as cycloxanone are industrially useful as intermediates for nylon raw materials.

[0002]

Cycloalkanones are usually produced by the dehydrogenation reaction of cycloalkanols. In this dehydrogenation reaction, copper oxide, chromium oxide, calcium oxide, zinc oxide and their composites are used as catalysts. Further, as a method for producing cycloalkanol, industrially, a cycloalkane is oxidized with molecular oxygen to obtain a mixture of cycloalkanol and cycloalkanone, and cycloalkanol and cycloalkanone are separated by distillation, and the separated cycloalkanol is separated. The most common method is to dehydrogenate an alkanol to obtain a cycloalkanone.

On the other hand, as a method for producing a cycloalkanol, a method based on a hydration reaction of cycloalkene has recently attracted attention. For example, in the production of cyclohexanol by hydration of cyclohexene, a method using a solid acid catalyst such as zeolite is known, and according to this method, cyclohexanol with few by-products may be efficiently produced. .

[0004]

In the conventional dehydrogenation reaction of cycloalkanol, the selectivity of cycloalkanone itself is at a relatively high level, but it is not always sufficient. A method for producing cycloalkanones with less by-products is desired.

Further, in a method for producing a cycloalkanone using a cycloalkanol produced by hydration of a cycloalkene, the cycloalkanol is obtained by oxidation of a conventional cycloalkanol, for example, the above cycloalkane. Since it is different in quality from alkanol, there is a point that the same cycloalkanol dehydrogenation reaction cannot be discussed in the same way as the conventional method.

[0006]

Means for Solving the Problems The inventors of the present invention have made earnest studies on improvement of selectivity of dehydrogenation reaction in a method for producing cycloalkanone using cycloalkanol produced by hydration of cycloalkene as described above. The inventors have found that high selectivity can be achieved by adding a specific compound into the dehydrogenation reaction system, and have reached the present invention.

That is, the gist of the present invention is a method for producing a cycloalkanone for dehydrogenating a cycloalkanol obtained by hydrating a cycloalkene, wherein a cycloalkanone and / or a cycloalkyl is contained in the reaction system for dehydrogenation. A method for producing a cycloalkanone, which comprises adding a compound having a group. Hereinafter, the present invention will be described in detail.

In the present invention, examples of the cycloalkene used for the hydration reaction include cyclopropene, cyclopentene, methylcyclopentenes, cyclohexene, methylcyclohexenes, cyclooctene, cyclododecene, etc., but preferably 5 to 8 Cycloalkenes having 4 carbocycles are preferred, and cyclohexene is particularly preferred. The cycloalkanol obtained by the hydration reaction corresponds to the starting cycloalkene. For example, when cyclohexene is used as the cycloalkene, cyclohexanol can be obtained by the hydration reaction.

The catalyst used for the hydration reaction is an acid catalyst, particularly a solid acid catalyst. As the solid acid catalyst, zeolite, a strongly acidic ion exchange resin having a sulfonic acid group, zirconium dioxide, titanium dioxide, aluminum oxide, an inorganic compound such as silicon dioxide, smectite, kaolinite, a layered compound such as vermiculite is aluminum, silicon. The ion-exchange layered compound treated with one or more kinds of metal oxides selected from titanium, zirconium and the like is exemplified, and zeolite is preferable.
Preferred examples of zeolites include mordenite, erionite, ferrierite, and ZSM-disclosed by Mobil.
5, crystalline aluminosilicates such as ZSM-based zeolites containing ZSM-11 and the like, and metalloaluminosilicates and metallosilicates containing foreign elements such as boron, iron, gallium, titanium, copper and silver. . As the exchangeable cation species of zeolite, a proton exchange type (H type) is usually used, but alkaline earth elements such as Mg, Ca and Sr, rare earth elements such as La and Ce, Fe and Co,
Those exchanged with at least one cation species of Group 8 to 10 elements such as Ni, Ru, Pd and Pt are also effective, or those containing Ti, Zr, Hf, Cr, Mo, W, Th and the like. Is also effective.

In the hydration reaction, the molar ratio of cycloalkene to water is selected from a wide range and varies depending on whether the reaction system is a continuous system or a batch system. However, when the cycloalkene or water is in a large excess as compared with other raw materials, the reaction rate decreases, which is not practical. The molar ratio of water to cycloalkene in the reactor is usually 1 to 100, preferably 5 to 30. The weight ratio of the catalyst to the cycloalkene in the reactor is usually 0.01 to 200, preferably 0.1 to 20.

In addition to the reaction starting material cycloalkene and water, the reaction system also contains nitrogen, hydrogen, helium, argon,
It is preferable to use an inert gas such as carbon dioxide.
In this case, it is desirable that the content of oxygen in the inert gas is small, and the content of oxygen is usually 100 ppm or less, preferably 50 ppm or less, and particularly preferably 20 ppm or less. Further, an aliphatic hydrocarbon, an aromatic hydrocarbon, an oxygen-containing organic compound, a sulfur-containing organic compound, a halogen-containing organic compound and the like may coexist in the reaction system.

Regarding the temperature of the hydration reaction, a low temperature is advantageous in terms of the hydration equilibrium of cycloalkene and an increase in side reactions, but a high temperature is advantageous in terms of the reaction rate. The reaction temperature varies depending on the cycloalkene used, but is usually 70 to 200 ° C., preferably 80 to 16
0 ° C. The reaction pressure is not particularly limited, but it is preferable to set the pressure at which cycloalkene and water can be kept in a liquid phase, usually 50 kg / cm ² or less, preferably 20 kg / cm ^2.
~ ² kg / cm ² . Furthermore, the reaction time or residence time is usually 0.1 to 10 hours, preferably 0.5 to
5 hours.

In the present invention, the cycloalkanol obtained by the above hydration reaction is subjected to a dehydrogenation reaction, but this cycloalkanol also includes one obtained by a method other than the hydration reaction of cycloalkene. You may have.
The dehydrogenation reaction is preferably carried out as a gas phase flow reaction,
The reaction system may be either a fixed bed or a fluidized bed for the catalyst, but the fixed bed is industrially preferable. The dehydrogenation catalyst is not particularly limited as long as it is a catalyst generally used for the dehydrogenation reaction of cycloalkanol such as cyclohexanol, and a copper-zinc catalyst (US Pat. No. 4,250,118).
No.), a copper-chromium catalyst (Japanese Patent Laid-Open No. 58-157741, US Pat. No. 4,310,703, British Patent No. 1444484.
No. 1,500,884), copper-cobalt catalyst (JP-A-55-136241), zinc-calcium catalyst (Japanese Patent Publication No. 52-48977, Canadian Patent No. 862799).
Are exemplified.

The temperature of the dehydrogenation reaction varies depending on the type of catalyst used, but is usually 200 to 400 ° C. If the temperature is too low, the conversion rate will be small, and if it is too high, the conversion rate will be large, but byproducts will increase, which is not preferable. The reaction pressure is not particularly limited and can be applied from reduced pressure to increased pressure, but usually around normal pressure, preferably 0.1 to 10 kg.
/ Cm ² , and particularly preferably 0.5 to 5.0 kg / cm ² . The feed rate of the reaction raw material mixture is usually 0.1 to 100 hr ⁻¹ , preferably 0.5 to 20 hr ⁻¹ in liquid hourly space velocity (LHSV), and the reaction raw material mixture is inert to the reaction such as nitrogen. You may supply it after diluting with a suitable gas.

The present invention is characterized in that a compound having a cycloalkanone and / or a cycloalkyl group is added to the above dehydrogenation reaction system. The cycloalkanone to be added may be one kind or plural kinds, and examples thereof include cyclopropanone, cyclopentanone, cyclohexanone, methylcyclohexanone, cyclooctanone, cyclodecanone, and the like, but preferably 5 to 8 It is a cycloalkanone having a carbocycle. Among these, it is particularly preferable to previously add the same cycloalkanone as the cycloalkanone obtained by the dehydrogenation reaction to the reaction system for dehydrogenation,
For example, when cyclohexanol produced by hydration of cyclohexene is used as a raw material for the dehydrogenation reaction, the cycloalkanone added in advance is preferably cyclohexanone.

Further, the compound having a cycloalkyl group is preferably a compound having the same cyclic alkyl group as the cycloalkanol which is the raw material compound of the present invention. For example, when performing hydration of cyclohexanol, a compound having a cyclohexyl group is preferable as the compound having a cycloalkyl group, and specifically, cyclohexyl acetate, cyclohexyl propionate, cyclohexyl butyrate, cyclohexyl valerate, cyclohexyl caproate. Carboxylic acid cyclohexyl ester such as, methylcyclohexane, ethylcyclohexane, propylcyclohexane, butylcyclohexane, amylcyclohexane, hexylcyclohexane, dicyclohexyl, cyclohexylcyclohexene, cyclohexylcyclohexadiene, cyclohexylcyclohexanone, etc., alkylcyclohexane or alkenylcyclohexane, arylcyclohexane such as cyclohexylphenol , Methylcyclohexyl Ether, ethyl cyclohexyl ether, propyl cyclohexyl ether, butyl cyclohexyl ether, amyl cyclohexyl ether, hexyl cyclohexyl ether, alkyl cyclohexyl ether or alkenyl cyclohexyl ethers such as dicyclohexyl ether. The cyclohexyl group-containing compound also includes those having a substituent in the cyclohexyl group, alkyl group, alkenyl group or the like. Among the compounds having the above cyclohexyl group,
Cyclohexyl acetate, amyl cyclohexane, butyl cyclohexyl ether and the like are exemplified as particularly preferable ones. These may be used alone or in plural, but it is preferable to add plural kinds in practical use.

The amount of the compound having a cycloalkanone and / or cycloalkyl group added to the dehydrogenation reaction system is usually 0. 1 with respect to the cycloalkanol used for the dehydrogenation reaction.
0001 to 20% by weight, preferably 0.01 to 1
0% by weight. This is a compound having a cycloalkanone and / or a cycloalkyl group to be added (excluding corresponding dehydrogenated cycloalkanol when cycloalkanol is used as a dehydrogenation reaction raw material. For example, cyclohexanol is used as a dehydrogenation reaction raw material. The total amount of cyclohexanol is excluded.). When cycloalkanone is added, the amount of cycloalkanone added is 0.
It is preferably 0001 to 15% by weight, particularly 0.01 to 6% by weight. If the addition amount is too small, the effect may not be sufficiently exhibited. On the other hand, if the amount is too large, the selectivity may decrease. When a compound having a cycloalkyl group is added, the amount of the compound having a cycloalkyl group added is 0.001 to 10% by weight, particularly 0.01 to 5% by weight.
It is preferred that If the addition amount is too small, the effect may not be sufficiently exhibited. Further, if the amount is too large, the purity of the starting material for cycloalkanol is lowered, so that the concentration of cycloalkanone in the obtained reaction product is lowered. Even if the cycloalkanone is excessively added to lower the selectivity, it is possible to improve the selectivity by further adding a compound having a cycloalkyl group.

The method of adding the compound having a cycloalkanone and / or cycloalkyl group to the reaction system is not particularly limited, but it may be added in advance to the starting material cycloalkanol, or separately to the reaction system. A method of adding and supplying it, or a method of adding it at the stage of the hydration reaction of cycloalkene may be used. Further, in the present invention, when the dehydrogenation reaction is carried out in the presence of water, the selectivity of cycloalkanone to be formed and the conversion rate of cycloalkanol can be further improved. Any existing form of water may be used, and it may be liquid or gaseous. The amount of water present in the reaction system is usually 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the starting cycloalkanol. If the amount of water is too large, the conversion rate of the dehydrogenation reaction may be significantly reduced, and if it is too small, the effect may not be sufficiently exhibited. Water is allowed to exist in the reaction system by, for example, a method of adding it to cycloalkanol in advance, a method of using the cycloalkanol used in the hydration reaction system containing water in the dehydrogenation reaction, a reaction separately from cycloalkanol. Examples include a method of adding water to the system.

[0019]

The present invention will be described in more detail based on the following examples, but the present invention is not limited to the following examples without departing from the gist thereof. The analysis of the reaction liquid in the examples was performed by gas chromatography.

Example 1 15 parts by weight of cyclohexane obtained by a partial hydrogenation reaction of benzene and 3 parts of water were placed in an autoclave equipped with a stirring blade.
0 parts by weight and 10 parts by weight of gallium silicate catalyst (Si / Ga atomic ratio = 25/1) were added, and the mixture was placed under a nitrogen atmosphere for 12 hours.
The reaction was carried out at 0 ° C. under 5 atmospheric pressure for 1 hour. The oil phase was separated from the obtained reaction solution, and the oil phase was purified by distillation to obtain cyclohexanol having a purity of 99.5% or more. Diameter 2
A cylindrical tube having a length of 7 mm and a length of 200 mm was charged with 100 ml of a copper-chromium-potassium dehydrogenation catalyst and set in an electric furnace. To the above-mentioned cyclohexanol obtained by hydration of cyclohexene, 4.0% by weight of cyclohexanone was added, and this was supplied to the electric furnace at a rate of 240 ml / hr.
The dehydrogenation reaction was performed under the conditions of 155 ° C and 155 ° C. As a result, cyclohexanol conversion was 57.5%, cyclohexanone selectivity was 99.1%, and phenol selectivity was 0.3.
%, And the cyclohexylcyclohexanone selectivity was 0.4%. A summary of the results is shown in Table-1.

Comparative Example 1 Under the reaction conditions of Example 1, a dehydrogenation reaction was carried out without adding anything to cyclohexanol. Cyclohexanol conversion was 56.5% and cyclohexanone selectivity was 98.8.
%, Phenol selectivity 0.4%, cyclohexylcyclohexanone selectivity 0.6%. A summary of the results is shown in Table-1.

EXAMPLE 2 Under the reaction conditions of Example 1, cyclohexanol contained 0.001.0% by weight of cyclohexanone and 1.7% by weight of water.
A dehydrogenation reaction was performed by addition. As a result, the conversion of cyclohexanol was 61.2% and the selectivity of cyclohexanone was 9
The selectivity was 9.0%, the phenol selectivity was 0.2%, and the cyclohexylcyclohexanone selectivity was 0.5%. A summary of the results is shown in Table-1.

Example 3 Under the reaction conditions of Example 1, cyclohexanol was added with 0.01 wt% of cyclohexanone and 1.7 wt% of water to carry out a dehydrogenation reaction. As a result, the conversion of cyclohexanol was 61.5% and the selectivity of cyclohexanone was 99.1.
%, Phenol selectivity 0.2%, cyclohexylcyclohexanone selectivity 0.5%. A summary of the results is shown in Table-1.

Example 4 Under the reaction conditions of Example 1, 0.1% by weight of cyclohexanone and 1.7% by weight of water were added to cyclohexanol to carry out a dehydrogenation reaction. As a result, the conversion of cyclohexanol was 60.8%, the selectivity of cyclohexanone was 99.3%,
The phenol selectivity was 0.3% and the cyclohexylcyclohexanone selectivity was 0.2%. The summary of the results is shown in Table-1.
Shown in

Example 5 Under the reaction conditions of Example 1, 4.0% by weight of cyclohexanone and 1.7% by weight of water were added to cyclohexanol to carry out a dehydrogenation reaction. As a result, the conversion of cyclohexasanol was 60.0% and the selectivity of cyclohexanone was 99.5.
%, Phenol selectivity 0.3%, cyclohexylcyclohexanone selectivity 0.2%. A summary of the results is shown in Table-1.

Comparative Example 2 Under the reaction conditions of Example 1, 1.7% by weight of water was added to cyclohexanol to carry out a dehydrogenation reaction. as a result,
The conversion of cyclohexanol was 59.2%, the selectivity of cyclohexanone was 98.6%, the selectivity of phenol was 0.3%, and the selectivity of cyclohexylcyclohexanone was 0.8%.
A summary of the results is shown in Table-1.

[0027]

[Table 1]

Example 6 Under the reaction conditions of Example 1, cyclohexyl acetate, amylcyclohexane and butylcyclohexyl ether were mixed with 1
The dehydrogenation reaction was carried out by adding 1% by weight and 1.5% by weight of water in a ratio of 4: 19: 1. As a result, the conversion of cyclohexanol was 60.6%, the selectivity of cyclohexanone was 99.5%, the selectivity of phenol was 0.2%, and the selectivity of cyclohexylcyclohexanone was 0.2%.

Example 7 Under the reaction conditions of Example 1, dehydrogenation reaction was carried out by adding cyclohexyl acetate and amylcyclohexane in a ratio of 3: 4 at a total of 0.14% by weight and water at 1.5% by weight. . As a result, the conversion of cyclohexanol was 60.1%, the selectivity of cyclohexanone was 99.1%, and the selectivity of phenol was 0.3.
%, And the cyclohexylcyclohexanone selectivity was 0.5%.

Example 8 Under the reaction conditions of Example 1, a dehydrogenation reaction was carried out by adding cyclohexyl acetate and amylcyclohexane in a ratio of 3: 4 and 0.014% by weight in total and 1.5% by weight of water. .
As a result, the conversion of cyclohexanol was 60.0%, the selectivity of cyclohexanone was 98.9%, and the selectivity of phenol was 0.
3%, cyclohexylcyclohexanone selectivity 0.6%
Met.

Example 9 Under the reaction conditions of Example 1, cyclohexanol was added with cyclohexanone, cyclohexyl acetate, amylcyclohexane, and butylcyclohexyl ether at 2:14:19:
1.0% by weight in total, 1.5% by weight in water
A dehydrogenation reaction was performed by addition. As a result, the conversion of cyclohexanol was 60.6%, and the selectivity of cyclohexanone was 9
The selectivity was 9.5%, the phenol selectivity was 0.2%, and the cyclohexylcyclohexanone selectivity was 0.1%.

Example 10 Under the reaction conditions of Example 1, cyclohexanol was added with cyclohexanone, cyclohexyl acetate and amylcyclohexane at a ratio of 1.7: 1: 1.3 to give a total of 3.0% by weight and a water content of 1. A dehydrogenation reaction was carried out by adding 5% by weight.
As a result, the conversion of cyclohexanol was 60.0%, the selectivity of cyclohexanone was 99.4%, and the selectivity of phenol was 0.
2%, cyclohexylcyclohexanone selectivity 0.2%
Met.

Example 11 Under the reaction conditions of Example 1, cyclohexanol was mixed with cyclohexanone, cyclohexyl acetate, and amylcyclohexane at a ratio of 17: 1: 1.2 to give a total of 18% by weight.
A dehydrogenation reaction was performed by adding 1.5% by weight of water. As a result, the conversion of cyclohexanol was 62.5%, the selectivity of cyclohexanone was 99.0%, and the selectivity of phenol was 0.4.
%, And cyclohexylcyclohexanone selectivity was 0.1%.

Example 12 Under the conditions of Example 1, the catalyst system was changed to a copper-zinc dehydrogenation catalyst (manufactured by JGC Chemicals), and 1.8% by weight of cyclohexanone was added to the starting material cyclohexanol to carry out dehydrogenation. The reaction was carried out. As a result, the conversion of cyclohexanol was 58.4.
%, Cyclohexane selectivity was 99.5%, phenol selectivity was 0.1%, and cyclohexylcyclohexanone selectivity was 0.1%. A summary of the results is shown in Table-2.

Comparative Example 3 Under the reaction conditions of Example 12, a dehydrogenation reaction was carried out without adding anything to cyclohexanol. Cyclohexanol addition rate was 58.6% and cyclohexane selectivity was 99.3.
%, Phenol selectivity 0.2%, cyclohexylcyclohexanone selectivity 0.2%. A summary of the results is shown in Table-2.

Example 13 Under the reaction conditions of Example 12, 0.3% by weight of cyclohexanone was added to cyclohexanol to carry out a dehydrogenation reaction. As a result, the cyclohexanol conversion rate was 58.0%,
Cyclohexane selectivity 99.5%, phenol selectivity 0.2%, cyclohexylcyclohexanone selectivity 0.
It was 1%. A summary of the results is shown in Table-2.

Example 14 Under the reaction conditions of Example 12, 4.0% by weight of cyclohexanone and 1.7% by weight of water were added to cyclohexanol to carry out a dehydrogenation reaction. As a result, the conversion of cyclohexanol was 66.4% and the selectivity of cyclohexane was 99.3.
%, Phenol selectivity 0.1%, cyclohexylcyclohexanone selectivity 0.2%. A summary of the results is shown in Table-2.

Comparative Example 4 Under the reaction conditions of Example 12, 1.7% by weight of water was added to cyclohexanol to carry out a dehydrogenation reaction. As a result, the conversion of cyclohexanol was 65.8%, the selectivity of cyclohexane was 99.1%, the selectivity of phenol was 0.2%, and the selectivity of cyclohexylcyclohexanone was 0.3%. A summary of the results is shown in Table-2.

Example 15 Under the reaction conditions of Example 12, 0.1% by weight of cyclohexanone and 1.7% by weight of water were added to cyclohexanol to carry out a dehydrogenation reaction. As a result, the conversion of cyclohexanol was 65.2% and the selectivity of cyclohexane was 99.3.
%, Phenol selectivity 0.1%, cyclohexylcyclohexanone selectivity 0.2%. A summary of the results is shown in Table-2.

[0040]

[Table 2]

Example 16 Under the reaction conditions of Example 12, cyclohexanol was added with cyclohexanone, cyclohexyl acetate and amylcyclohexane in a ratio of 3.4: 0.8: 1, for a total of 4.4.
The dehydrogenation reaction was performed by adding the mixture in an amount of wt%. As a result, the conversion of cyclohexanol was 59.3%, the selectivity of cyclohexanone was 99.5%, the selectivity of phenol was 0.1%, and the selectivity of cyclohexylcyclohexanone was 0.1%.

[0042]

According to the present invention, when the cycloalkanol obtained by the hydration reaction of cycloalkene is subjected to the dehydrogenation reaction, the cycloalkanol conversion rate is high and the cycloalkanone is obtained with high selectivity. be able to.

Claims (9)

[Claims] 1. A method for producing a cycloalkanone for dehydrogenating a cycloalkanol obtained by hydrating a cycloalkene, comprising:
Alternatively, a method for producing a cycloalkanone, which comprises adding a compound having a cycloalkyl group. 2. The method for producing cycloalkanone according to claim 1, wherein 0.0001 to 20% by weight of the compound having a cycloalkanone and / or a cycloalkyl group is added to the cycloalkanol. 3. The method for producing cycloalkanone according to claim 1, wherein the same cycloalkanone as the cycloalkanone obtained by the dehydrogenation reaction is added in advance to the dehydrogenation reaction system. 4. The method for producing cycloalkanone according to claim 1, wherein 0.0001 to 15% by weight of cycloalkanone is added to cycloalkanol. 5. The method for producing cycloalkanone according to claim 1, wherein the compound having a cycloalkyl group is added in an amount of 0.001 to 10% by weight based on the cycloalkanol. 6. The compound having a cycloalkyl group is at least one selected from carboxylic acid cycloalkyl ester, alkyl cycloalkane, alkenyl cycloalkane, aryl cycloalkane, alkyl cycloalkyl ether alkyl, and alkenyl cycloalkyl ether. 6. The method for producing a cycloalkanone according to claim 1, 2, or 5. 7. The method for producing a cycloalkanone according to claim 1, wherein the cycloalkyl group is a cyclohexyl group. 8. 0.1 to 1 relative to cycloalkanol
The method for producing cycloalkanone according to any one of claims 1 to 7, wherein the dehydrogenation reaction is carried out in the presence of 0% by weight of water. 9. The method for producing a cycloalkanone according to claim 1, wherein the cycloalkene is cyclohexene.