JP2004059515A - Method for producing cycloalkanone and cycloalkanol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for highly selectively converting a cycloalkyl hydroperoxide to a cycloalkanone and a cycloalkanol in good selectivity of the cycloalkanone. <P>SOLUTION: The cycloalkanone and the cycloalkanol are produced by mixing a liquid containing the cycloalkyl hydroperoxide with a transition metal hydroxide and an aqueous alkali solution to react the cycloalkyl hydroperoxide. The transition metal hydroxide containing group 6A, 7A or 8 transition metal in the periodic table is preferable as the transition metal hydroxide. <P>COPYRIGHT: (C)2004,JPO

Description

【００２８】
この表に示されるように、硫酸コバルトを使用した比較例１では、シクロヘキサノンの選択率が４８％と高くなっているが、シクロヘキサノンとシクロヘキサノールの合計選択率は８６％に留まっている。一方、酢酸コバルトを使用した比較例２および２−エチルヘキサン酸コバルトを使用した比較例３では、シクロヘキサノンの選択率がそれぞれ４２％および３８％、またシクロヘキサノンとシクロヘキサノールの合計選択率がそれぞれ８９％および９１％に留まっている。これに対し、本発明に従って水酸化コバルトを使用した実施例１は、比較例２および３に比べて、シクロヘキサノンの選択率およびシクロヘキサノンとシクロヘキサノールの合計選択率をともに向上させており、また比較例１に比べては、シクロヘキサノンの選択率を同等に保ちながら、シクロヘキサノンとシクロヘキサノールの合計選択率を向上させている。
【００２９】
【発明の効果】
本発明によれば、シクロアルカノンの選択性良く、シクロアルキルヒドロペルオキシドを高選択的にシクロアルカノンとシクロアルカノールに変換することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing cycloalkanone and cycloalkanol by decomposing a cycloalkyl hydroperoxide.
[0002]
[Prior art]
The reaction of converting a cycloalkyl hydroperoxide into a cycloalkanone and a cycloalkanol is one of the industrially useful reactions. For example, in a process for producing KA oil (a mixture of cyclohexanone and cyclohexanol) by oxygen oxidation of cyclohexane, , The post-treatment step of the oxidation reaction mixture. This reaction is usually performed by mixing a cycloalkyl hydroperoxide-containing liquid with a metal catalyst, an aqueous alkali solution, or the like, and many methods have been proposed so far.
[0003]
For example, JP-A-8-34751 discloses a triarylphosphine complex of iron, cobalt, nickel or copper, and JP-A-9-77704 discloses a ruthenium or cobalt halide or an organic acid as the mixed component. JP-A-9-194408 discloses an aqueous solution containing an alkali metal hydroxide and an alkali metal salt, and JP-A-10-1449 discloses an aqueous solution containing a combination of a compound such as a salt or a complex and an N-substituted imidazole. Combinations of compounds such as cobalt halides, organic acid salts, and complexes with quaternary ammonium salts or pyridinium salts have been proposed, respectively.
[0004]
[Problems to be solved by the invention]
However, in these conventional methods, when it is desired to obtain more cycloalkanone having a higher utility value than cycloalkanol, the selectivity of cycloalkanone is not always sufficient or the total selectivity of cycloalkanone and cycloalkanol is not sufficient. Was not always enough. Therefore, an object of the present invention is to provide a method capable of converting cycloalkyl hydroperoxide into cycloalkanone and cycloalkanol with high selectivity and high selectivity.
[0005]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that the above object can be achieved by mixing and reacting a cycloalkyl hydroperoxide-containing liquid with a specific component, and have completed the present invention. That is, the present invention relates to a method for producing cycloalkanone and cycloalkanol by mixing a liquid containing a cycloalkyl hydroperoxide with a transition metal hydroxide and an aqueous alkali solution and reacting the cycloalkyl hydroperoxide. It is.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail. The cycloalkyl hydroperoxide used in the method of the present invention has usually 5 to 20, preferably 5 to 10 carbon atoms. Specifically, for example, cyclopentyl hydroperoxide, cyclohexyl hydroperoxide, cycloheptyl hydroperoxide, cyclooctyl hydroperoxide, cyclononyl hydroperoxide, cyclodecyl hydroperoxide, cyclododecyl hydroperoxide, cyclopentadecyl hydroperoxide, cyclohexadecyl hydroperoxide Peroxides and the like can be mentioned, and if necessary, two or more of them can be used.
[0007]
The liquid containing the above cycloalkyl hydroperoxide is mixed with a transition metal hydroxide and an aqueous alkali solution to carry out a reaction to convert the cycloalkyl hydroperoxide into the corresponding cycloalkanone and cycloalkanol. By treating the cycloalkyl hydroperoxide-containing liquid with a specific component in this manner, cyclohexanone and cyclohexanol can be produced with high selectivity for cycloalkanone with high selectivity.
[0008]
As the cycloalkyl hydroperoxide-containing liquid, a liquid having a cycloalkyl hydroperoxide concentration of about 0.1 to 20% by weight is usually used. For example, a solution in which a cycloalkyl hydroperoxide is dissolved in an organic solvent such as an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon may be used, or the corresponding cycloalkane may be used in a molecular form. A reaction mixture containing cycloalkyl hydroperoxide obtained by performing a liquid phase catalytic oxidation reaction with oxygen may be used.
[0009]
When a reaction mixture obtained by the above liquid phase catalytic oxidation reaction is used as the cycloalkyl hydroperoxide-containing liquid, the mixture usually contains unreacted cycloalkane, cycloalkanone, or cycloalkanone, together with cycloalkyl hydroperoxide. Oxidation products such as cycloalkanols, carboxylic acids, and esters are included, and these can be separated and recovered after treating the mixture by the method of the present invention, and at that time, contained in the mixture. The cycloalkanone or cycloalkanol used can be separated and recovered together with the cycloalkanone or cycloalkanol produced by the method of the present invention.
[0010]
Examples of the transition metal hydroxide mixed with the cycloalkyl hydroperoxide-containing liquid include, for example, chromium hydroxide, manganese hydroxide, iron hydroxide, cobalt hydroxide, nickel hydroxide, copper hydroxide, zirconium hydroxide, and hydroxide. Examples thereof include ruthenium, rhodium hydroxide, palladium hydroxide, cerium hydroxide, and platinum hydroxide, and two or more of these can be used as necessary. Of these, hydroxides of transition metals of Groups 6A, 7A and 8 of the periodic table are preferably used.
[0011]
The mixing ratio of the transition metal hydroxide is usually from 0.001 to 10 ppm by weight, preferably from 0.01 to 1 ppm by weight, more preferably from 0.05 to 1 ppm by weight, as a metal, based on the cycloalkyl hydroperoxide-containing liquid. ~ 0.2 ppm by weight.
[0012]
Examples of the aqueous alkali solution to be mixed with the cycloalkyl hydroperoxide-containing solution include metal hydroxides such as sodium hydroxide and potassium hydroxide; metal carbonates such as sodium carbonate and potassium carbonate; sodium acetate and potassium acetate. An aqueous solution containing one or more alkalis such as metal acetates is used. The concentration of the alkali in the aqueous solution is usually 1 to 50% by weight, preferably 10 to 50% by weight, and more preferably 20 to 30% by weight.
[0013]
The mixing ratio of the alkali aqueous solution is usually 0.1 to 10% by weight based on the cycloalkyl hydroperoxide-containing liquid. When the cycloalkyl hydroperoxide-containing liquid contains an acid or an ester, the acid or ester is usually used in an amount of 0.5 to 5 moles, preferably 1 to 3 moles as an alkali relative to the acid or ester. It is desirable to mix an alkaline aqueous solution.
[0014]
The temperature of the above reaction is usually 20 to 200 ° C, preferably 50 to 160 ° C, more preferably 80 to 140 ° C. The reaction pressure is usually 0.1 to 3 MPa. The reaction may be carried out batchwise or continuously.
[0015]
For the post-treatment operation after the reaction, a known method can be appropriately selected.For example, the cycloalkanone and the cycloalkanol are separated by separating the reaction mixture into oil and water and subjecting the obtained oil layer to distillation. can do.
[0016]
【Example】
Hereinafter, examples of the present invention will be described, but the present invention is not limited thereto.
[0017]
Reference Example 1 (Preparation of liquid containing cyclohexyl hydroperoxide)
252.51 g of cyclohexane, 0.044 g of cyclohexane containing 0.47% by weight of cobalt (II) octylate, 0.51 g of cyclohexanone, and 0.52 g of cyclohexanol were placed in a 1 L autoclave, and stirred under a nitrogen atmosphere. The pressure and the temperature were adjusted to 0.93 MPa and 140 ° C., respectively. After a mixed gas of 300 ml / min of nitrogen and 100 ml / min of air was blown into the mixture for 1 hour, the mixed gas was switched to 100 ml / min of air, and the flow rate was gradually increased to 275 ml / min after 45 minutes. Simultaneously with this switching, cyclohexane containing 1.0 ppm by weight of cobalt (II) octylate was added at 4 g / min and 1 g of cyclohexane containing 0.1% by weight of cyclohexanone and 0.1% by weight of cyclohexanol. At the same time, the supply was started at the same time, and withdrawal of the reaction liquid was started at almost the same rate as the supply rate. After 1.5 hours from the start of the continuous reaction, the reaction temperature was adjusted to 145 ° C. After 3.5 hours from the start of the continuous reaction, the extracted reaction solution was continuously introduced into a 200 mL autoclave. After continuously mixing with water at 0.25 ml / min, the mixture was separated into an oil layer and an aqueous layer. This oil layer was used as a cyclohexyl hydroperoxide-containing liquid in the following examples.
[0018]
Example 1
When the oil layer obtained in Reference Example 1 and used here was analyzed immediately before, it was found to be 96% by weight of cyclohexane, 1.33% by weight of cyclohexanone, 1.92% by weight of cyclohexanol, and 0.67% by weight of cyclohexyl hydroperoxide. Was. The oil layer contained a total of 0.36% by weight of carboxylic acids and esters, of which 0.032% by weight of cyclohexyl esters was calculated as cyclohexanol. In a 200 mL autoclave, 50.14 g of the oil layer, a 10 wt ppm aqueous solution of cobalt (II) hydroxide (0.80 g) in an amount of 0.1 ppm by weight of cobalt with respect to the oil layer, and a mixture of carboxylic acids and esters. A 25 wt% aqueous solution of sodium hydroxide (0.43 g) was added in an amount 1.4 mol times as much as sodium hydroxide to the total, and the mixture was stirred at 130 ° C. for 30 minutes under a nitrogen atmosphere.
[0019]
As a result of analyzing the obtained reaction mixture, the reaction mixture contained 0.78 g of cyclohexanone, 1.10 g of cyclohexanol, 0.05 g of cyclohexyl hydroperoxide, and 0.013 g of esters (in which cyclohexyl esters were converted to cyclohexanol. 0.007 g). The conversion of cyclohexyl hydroperoxide was 85%, the selectivity for cyclohexanone based on cyclohexyl hydroperoxide was 48%, and the selectivity for cyclohexanol was 52%.
[0020]
Comparative Example 1
When the oil layer obtained in Reference Example 1 and used here was analyzed immediately before, it was found to be 95% by weight of cyclohexane, 1.32% by weight of cyclohexanone, 1.94% by weight of cyclohexanol, and 0.71% by weight of cyclohexyl hydroperoxide. Was. The oil layer contained a total of 0.36% by weight of carboxylic acids and esters, of which the content of cyclohexyl esters was 0.032% by weight in terms of cyclohexanol. In a 200 mL autoclave, 50.32 g of this oil layer, 100 wt ppm aqueous solution of cobalt (II) sulfate (0.26 g) in an amount of 0.1 ppm by weight of cobalt with respect to this oil layer, and the total of carboxylic acids and esters Then, an aqueous solution of sodium hydroxide (0.42 g) in an amount of 1.4 mol times as sodium hydroxide was added thereto, and the mixture was stirred at 130 ° C. for 30 minutes under a nitrogen atmosphere.
[0021]
As a result of analyzing the obtained reaction mixture, the reaction mixture contained 0.76 g of cyclohexanone, 1.06 g of cyclohexanol, 0.12 g of cyclohexyl hydroperoxide, and 0.023 g of esters (in which cyclohexyl esters were converted to cyclohexanol. 0.013 g). The conversion of cyclohexyl hydroperoxide was 66%, the selectivity for cyclohexanone based on cyclohexyl hydroperoxide was 48%, and the selectivity for cyclohexanol was 38%.
[0022]
Comparative Example 2
In a 200 mL autoclave, 50.00 g of the oil layer obtained in Reference Example 1 (the analysis result immediately before use is the same as that of Comparative Example 1), and the weight of the oil layer was 0.1% by weight of cobalt to 100% by weight. ppm cobalt acetate (II) aqueous solution (0.21 g) and a 25 wt% sodium hydroxide aqueous solution (0.47 g) in an amount 1.4 mol times as sodium hydroxide based on the total of carboxylic acids and esters. And stirred at 130 ° C. for 30 minutes under a nitrogen atmosphere.
[0023]
As a result of analyzing the obtained reaction mixture, the reaction mixture contained 0.77 g of cyclohexanone, 1.10 g of cyclohexanol, 0.04 g of cyclohexyl hydroperoxide, and 0.017 g of esters (in which cyclohexyl esters were converted to cyclohexanol. 0.011 g). The conversion of cyclohexyl hydroperoxide was 88%, the selectivity for cyclohexanone based on cyclohexyl hydroperoxide was 42% and the selectivity for cyclohexanol was 47%.
[0024]
Comparative Example 3
In a 200 mL autoclave, 50.33 g of the oil layer obtained in Reference Example 1 (the analysis result immediately before use is the same as in Comparative Example 1) was added in an amount of 0.1 ppm by weight of cobalt to the oil layer. Cyclohexane solution of cobalt (II) ethylhexanoate (concentration: 50 ppm by weight, 0.63 g), and 25% by weight of 25% by weight sodium hydroxide in an amount of 1.4 mol times as much as sodium hydroxide based on the total of carboxylic acids and esters. A sodium aqueous solution (0.44 g) was added, and the mixture was stirred at 130 ° C. for 30 minutes under a nitrogen atmosphere.
[0025]
As a result of analyzing the obtained reaction mixture, the reaction mixture contained 0.77 g of cyclohexanone, 1.13 g of cyclohexanol, 0.02 g of cyclohexyl hydroperoxide, and 0.016 g of esters (in which cyclohexyl esters were converted to cyclohexanol. 0.009 g). The conversion of cyclohexyl hydroperoxide was 94%, the selectivity for cyclohexanone based on cyclohexyl hydroperoxide was 38%, and the selectivity for cyclohexanol was 53%.
[0026]
Table 1 summarizes the above results.
[0027]
[Table 1]

[0028]
As shown in this table, in Comparative Example 1 using cobalt sulfate, the selectivity for cyclohexanone was as high as 48%, but the total selectivity for cyclohexanone and cyclohexanol was only 86%. On the other hand, in Comparative Example 2 using cobalt acetate and Comparative Example 3 using cobalt 2-ethylhexanoate, the selectivity of cyclohexanone was 42% and 38%, respectively, and the total selectivity of cyclohexanone and cyclohexanol was 89%, respectively. And 91%. On the other hand, in Example 1 using cobalt hydroxide according to the present invention, both the selectivity of cyclohexanone and the total selectivity of cyclohexanone and cyclohexanol were improved as compared with Comparative Examples 2 and 3. Compared with 1, the total selectivity of cyclohexanone and cyclohexanol is improved while keeping the selectivity of cyclohexanone equivalent.
[0029]
【The invention's effect】
According to the present invention, cycloalkyl hydroperoxide can be converted into cycloalkanone and cycloalkanol with high selectivity and high selectivity.

Claims (2)

A method for producing cycloalkanones and cycloalkanols, comprising mixing a liquid containing a cycloalkyl hydroperoxide with a transition metal hydroxide and an aqueous alkali solution to react the cycloalkyl hydroperoxide. The method according to claim 1, wherein the transition metal hydroxide contains a transition metal belonging to Group 6A, 7A or 8 of the periodic table.