JP2002047220A - Method for producing cycloalkanol and cycloalkanone - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a cycloalkanol and a cycloalkanone from the corresponding 6 to 12-membered epoxycycloalkane and hydrogen gas, by which the cycloalkanol and the cycloalkanone are industrially produced in high yields in a catalyst-reusable state. SOLUTION: The method for producing the cycloalkanol and the cycloalkanone, comprising bringing the corresponding 6 to 12-membered epoxycycloalkane into contact with hydrogen gas in the presence of a nickel catalyst, is characterized by allowing 10 to 90 wt.% of an alcohol to exist in the reaction system.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a corresponding cycloalkanol and cyclodalkanone in one step from an epoxycycloalkane having 6 to 12 carbon atoms. Cycloalkanols and cycloalkanones can be derived from lactams, lactones, alkanediols or alkanedicarboxylic acids by known methods, and are useful compounds as intermediate materials for polyamides and polyesters.

[0002]

2. Description of the Related Art Cycloalkanol or cycloalkanone is produced, for example, by an air oxidation method of cycloalkane in the presence of a boric acid catalyst. By the way, in such an air oxidation method, since many by-products are generated by successive reactions, it is necessary to suppress the conversion of cycloalkane to a low level, and cycloalkanol and cycloalkanone, which are the target products, are required. The current situation is that the yield of is generally low. For example, in the air oxidation method of cyclododecane in the presence of a boric acid catalyst, the total yield of cyclododecanol and cyclododecanone is only 20%.

On the other hand, epoxycycloalkanes and / or epoxycycloalkenes can be produced in high yields by the epoxidation reaction of cycloalkenes, so that such epoxide compounds can be produced with high efficiency in cycloalkanols. And cycloalkanone, it is possible to industrially produce cycloalkanol and cycloalkanone from cycloalkenes with high yield. However, there are only a few reports of converting such epoxycycloalkanes and / or epoxycycloalkenes to cycloalkanols and cycloalkanones.

[0004] For example, Japanese Patent Publication No. 47-38437 discloses a hydrogenation reaction using Raney nickel as a metal catalyst. However, when this method was repeated, a large amount of cyclic hydrocarbons such as cyclododecan, cyclododecene or cyclododecadien, which proceeded to the deoxygenation reaction of the epoxy group, were produced as by-products, and the selectivity of cyclododecanol and cyclododecanone was increased. Or the yield was not satisfactory. Further, it was recognized that cyclic hydrocarbons such as cyclododecane further increased by repeated use of the catalyst.

As a method for suppressing such by-products of cyclic hydrocarbons, Japanese Patent Application Laid-Open No. 2000-136156 discloses a production method characterized by allowing a basic substance to be present in a nickel catalyst or a reaction system. . In this method, cyclododecane by-produced from epoxycyclododecanes,
The cyclic hydrocarbons of cyclododecene or cyclododecadien are greatly suppressed, and cyclododecanol and cyclododecanone are obtained with high selectivity. However, it does not disclose industrially important problems such as repeated use of the catalyst.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a method for producing corresponding cycloalkanols and cycloalkanones from epoxycycloalkanes and hydrogen gas in high yield in the presence of a nickel catalyst, so that the catalyst can be used repeatedly. Establish an industrial manufacturing method.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, in the presence of a nickel catalyst, a hydrogen gas was brought into contact with epoxycycloalkanes having 6 to 12-membered carbon atoms to respond thereto. In a method for producing cycloalkanol and cycloalkanone, a method for producing cycloalkanol and cycloalkanone, which comprises reacting in the presence of 10 to 90% by weight of an alcohol in a reaction system, was found, and the present invention was completed. Was.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The epoxycycloalkane used in the present invention is not particularly limited, but has 6 carbon atoms having an epoxy group.
A saturated or unsaturated cyclic hydrocarbon having a to 12-membered ring is preferable, and may be partially substituted with a methyl group or an ethyl group. More preferred are epoxy cyclic decane compounds having a 12-membered carbon ring. Specific examples of epoxycycloalkanes include epoxy compounds such as epoxycyclohexane, epoxycyclohexene, epoxycyclooctane, epoxycyclooctene, epoxycyclododecane, epoxycyclododecene, and epoxycyclododecadien. These epoxy compounds may be used alone or in a mixture. When various isomers exist in these epoxy compounds, the structure of the isomers is not particularly limited.

The nickel catalyst used in the present invention includes, for example, Raney nickel, nickel oxide, stabilized nickel and the like, but preferably stabilized nickel. Stabilized nickel has the advantage of being stable in air and easy to handle. The nickel catalyst may be supported on diatomaceous earth, silica, alumina, silica alumina, zeolite, or carbon. These nickel catalysts may be used alone or in combination of two or more.

The amount of the supported nickel catalyst is not particularly limited, but is usually 90 to 10% by weight, preferably 70 to 2% by weight, based on the weight of the carrier as nickel atoms.
5% by weight. Further, these nickel catalysts may contain a co-catalyst for improving the activity, selectivity, and other properties such as an alkali metal and an alkaline earth metal.

The alkali metal and alkaline earth metal as co-catalysts include alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal carbonates, alkali metal and alkaline earth metal alkoxides. It consists of at least one selected. For example, alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkaline earth metal carbonates such as calcium and magnesium carbonate; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide and potassium ethoxide; alkaline earth metal alkoxides such as magnesium methoxide and magnesium ethoxide; No. These compounds may be used alone or as a mixture of two or more.

The method for supporting the alkali metal and the alkaline earth metal is not particularly limited. In the production process of supporting the nickel compound on the carrier, the processing system may contain the alkali metal and the alkaline earth metal. Or,
A liquid containing an alkali metal and an alkaline earth metal may be supported on a nickel-supported catalyst at 0 to 100 ° C (by an impregnation method, a spray method, or the like), and may be dried at 60 to 120 ° C, for example.

The amount of the alkali metal and alkaline earth metal carried is not particularly limited, and is preferably 0 to 10 times the molar amount of nickel atoms in the nickel catalyst. More preferably, it is 0 to 5 times, and further preferably 0.05 to 1 time. If the amount is too large, the effect of adding the alkali metal and the alkaline earth metal is saturated, which is not only economically disadvantageous but also may cause a significant decrease in activity and an increase in by-products.

The amount of nickel catalyst used is such that the molar ratio of nickel atoms to epoxycycloalkanes is 1/3.
A nickel catalyst is allowed to coexist so as to be 00000 or more. If the amount is too small, the reaction time becomes longer.

The form of the nickel catalyst for bringing hydrogen gas into contact with the epoxycycloalkane is not particularly limited, but is preferably in the form of a powder when used in a suspension-bed liquid phase reaction.
In the case of shaped pellets, it is used for fixed bed catalysis. The fixed bed catalytic reaction can be performed by a trickle reaction, a liquid phase reaction, a gas phase reaction or the like depending on conditions.

In the case of a powdery catalyst used in a liquid phase suspension bed reaction, it is preferable to use a catalyst having an average particle size of several μm to several hundred μm. In the case of shaped pellets used for fixed bed catalysis, the average length of the pellets is 1 to 10 m
Those having an m size are preferably used.

In the present invention, alcohol is present in the reaction system for both the liquid phase suspension bed reaction and the fixed bed reaction. The alcohol used is not particularly limited, but has 1 to 20 carbon atoms.
Or an alicyclic alcohol having 5 to 20 carbon atoms or a polyhydric alcohol having 2 to 12 carbon atoms. Specifically, methanol, ethanol, n-propanol, iso-propanol, n-butanol, is
o-butanol, 2-methylpropanol, n-pentanol and its isomers, n-hexanol and its isomers, cyclopentanol, cyclohexanol, cyclooctanol, cyclododeanol, ethylene glycol, propylene glycol, butanediol hexanediol , Dodecanediol and the like. Preferred are cycloalkanols corresponding to epoxycycloalkanes.

The amount of the alcohol used is 10 to 10 parts by weight based on the total weight of the reaction raw materials including the epoxycycloalkanes.
It is 90% by weight, preferably 20-80% by weight, more preferably 30-70% by weight. If the amount of the alcohol used is small, the yield of cycloalkanol and cycloalkanone is low, and the effect of reusing the catalyst becomes insufficient. If the amount of the alcohol used is large, the productivity of cycloalkanol and cycloalkanone decreases, which is not preferable.

In the present invention, there is no problem even if a solvent other than alcohol is used as long as the reaction is not adversely affected, such as formation of by-products. However, even in such a case, the amount of alcohol used is 1 to the total weight.
It is 0 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight. Preferred solvents include, for example, hydrocarbons such as n-hexane, n-heptane, cyclohexane, cyclooctane and cyclododecane. Further, a small amount of water may coexist.

The reaction conditions of the present invention vary somewhat depending on the type and proportion of the epoxycycloalkane used, but the reaction temperature is 60-280 ° C., preferably 110-110 ° C.
２５０250 ° C. and the hydrogen pressure is 1-15 MPa, preferably 2-10 MPa. If the hydrogen pressure is too low or the reaction temperature is too low, the hydrogenation reaction of the epoxy group or the hydrogenation of the double bond does not proceed sufficiently, and the yield of cycloalkanol and cycloalkanone decreases. If the hydrogen pressure is too high, the hydrogenation rate is improved to some extent but does not significantly contribute to productivity. If the reaction temperature is too high, the generation of by-products such as high-boiling substances increases, which is not preferable. The reaction time and contact time are not particularly limited, but usually 3 hours or less is sufficient.

In the present invention, the reaction product can be isolated and separated from the reaction system, if necessary, for example, by distillation, crystallization, etc., and purified.

[0023]

EXAMPLES The technology of the present invention will be described below with specific examples, but the present invention is not limited to these examples.

Example 1 A stabilized nickel catalyst containing MgO (containing 63% by weight as Ni, containing 5% by weight of MgO, SiO ₂ base, and this catalyst as catalyst A) was placed in a stainless steel autoclave having an inner volume of 120 ml equipped with a stirrer. 0.297 g, 1,2-epoxy-5,9-cyclododecadiene (hereinafter referred to as ECDD) 8.92 g and ethanol 20.81 g were added,
After pressurizing to 5 MPa with hydrogen at room temperature, the temperature was raised to 150 ° C. After the temperature of the reaction solution reached 150 ° C., the hydrogen pressure was adjusted again to 5 MPa, and the mixture was heated and stirred at 150 ° C. for 1 hour. After the reaction, the reaction solution was cooled to room temperature, and the obtained reaction solution was analyzed by gas chromatography. As a result, ECD
D is completely consumed, and 90.9 mol% of cyclododecanol (hereinafter referred to as CDOL) and 0.8 mol% of cyclododecanone (hereinafter referred to as CDON) are produced, and cyclododecan (hereinafter referred to as CDAN) is produced. ) Was formed at 7.8 mol%.

Comparative Example 1 A reaction was carried out in the same manner as in Example 1, except that ECDD was changed to 30 g and ethanol was not added. As a result, the ECDD is completely consumed and the CDO
63.1 mol% of L and 9.2 mol% of CDON are produced,
CDAN was produced at 17.8 mol%.

Comparative Example 2 A reaction was carried out in the same manner as in Example 1 except that cyclohexane was used instead of ethanol.
As a result, the ECDD was completely consumed, and 76.1 mol% of CDOL and 2.6 mol% of CDON were formed.
AN was produced at 20.5 mol%.

Example 2 A reaction was carried out in the same manner as in Example 1 except that the ECDD was changed to 20.8 g and the ethanol was changed to 8.9 g. As a result, the ECDD is completely consumed,
CDOL was produced at 89.1 mol%, CDON was produced at 1.1 mol%, and CDAN was produced at 9.2 mol%.

Example 3 A reaction was carried out in the same manner as in Example 1 except that n-propanol was used instead of ethanol. As a result, the ECDD is completely consumed and the CDO
L is 89.7 mol% and CDON is 0.7 mol%,
CDAN was produced at 8.8 mol%.

Example 4 In Example 1, a stabilized nickel catalyst (Ni as 5
7% by weight, SiO _TwoBase, this catalyst is called catalyst B
Reaction was performed in the same manner as in Example 1 except that
Was. As a result, the ECDD has been completely consumed and the CDO
L is 89.8 mol%, CDON is formed at 1.1 mol%,
CDAN was produced at 7.9 mol%.

Comparative Example 3 A reaction was carried out in the same manner as in Example 4 except that cyclohexane was used instead of ethanol.
As a result, ECDD was completely consumed, CDOL was formed at 68.7 mol%, CDON was formed at 6.8 mol%, and CDON was produced.
AN was produced at 20.3 mol%.

Example 5 A K-modified stabilized nickel catalyst (Ni as 3%) was placed in a 120 ml stainless steel autoclave equipped with a stirrer.
0% by weight, 5% by weight as K, Al ₂ O ₃ base, this catalyst is referred to as catalyst C) 0.297 g, ECD
8.92 g of D and 20.81 g of cyclododecanol were added, and the mixture was pressurized to 3.5 MPa with hydrogen at room temperature.
The temperature was raised to 50 ° C. After the reaction solution temperature reaches 220 ° C,
The hydrogen pressure was increased to 5 MPa, and the mixture was heated and stirred at 220 ° C. for 1 hour. After the reaction, the reaction solution was cooled to 80 ° C., 100 ml of cyclohexane was added, the mixture was cooled to room temperature, and the obtained reaction solution was analyzed by gas chromatography. as a result,
ECDD is completely consumed, and CDOL and CDO formed from ECDD excluding the solvent cyclododecanol
The total yield of N was 94.9 mol% and the yield of CDAN was 4.7 mol%.

Example 6 A reaction was carried out in the same manner as in Example 5 except that the ECDD was changed to 15.0 g, the cyclododecanol was changed to 15.0 g, and the reaction temperature was changed to 240 ° C. As a result, ECDD is completely consumed, and CDOL and CD
The total yield of ON was 92.3 mol%, and CDAN was formed at 7.3 mol%. Comparative Example 4 A reaction was carried out in the same manner as in Example 6, except that cyclohexane was used instead of cyclododecanol. As a result, the ECDD is completely consumed,
The total yield of CDOL and CDON was 87.9 mol%, and CDAN was formed at 11.7 mol%.

The results of Examples 1 to 6 and Comparative Examples 1 to 4 are summarized in Table 1.

[Table 1]

Example 7 (Reaction of repeated use of catalyst) In Example 1, after the reaction, the same reaction as in Example 1 was performed again using the separated and recovered catalyst. This operation was repeated 10 times. Table 2 shows the reaction results of the first use, the fifth use and the tenth use of the catalyst.

Comparative Example 5 (Reaction of repeatedly using catalyst) In Comparative Example 2, the same reaction as in Comparative Example 2 was carried out again using the separated and recovered catalyst after the reaction. This operation was repeated 10 times. Table 2 shows the reaction results of the first use, the fifth use and the tenth use of the catalyst.

Example 8 (Reaction of repeated use of catalyst) In Example 5, after the reaction, the same reaction as in Example 5 was performed again using the separated and recovered catalyst. This operation was repeated five times. Table 2 shows the reaction results of the first use, the third use and the fifth use of the catalyst.

[0037]

[Table 2]

[0038]

According to the present invention, the corresponding cycloalkanol and cycloalkanone can be produced in high yield from epoxycycloalkanes and hydrogen gas, and an industrial production method capable of repeatedly using the catalyst can be established. .

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Claims (3)

[Claims] 1. A method for producing a corresponding cycloalkanol and a cycloalkanone by contacting a hydrogen gas with an epoxycycloalkane having a carbon number of 6 to 12 in the presence of a nickel catalyst. A method for producing cycloalkanol and cycloalkanone, wherein the reaction is carried out in the presence of about 90% by weight. 2. The epoxycycloalkane has 12 carbon atoms.
The process for producing cycloalkanol and cycloalkanone according to claim 1, which is a membered ring epoxycyclododecane. 3. The method for producing cycloalkanol and cycloalkanone according to claim 2, wherein the alcohol is cyclododecanol.