JP2001187765A - Method for producing cyclohexanebis(methylamine)s - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for economically elongating the life of a catalyst to be used in the reaction when producing cyclohexanebis(methylamine)s by hydrogenating cyclohexanedicarbonitriles. SOLUTION: This method for producing the cyclohexanebis(methylamine)s is characterized in that the hydrogenation is carried out by using a Raney cobalt catalyst containing manganese and carrying out the reaction in the presence of 0.1-1.5 mol water per mol of the cyclohexanedicarbonitriles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing cyclohexanebis (methylamine) by hydrogenating cyclohexanedicarbonitrile.

[0002]

2. Description of the Related Art It has been known that diamines are produced by hydrogenating dinitrile in the presence of a metal catalyst such as cobalt, nickel or platinum. At present, it differs greatly depending on the type of individual dinitrile and has not reached the industrial level.

A method for producing cyclohexanebis (methylamine) by hydrogenating cyclohexanedicarbonitrile is a method using Raney cobalt or Raney nickel catalyst (Japanese Patent No. 2718740), a method using these Raney catalysts, and diatomaceous A method using cobalt supported on earth and nickel supported on diatomaceous earth as catalyst (Japanese Patent Publication No.
No. 1338).

[0004] However, in the above-mentioned methods of Japanese Patent No. 2718740 and Japanese Patent Publication No. 41-21338, a sufficient yield of cyclohexanebis (methylamine) to be produced can be obtained in consideration of industrial production. In order to
Despite the fact that the amount of catalyst used requires a considerable amount with respect to the raw material cyclohexanedicarbonitrile,
The catalyst life is not disclosed.

[0005] That is, in the method described in the above publication, not only the amount of the catalyst but also a large amount of cost is required in the process of discarding the used catalyst or regenerating the catalyst. In terms of producing methylamines), further improvement is desired.

On the other hand, Japanese Patent No. 2713623 discloses a method for hydrogenating norbornane dicarbonitrile in the presence of an organic solvent and ammonia to form norbornane bis (methylamine), wherein silica, alumina and silica are used as catalysts. It is known that when a supported cobalt catalyst in which cobalt is supported on a carrier such as alumina is used, the activity of the catalyst can be maintained for a long time, so that it can be repeatedly used about several times.

However, although the catalyst described in the above-mentioned Japanese Patent No. 2713623 can be reused, the number of reusable catalysts is not sufficient in view of industrial production, and norbornane dicarbonitrile is used. Hydrogenation of the compounds to produce norbornane bis (methylamine) still requires considerable catalyst. In addition, not only the amount of the catalyst but also the disposal of the used catalyst or a large amount of cost in the process of regenerating the catalyst, such as the costly and industrial production of norbornane bis (methylamine), This is a method in which further improvement is desired.

Japanese Patent Publication No. 1-52381 discloses a method of hydrogenating an aliphatic nitrile, an alkyleneoxynitrile, or an alkyleneaminonitrile into a primary amine by using an ether solvent containing ammonia, By performing the hydrogenation using a cobalt or ruthenium catalyst in the presence of water in an amount of from about 5% to about 15% by volume of the ether solvent, the use time of the catalyst is reduced as compared to the absence of water. About twice as long.

However, the type of dinitrile used in the method described in the above publication is different from the type of dinitrile used as a raw material in the present invention, and although the use time of the catalyst is improved, the use time is still insufficient. It is not. Furthermore, in order to obtain a sufficient yield of the primary amine to be produced, about 75% by mass to about 95% by mass of the ether solvent is required based on the starting nitrile. 20% by mass to approx. 30
It has been shown that 0% by weight of water is required.

That is, in the method described in Japanese Patent Publication No. 1-52381, since a large amount of solvent and water are used for the starting nitrile, the productivity of the desired primary amine is low, and the solvent is not sufficient after the reaction. In addition, a large amount of energy is required for separating or recovering water, and it cannot be said that the method can be efficiently and economically produced on an industrial scale.

Further, Japanese Patent Publication No. 54-40524 discloses a method of producing tetramethylenediamine by hydrogenating succinonitrile in the presence of a Raney cobalt catalyst containing manganese. In the examples, it is described that the catalyst was repeatedly used up to 50 times in a hydrogenation reaction.

However, the dinitrile described in the above-mentioned publication not only differs in type from the raw material used in the present invention, but even though the catalyst was used repeatedly, this result shows that the amount of the catalyst was different from the raw material succinonitrile. Is 39% by mass as metal cobalt, the amount of solvent dioxane used is 600% by mass,
And can be achieved under a large number of catalyst and solvent and ammonia usage conditions, such as liquid ammonia usage of 600% by weight.

[0013] That is, the method described in Japanese Patent Publication No. 54-40524 cannot be said to have a sufficient number of repetitive uses in view of the amount of catalyst used. Also,
Since this method uses not only the amount of the catalyst but also a large amount of solvent and liquid ammonia with respect to the raw material succinonitrile, the productivity of the target tetramethylenediamine is low, and the solvent used after the reaction is low. And require a lot of energy to separate or recover ammonia,
For this reason, this method cannot be said to be a method for efficiently and economically obtaining the desired product on an industrial scale.

[0014]

In order to economically and inexpensively produce cyclohexanebis (methylamine) by hydrogenating cyclohexanedicarbonitrile on an industrial scale, a long catalyst life for hydrogenation is required. It becomes essential. However, as described above, the catalyst life is not sufficient in the method of the prior art, and the catalyst life is sufficient even in a method using a large amount of solvent or water. Not reached.

An object of the present invention is to increase the life of the catalyst used in the reaction sufficiently and to obtain the desired cyclohexanebis (methylamine) with a higher yield than in the prior art described above. Another object of the present invention is to provide a method which can be manufactured economically and inexpensively.

[0016]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems in hydrogenating cyclohexanedicarbonitrile. As a result, hydrogenation was carried out using a Raney cobalt catalyst containing manganese. The inventors have found that the above-mentioned problems can be solved only when the reaction is performed in the presence of water in the specified range, and have completed the present invention.

That is, the present invention relates to (1) a compound represented by the general formula (I):
[Formula 3]

Embedded image (In the formula (I), X ₁ and X ₂ represent H or CN and are not the same.) A cyclohexanedicarbonitrile represented by the following formula is hydrogenated to obtain a compound represented by the general formula (II)

Embedded image (In the formula (II), Y ₁ and Y _{2 each} represent H or CH ₂ NH ₂ and are not the same.) In producing cyclohexanebis (methylamine) s represented by the formula, a Raney cobalt catalyst containing manganese is used. And hydrogenation in the presence of 0.1 to 1.5 moles of water per mole of cyclohexanedicarbonitrile, and a process for producing cyclohexanebis (methylamine). Is carried out in the presence of ammonia. (3) The method according to (2), wherein the amount of ammonia is 0.05 to 5 mol per 1 mol of cyclohexanedicarbonitrile. Manufacturing method, and (4) the amount of the catalyst is
The production method according to any one of the above (1) to (3), which is 0.1 to 10% by mass based on cyclohexanedicarbonitrile, and (5) a temperature at the time of hydrogenation is 50 to 250 ° C The method according to any one of (1) to (4), wherein (6) the pressure at the time of hydrogenation is 0.5 to 20 MPaG, It is a manufacturing method of description.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, cyclohexanedicarbonitrile as a raw material is represented by the general formula (I)
Which is 1,3-cyclohexanedicarbonitrile, 1,4-cyclohexanedicarbonitrile, or a mixture of both compounds. In addition, these cyclohexanedicarbonitrile compounds have stereoisomers, and a mixture thereof may be used, and any of them can be used as a starting material.

The above cyclohexanedicarbonitrile can be obtained, for example, by adding hydrogen cyanide to cyclohexene-4-carbonitrile using a zero-valent nickel complex and a cocatalyst, as described in Japanese Patent No. 2642457. be able to.

The hydrogenation in the present invention is performed in the presence of water. The amount of the water used is preferably in the range of 0.1 to 1.5 mol, more preferably in the range of 0.2 to 1.5 mol, per 1 mol of the starting material cyclohexanedicarbonitrile. If the amount is less than 0.1 mol, it is difficult to obtain a sufficient catalyst life. Use of an amount exceeding 1.5 mol is not preferable because the amount of by-products such as amides other than the target compound is extremely increased. Furthermore, a large amount of energy is required in the dehydration and purification step after the reaction, and it is preferable to carry out the reaction in the presence of water in the above range.

The catalyst used in the present invention contains manganese in an amount of 0.1%.
A Raney cobalt catalyst containing up to 15% by mass, more preferably 0.5 to 10% by mass, and alkali-developed Raney cobalt alloy powder containing manganese by a conventional method (for example, Catalyst Engineering Course, 10 Catalysts by Element, p. 528). Can be used.

The amount of the catalyst to be charged into the reaction vessel is not particularly limited. However, in order to maintain good fluidity of the reaction solution and to reduce the cost of the catalyst, the amount of the catalyst is usually reduced to cyclohexanedicarbonitrile as a raw material. It is preferable to use an amount up to about 10% by mass, more specifically, an amount of 0.1 to 10% by mass.

As for the method of adding the catalyst to the reactor, the amount of the catalyst to be used can be added all at once, but from the viewpoint of suppressing chemical catalyst poisoning, the catalyst required for one reaction is required. It is preferable to adopt a method in which the amount is added and the reaction is added sequentially each time the reaction is repeated.

In the present invention, the hydrogenation of cyclohexanedicarbonitrile is preferably carried out in the presence of ammonia. This ammonia has a function of suppressing the by-product of high-boiling substances such as secondary amines, tertiary amines, and polyamines other than the intended cyclohexanebis (methylamine) s, thereby improving selectivity. The amount of ammonia used is one of cyclohexanedicarbonitrile from the viewpoint of suppressing the by-product of the high-boiling substances, preventing a decrease in the hydrogenation rate, and facilitating the treatment or recovery of ammonia after the reaction. It is preferably in the range of 0.05 to 5 mol, and more preferably in the range of 0.1 to 2.5 mol, per mol.

In the present invention, the temperature at which the hydrogenation is carried out depends on the point of maintaining good productivity of cyclohexanebis (methylamine) s and suppressing by-products.
The range is preferably from 250 to 250 ° C, and more preferably from 80 to 200 ° C.

The hydrogen used for the hydrogenation is usually preferably 100% pure, but it does not matter at all if the reaction contains an inert gas such as a gas such as nitrogen, argon, helium or methane. . The pressure during hydrogenation is preferably in the range of 0.5 to 20 MPaG, more preferably 1 to 10 MPaG.
More preferably, it is within the range. At a pressure of less than 0.5 MPaG, it takes a long time to complete the hydrogenation, which leads to a decrease in the productivity of the desired cyclohexanebis (methylamine), and at a pressure exceeding 20 MPaG,
The effect of increasing the pressure is hardly observed, and the construction cost of the high-pressure equipment is rather increased, which is not preferable.

Although the hydrogenation in the present invention can be carried out without using a solvent, the starting material cyclohexanedicarbonitrile is also relatively high in viscosity, and the operability and the fluidity of the catalyst in the reactor are high. A solvent may be used for improvement or the like. Solvents that can be used are compounds inert to the hydrogenation reaction, for example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, mesitylene, methanol, ethanol, 1-
Alcohols such as propanol, 2-propanol, 1-butanol and 2-butanol, and similar compounds thereof are preferred.

When the above-mentioned solvent is used, the amount of the solvent used may be any amount. However, it is possible to maintain good productivity of the obtained cyclohexanebis (methylamine) and to use energy for distilling off the solvent. From the viewpoint of reducing the amount, the content is preferably up to 50% by mass, more preferably up to 20% by mass, and even more preferably up to 10% by mass of the starting cyclohexanedicarbonitrile.

In the present invention, the type of reaction for hydrogenating cyclohexanedicarbonitrile is not particularly limited, and the reaction may be carried out in any of batchwise, semi-batchwise, and flow-through systems. Is possible.

[0030]

The usefulness of the present invention will be described in more detail with reference to the following examples. In the following, analysis of the reaction solution was performed using gas chromatography.

Example 1 A stainless steel electromagnetically stirred autoclave having an inner volume of 0.5 L was placed in a 300 g solution of cyclohexanedicarbonitrile containing about 8% by mass of toluene (2.06 mol of cyclohexanedicarbonitrile) and 25.6 g of water (1.42 g). mol), and 1.8 g (dry weight) of a Raney cobalt catalyst (Co 75.7% by mass, Al 2.7% by mass, Mn 1.5% by mass) obtained by developing a manganese-containing Co-Al alloy. After sufficiently substituting with nitrogen, subsequently substituting with hydrogen and further adding liquid ammonia 1
0.5 g (0.62 mol) was injected. Next, hydrogen was injected into the autoclave until the pressure in the autoclave reached 2.5 MPaG.
The temperature was raised to ° C. to start the hydrogenation reaction. As the pressure inside the autoclave decreases with the progress of the reaction,
Supply hydrogen continuously to maintain aG, and keep the liquid temperature at 120
The hydrogenation reaction was carried out for 7 hours while adjusting to maintain the temperature. After the completion of the reaction, the autoclave is cooled to room temperature, and hydrogen and ammonia in the gas phase are expelled. The precipitated catalyst is left in the autoclave as it is, and the supernatant of the reaction solution is extracted. The same amount of the cyclohexanedicarbonitrile solution, ammonia, and water as described above are again charged, and a hydrogenation reaction is performed. This operation can be performed without additional catalyst.
Repeated times. As a result, the conversion of cyclohexanedicarbonitrile in the first reaction was 100% and the yield of cyclohexanebis (methylamine) was 94.4%, and the conversion and yield in the 20th reaction were They were 100% and 94.1%, respectively, and no deterioration of the catalyst was observed. The yield of the amide in which the cyano group of the starting cyclohexanedicarbonitrile was hydrolyzed in the first reaction was 0.4%, and the yield did not change in the twentieth reaction.

Example 2 Continuing with Example 1, the same amount of cyclohexanedicarbonitrile solution, ammonia and water were charged.
The operation of repeating the hydrogenation reaction was performed up to 50 times in the same manner as in Example 1. At this time, the catalyst was added 0.6 g each at the 21st, 31st and 41st times. As a result, the conversion of cyclohexanedicarbonitrile in the 21st reaction was 100%.
% And the yield of cyclohexanebis (methylamine)
The conversion and the yield in the 50th reaction were 100% and 93.8%, respectively, and no deterioration of the catalyst was observed. The yield of the amide in which the cyano group of the raw material cyclohexanedicarbonitrile was hydrolyzed in the 21st reaction was 0.4%, and was 0.5% in the 50th reaction.

Example 3 A stainless steel electromagnetic stirring type autoclave having an inner volume of 0.5 L was charged with 300 g of a cyclohexanedicarbonitrile solution containing about 8% by mass of toluene (2.06 mol of cyclohexanedicarbonitrile) and 51.9 g of water (2.88 g). mol), and 1.8 g of a Raney cobalt catalyst (Co 75.7% by mass, Al 2.7% by mass, Mn 1.5% by mass) obtained by developing a manganese-containing Co-Al alloy. After the replacement, the replacement with hydrogen was carried out, and 10.5 g of liquid ammonia (0.62 m
ol). Next, the pressure in the autoclave was increased to 3.9.
After injecting hydrogen to MPaG, the temperature was raised to 120 ° C. with stirring to start the hydrogenation reaction. Since the pressure in the autoclave decreases with the progress of the reaction, hydrogen was continuously supplied to maintain the pressure at 4.9 MPaG, and the hydrogenation reaction was performed for 7 hours by adjusting the liquid temperature to 120 ° C. . After the reaction,
The autoclave is cooled to room temperature and the hydrogen and ammonia in the gas phase are expelled. The precipitated catalyst is left in the autoclave as it is, and the supernatant of the reaction solution is extracted. The same amount of the cyclohexanedicarbonitrile solution, ammonia, and water as described above are again charged, and a hydrogenation reaction is performed.
This operation was repeated 20 times without adding any catalyst. As a result, the conversion of cyclohexanedicarbonitrile in the first reaction was 100% and the yield of cyclohexanebis (methylamine) was 94.4%.
100% conversion and yield in the second reaction
And 93.4%, and no catalyst deterioration was observed.
The yield of the amide in which the cyano group of the starting cyclohexanedicarbonitrile was hydrolyzed in the first reaction was 1.7%, and was 2.1% in the 20th reaction.

Example 4 A stainless steel electromagnetic stirring autoclave having an internal volume of 0.5 L was placed in a 300 g cyclohexanedicarbonitrile solution containing about 8% by mass of toluene (cyclohexanedicarbonitrile 2.06 mol), and 5.6 g water (0.31 g). mol) and a Raney cobalt catalyst obtained by developing a manganese-containing Co-Al alloy (Co 75.7% by mass, Al 2.7% by mass, Mn 1.5% by mass)
After charging 1.8 g, the inside of the system is sufficiently replaced with nitrogen, and then replaced with hydrogen, and then 10.5 g (0.62 mol) of liquid ammonia is further added.
Was injected. Next, the pressure inside the autoclave is 6.8MPaG
After hydrogen was injected under pressure, the temperature was raised to 120 ° C. with stirring to start the hydrogenation reaction. As the pressure inside the autoclave decreases as the reaction proceeds, hydrogen is continuously supplied to maintain the pressure at 7.8 MPaG, and the liquid temperature is adjusted to 120 ° C, and the hydrogenation reaction is performed for 3 hours. did. After the completion of the reaction, the autoclave is cooled to room temperature, and hydrogen and ammonia in the gas phase are expelled. The precipitated catalyst is left in the autoclave as it is, and the supernatant of the reaction solution is extracted. The same amount of the cyclohexanedicarbonitrile solution, ammonia, and water as described above are again charged, and a hydrogenation reaction is performed.
This operation was repeated 20 times without adding any catalyst. As a result, the conversion of cyclohexanedicarbonitrile in the first reaction was 100% and the yield of cyclohexanebis (methylamine) was 95.3%.
100% conversion and yield in the second reaction
And 90.9%, and no deterioration of the catalyst was observed.
The yield of the amide in which the cyano group of the starting cyclohexanedicarbonitrile was hydrolyzed in the first reaction was 0.3%, and the yield did not change even in the twentieth reaction.

Example 5 The same operation as in Example 1 was carried out except that the amount of ammonia charged into the autoclave was changed to 3.6 g (0.21 mol). As a result, the conversion of cyclohexanedicarbonitrile in the first reaction was 100% and the yield of cyclohexanebis (methylamine) was 90.9%, and the conversion and yield in the twentieth reaction were Respectively
It was 100% and 90.5%, and no deterioration of the catalyst was observed. The yield of the amide in which the cyano group of the raw material cyclohexanedicarbonitrile was hydrolyzed in the first reaction was 0.5%, and the yield did not change even in the twentieth reaction.

Example 6 The procedure of Example 1 was repeated except that the amount of ammonia charged into the autoclave was changed to 140.8 g (8.27 mol). As a result, the conversion of cyclohexanedicarbonitrile in the first reaction was 100%, and the yield of cyclohexanebis (methylamine) was 96.0%.
The conversion and yield in the twentieth reaction were 100% and 95.7%, respectively, and no deterioration of the catalyst was observed. The yield of the amide in which the cyano group of the starting cyclohexanedicarbonitrile was hydrolyzed in the first reaction was 0.8%, and was 1.0% in the twentieth reaction.

Example 7 A stainless steel electromagnetic stirring type autoclave having an inner volume of 0.5 L was placed in a 300 g cyclohexanedicarbonitrile solution containing about 8% by mass of toluene (2.06 mol of cyclohexanedicarbonitrile) and 25.6 g of water (1.42 g). mol), and 5.5 g of Raney cobalt catalyst (Co 75.7% by mass, Al 2.7% by mass, Mn 1.5% by mass) obtained by developing a manganese-containing Co-Al alloy. After the replacement, the replacement with hydrogen was carried out, and 10.5 g of liquid ammonia (0.62 m
ol). Next, when the pressure in the autoclave is 2.0
After injecting hydrogen to MPaG, the temperature was raised to 120 ° C. with stirring to start the hydrogenation reaction. As the pressure in the autoclave decreases as the reaction proceeds, hydrogen is continuously supplied to maintain the pressure at 2.5 MPaG, and the liquid temperature is adjusted to 120 ° C to perform the hydrogenation reaction for 3 hours. did. After the completion of the reaction, the autoclave is cooled to room temperature, and hydrogen and ammonia in the gas phase are expelled. The precipitated catalyst is left in the autoclave as it is, and the supernatant of the reaction solution is extracted. The same amount of the cyclohexanedicarbonitrile solution, ammonia, and water as described above are again charged, and a hydrogenation reaction is performed. This operation was repeated 20 times without adding any catalyst. As a result, the conversion of cyclohexanedicarbonitrile in the first reaction was 100% and the yield of cyclohexanebis (methylamine) was 93.1%, and the conversion and yield in the 20th reaction were Respectively
It was 100% and 92.3%, and no catalyst deterioration was observed. Further, the yield of the amide in which the cyano group of the starting cyclohexanedicarbonitrile was hydrolyzed in the first reaction was 0.5%, and was 0.6% in the 20th reaction.

Example 8 In Example 1, the amount of the catalyst charged in the autoclave was changed to 5.
All operations were the same except that the amount was 5 g and the liquid temperature of the hydrogenation reaction was 100 ° C. As a result, the conversion of cyclohexanedicarbonitrile in the first reaction was 100%, and the yield of cyclohexanebis (methylamine) was 95.8.
%, And the conversion and yield in the twentieth reaction were 100% and 95.5%, respectively, and no deterioration of the catalyst was observed. The yield of the amide in which the cyano group of the raw material cyclohexanedicarbonitrile was hydrolyzed in the first reaction was 0.4%, and the yield did not change even in the twentieth reaction.

Example 9 In Example 1, a cyclohexanedicarbonitrile which does not contain toluene was used as the cyclohexane dicarbonitrile to be charged in the autoclave, the amount of the catalyst was adjusted to 0.55 g, and the liquid temperature of the hydrogenation reaction was adjusted.
All operations were the same except that the temperature was 180 ° C. as a result,
The conversion of cyclohexanedicarbonitrile in the first reaction was 100% and the yield of cyclohexanebis (methylamine) was 94.5%, and the conversion and yield in the twentieth reaction were 100%, respectively. And 9
It was 2.2%, and no catalyst deterioration was observed. Also,
In the first reaction, the yield of the amide in which the cyano group of the raw material cyclohexanedicarbonitrile is hydrolyzed is
It was 0.6%, and there was no change in the yield even at the 20th time.

EXAMPLE 10 A stainless steel electromagnetic stirring type autoclave having an inner volume of 0.5 L was charged with 300 g of cyclohexanedicarbonitrile solution containing about 8% by mass of toluene (2.06 mol of cyclohexanedicarbonitrile) and 25.6 g of water (1.42 g). mol), and 5.5 g of Raney cobalt catalyst (Co 68.5% by mass, Al 3.1% by mass, Mn 5.5% by mass) obtained by developing a manganese-containing Co-Al alloy. After the replacement, the hydrogen was subsequently replaced and 10.5 g of liquid ammonia (0.62 mol
l) was injected. Next, the pressure inside the autoclave is 3.9M
After injecting hydrogen to PaG, the temperature was raised to 140 ° C. with stirring to start the hydrogenation reaction. Since the pressure in the autoclave decreases as the reaction proceeds, hydrogen is continuously supplied to maintain the pressure at 4.9 MPaG, and the liquid temperature is adjusted to 140 ° C, and the hydrogenation reaction is performed for 2 hours. did. After the completion of the reaction, the autoclave is cooled to room temperature, and hydrogen and ammonia in the gas phase are expelled. The precipitated catalyst is left in the autoclave as it is, and the supernatant of the reaction solution is extracted. The same amount of the cyclohexanedicarbonitrile solution, ammonia, and water as described above are again charged, and a hydrogenation reaction is performed. This operation was repeated 20 times without adding any catalyst. As a result, the conversion of cyclohexanedicarbonitrile in the first reaction was 100% and the yield of cyclohexanebis (methylamine) was 93.0%, and the conversion and yield in the twentieth reaction were 100 each
% And 92.9%, and no catalyst deterioration was observed. The yield of the amide in which the cyano group of the raw material cyclohexanedicarbonitrile was hydrolyzed in the first reaction was 0.8%, and the yield did not change in the twentieth reaction.

Example 11 In Example 10, a Raney cobalt catalyst (Co 64.0% by mass, Al 3.3% by mass, Mn 8.5% by mass) obtained by developing a manganese-containing Co-Al alloy as the catalyst to be charged into the autoclave was 5.5. All operations were the same except that the reaction was performed for 3 hours as g. As a result, the conversion of cyclohexanedicarbonitrile in the first reaction was 100%, and the yield of cyclohexanebis (methylamine) was 92.4.
%, And the conversion and yield in the twentieth reaction were 100% and 92.1%, respectively, and no deterioration of the catalyst was observed. The yield of the amide in which the cyano group of the raw material cyclohexanedicarbonitrile was hydrolyzed in the first reaction was 0.7%, and the yield did not change in the twentieth reaction.

Example 12 In Example 10, a Raney cobalt catalyst (76.0% by mass of Co, 4.0% by mass of Al, 0.2% by mass of Mn) obtained by developing a Co—Al alloy containing manganese as a catalyst to be charged into the autoclave was 5.5. All operations were the same except that the reaction was carried out for 4 hours as g. As a result, the conversion of cyclohexanedicarbonitrile in the first reaction was 100%, and the yield of cyclohexanebis (methylamine) was 9%.
The conversion and yield in the twentieth reaction were 100% and 90.0%, respectively, and no deterioration of the catalyst was observed. The yield of the amide in which the cyano group of the starting cyclohexanedicarbonitrile was hydrolyzed in the first reaction was 0.8%, and was 0.9% in the twentieth reaction.

Example 13 In Example 10, a Raney cobalt catalyst (Co 57.5% by mass, Al 3.7% by mass, Mn 11.7% by mass) obtained by developing a Co—Al alloy containing manganese as a catalyst to be charged into the autoclave. All operations were the same except that the reaction was carried out for 4 hours with 5.5 g. As a result, the conversion of cyclohexanedicarbonitrile in the first reaction was 100%, and the yield of cyclohexanebis (methylamine) was 92.2%.
%, And the conversion and yield in the twentieth reaction were 100% and 92.0%, respectively, and no deterioration of the catalyst was observed. The yield of the amide in which the cyano group of the raw material cyclohexanedicarbonitrile was hydrolyzed in the first reaction was 0.7%, and the yield did not change in the twentieth reaction.

Comparative Example 1 The procedure of Example 1 was repeated, except that the hydrogenation reaction was carried out without charging water to the autoclave. As a result, the conversion of cyclohexanedicarbonitrile in the first reaction was 100% and the yield of cyclohexanebis (methylamine) was 93.5%, but the yield in the fourth reaction was 33.9%. And the raw material cyclohexanedicarbonitrile still remained, and deterioration of the catalyst was observed.

Comparative Example 2 In Example 1, the amount of water charged in the autoclave was 1.8 g.
(0.1 mol) except that the operation was the same. As a result, the conversion of cyclohexanedicarbonitrile in the first reaction was 100% and the yield of cyclohexanebis (methylamine) was 93.9%, but the yield in the sixth reaction was 38.1%. And the raw material cyclohexanedicarbonitrile still remained, and deterioration of the catalyst was observed.

Comparative Example 3 In Example 1, the amount of water charged to the autoclave was 73.
All operations were the same except that the amount was 9 g (4.1 mol). As a result, the conversion of cyclohexanedicarbonitrile in the first reaction was 100% and the yield of cyclohexanebis (methylamine) was 82.2%, and the conversion and yield in the 20th reaction were The yields were 100% and 78.2%, respectively, and the yield was low. Also, in the first reaction, the amount of by-products of the amide in which the cyano group of the raw material cyclohexanedicarbonitrile was hydrolyzed was large, and the yield in the first reaction was 8.3%.
It was 12.2%.

Comparative Example 4 In Example 10, a Raney cobalt catalyst (76.9% by mass of Co, 4.2% by mass of Al) obtained by developing a Co—Al alloy containing no manganese was used as a catalyst to be charged into the autoclave. All operations were performed in the same manner except that the reaction was performed for a time. As a result, the conversion of cyclohexanedicarbonitrile in the first reaction was 100% and the yield of cyclohexanebis (methylamine) was 90.0%, but the yield in the eighth reaction was 40.1%. And the raw material cyclohexanedicarbonitrile still remained, and deterioration of the catalyst was observed.

[0048]

As is clear from the above description, particularly from Examples 1 to 13 and Comparative Examples 1 to 4, 0.1 to 1.5 mol per mole of a manganese-containing Raney cobalt catalyst and cyclohexanedicarbonitrile are used. By employing the method of the present invention in which hydrogenation is carried out in the presence of water at a specific ratio, an extremely long catalyst life is achieved, and cyclohexanebis (methylamine) can be produced at low cost.

Further, according to the method of the present invention, not only the amount of ammonia and catalyst used at the time of hydrogenation, but also
Even if a solvent is used, they can be significantly reduced as compared with the prior art, and thus can be said to be extremely useful industrially.

Continued on the front page (72) Inventor Seichi Ishii 1144 Togo, Mobara-shi, Chiba Mitsui Chemicals Co., Ltd. (72) Inventor Hiroharu Kageyama 1900 Togo, Togo, Mobara-shi, Chiba F-term (reference) 4G069 AA02 BB03A BB03B BC62A BC62B BC67A BC67B CB02 CB77 DA05 4H006 AA02 AC10 AC52 BA16 BA20 BC10 BC11 BC34 BE14 BE20 BE60 4H039 CA71 CB30

Claims (6)

[Claims] 1. A compound of the general formula (I) (In the formula (I), X ₁ and X ₂ represent H or CN and are not the same.) A cyclohexanedicarbonitrile represented by the following formula is hydrogenated to obtain a compound represented by the general formula (II). (In the formula (II), Y ₁ and Y _{2 each} represent H or CH ₂ NH ₂ and are not the same.) In producing cyclohexanebis (methylamine) s represented by the formula, a Raney cobalt catalyst containing manganese is used. And hydrogenating in the presence of 0.1 to 1.5 moles of water per mole of cyclohexanedicarbonitrile. 2. The method according to claim 1, wherein the hydrogenation is performed in the presence of ammonia. 3. The method according to claim 2, wherein the amount of ammonia is 0.05 to 5 mol per 1 mol of cyclohexanedicarbonitrile. 4. The production method according to claim 1, wherein the amount of the catalyst is 0.1 to 10% by mass based on cyclohexanedicarbonitrile. 5. The production method according to claim 1, wherein the hydrogenation temperature is 50 to 250 ° C. 6. The method according to claim 1, wherein the pressure for hydrogenation is 0.5 to 20 MPaG.