JP3417597B2 - Method for producing 1,3-diaminopropane - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing 1,3-diaminopropane. 1,3-Diaminopropane is a compound having a very wide range of applications as a raw material for polymers such as polyamide, epoxy resin and polyurethane, or as an intermediate for chelating agents, pharmaceuticals and agricultural chemicals.

[0002]

2. Description of the Related Art As a method for producing 1,3-diaminopropane, various methods have been conventionally known. For example,
A method for obtaining 1,3-diaminopropane by reacting 1,3-dichloropropane or 1,3-dibromopropane with ammonia has long been known (LHAmundsen
et al, J. et al. Am. Chem. Soc. 67 493 (1945), v. Brau
nBer. 70 992 (1937), U.S. Pat. No. 3,333,763.
No. 0). However, this method cannot be an industrial production method because the raw material 1,3-dihalopropane cannot be obtained in large quantities at low cost, purification is complicated, and there is a problem of equipment corrosion.

A method for obtaining 1,3-diaminopropane by heating and reacting acrolein, ammonia and hydrogen in the presence of a Raney nickel catalyst is also known (US Pat. No. 2,452,602, US Pat. No. 2662080). Although this method uses industrially easily available raw materials, it is still unsuitable as an industrial production method because of difficulty in handling acrolein and low yield due to frequent side reactions.

On the other hand, a method considered to be advantageous as an industrial production method is a production method using acrylonitrile, ammonia and hydrogen, which are obtained as a large amount of an industrial raw material at low cost, and hydrogen as main raw materials. Various attempts have also been made to this method, for example, acrylonitrile and ammonia (or ammonia water).
A method of obtaining a mixture of 1,3-diaminopropane and propylamine by heating under pressure in the presence of hydrogen and a reducing catalyst (Raney Ni or Co, etc.) (French Patent Specification No. 1355309). Method carried out in a water-containing high-boiling point water-soluble solvent system (US Pat. No. 32607)
No. 52) has been proposed. However, according to these methods, the reaction yield is still insufficient even when a large excess of ammonia is used, and a large amount of propylamine by-product, high boiling solvent or reduction catalyst recovery, and recycling operation Many problems such as complexity are recognized.

As a method for improving these problems, a method of hydrogenating a heated reaction mixture of acrylonitrile and ammonia in the presence of a reducing catalyst (reduction-treated product of Co-based oxide, Raney Ni, etc.) (UK Patent Specification) Calligraphy 8
24535, U.S. Pat.No. 3,427,356, F.
C. Whitmore et al, J. Am. Chem. Soc. 66 725 (1944)) have been proposed. According to this method, by-product of propylamine can be prevented, but the amount of by-product of bis (aminopropyl) amine, which is a dimer, increases rapidly, and as a result, the yield of 1,3-diaminopropane is not improved. There are drawbacks. Further, there is also a proposal that a remarkable improvement in yield can be recognized by a method in which a Raney Co catalyst is made to coexist in the reaction system from the beginning to react acrylonitrile and ammonia, and then hydrogenation is achieved (Japanese Patent Publication No. 46-2482). However, this method also has a large catalyst deactivation, and it is difficult to recover and reuse the catalyst, and the effective Raney catalyst is limited to a relatively expensive Co type, and an inexpensive Ni type that is industrially frequently used. Is very problematic as an industrial production method such as that it has no effect.

[0006]

As described above, in the synthesis reaction of 1,3-diaminopropane by the integrated production method from acrylonitrile, a Ni-based reducing catalyst which is usually used can give a sufficient yield and can be used as a catalyst catalyst. An important issue is to establish an industrially advantageous production method that is less toxic and enables recycling and reuse of the catalyst.

The present invention has been made to meet the above-mentioned demands in the technical field of the art, and the object thereof is to provide a method for producing 1,3-diaminopropane which can be industrially advantageously carried out. And more specifically, 1,3
-When diaminopropane is produced by an integrated production method from acrylonitrile, the catalyst is less poisoned, the catalyst can be recycled and reused, and 1,3-diaminopropane can be obtained in a sufficient yield. It is to provide a method for producing 3-diaminopropane.

[0008]

According to the present invention, when 1,3-diaminopropane is produced by reacting ammonia with acrylonitrile by heating and then catalytically reducing the reaction product, these reactions are carried out with alcohol. It relates to a method for producing 1,3-diaminopropane, which is characterized in that it is carried out in a solvent.

The method of the present invention will be specifically described below.
The method of the present invention comprises, as shown in the following formula, a first step in which ammonia is heated and acrylonitrile is reacted to carry out a cyanoethylation reaction, and a second step in which the reaction product is subjected to a catalytic reduction reaction in the presence of a catalyst and hydrogen. . These reactions are
Perform in alcoholic solvent.

[0010]

The starting material, acrylonitrile, of the present invention may be obtained from any source, and it is convenient to use an appropriately selected one from commercially available acrylonitrile. The other raw material, ammonia, can be used in any form, but anhydrous is preferable, and liquid ammonia, ammonia gas, or a solution obtained by dissolving ammonia in an organic solvent such as alcohol is used. Is preferred. When ammonia water is used as a raw material, the yield may be slightly lower than that of the anhydrous type.

The amount of acrylonitrile and ammonia used is at least 1.5 times, preferably 2.0 to 30.0 times, and particularly preferably 3.0 to 20.0 times the amount of ammonia with respect to acrylonitrile. Used in a molar amount range.

The reaction between acrylonitrile and ammonia is carried out in an alcohol solvent. As the alcohol solvent, any solvent can be used as long as it dissolves acrylonitrile and ammonia and does not participate in the reaction, but preferably methanol, ethanol, propanol, isopropanol, butanol, secondary butanol, isobutanol, and tertiary butanol. , Methoxyethanol, ethoxyethanol, isopropoxyethanol, methoxyisopropanol, ethoxyisopropanol, isopropoxyisopropanol or the like is used. These alcohol solvents may be used alone or in combination of two or more. The amount of alcohol solvent used is not particularly limited, but the product concentration is 5 when considering operability and economy.
It is preferable to use it so as to be about 60%, more preferably about 10 to 40%.

Further, as the solvent, a mixture of the above alcohol solvent with an organic solvent other than alcohols can be used. Examples of organic solvents other than alcohols include ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, ethers such as dioxane and tetrahydrofuran, aprotic polar solvents such as dimethylformamide and N-methylpyrrolidone. To be The amount of the organic solvent other than alcohols used is 50% or less, preferably 25% or less of the total amount of the solvent. 50% of the total amount of organic solvents other than alcohols
When used in the above ratio, the reaction promoting effect and the catalyst deactivation preventing effect of the alcoholic solvent are reduced, which is not preferable.

The reduction reaction in the process of the present invention is carried out using hydrogen in the presence of a catalyst. The reducing catalyst used may be any reducing catalyst having the ability to convert a nitrile group into an amino group, but preferably Raney nickel catalyst, Raney cobalt catalyst, nickel or cobalt supported catalyst, for example, nickel-diatomaceous earth catalyst, Examples thereof include a cobalt-diatomaceous earth catalyst and the like, or a platinum or palladium oxide catalyst and the like. Particularly preferred are Raney nickel catalysts, nickel- or cobalt-supported catalysts, etc., which are relatively inexpensively available and easy to use industrially. The amount of the reducing catalyst to be used is not particularly limited, but it is usually 0.1 to 40% by weight, preferably 0.5 to 25% by weight based on the acrylonitrile as a raw material. Further, as a reducing aid, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide and barium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal alcoholates such as sodium methoxide. And basic compounds such as amines such as triethylamine may be used in combination with the above catalyst. The use of these reducing aids improves the selectivity of the target product, 1,3-diaminopropane. The amount of the reducing aid used is not limited, but it is usually 0.01 to 20% by weight, preferably 0.05 to 10% by weight, based on the raw material acrylonitrile. The reduction catalyst and the reduction auxiliary may be charged into the system from the beginning, or may be added to the reaction system immediately before the catalytic reduction.

The reaction temperature in the first step and the second step of the method of the present invention is usually in the range of 50 to 200 ° C., preferably 7
It is applied in the range of 0 to 160 ° C. The reaction is carried out in a pressurized system, and the reaction pressure is not particularly limited, but is usually at a pressure based on the vapor pressure of the raw material system during the heating reaction of acrylonitrile and ammonia, and at the catalytic reduction of 20 to 20 due to the injection of hydrogen gas. It is applied in the range 400 kg / cm @ 2, preferably in the range 25 to 200 kg / cm @ 2. The reaction time varies greatly depending on the reaction temperature and the reaction pressure in both the first step and the second step, but is usually in the range of 0.5 to 10 hours, preferably in the range of 1 to 8 hours.

The method for carrying out the present invention is usually carried out as follows. In an alcohol solvent or a mixed solvent of alcohol and another solvent, a predetermined amount of liquid ammonia and acrylonitrile are charged, the temperature is raised to a predetermined temperature to cause a heat reaction, and then a reducing catalyst and a reducing auxiliary agent are added, and then a predetermined pressure is reached. Inject hydrogen. Since the hydrogen pressure decreases with the progress of the reduction reaction, hydrogen is replenished so as to maintain the predetermined pressure. The reaction is complete when the pressure drop ceases. After completion of the heating reaction in the first step, unreacted excess ammonia may be removed or supplemented outside the system before addition of the reducing catalyst. Further, the reducing catalyst and the reducing aid may be charged in the system in advance before the first step reaction. The method of the present invention can be carried out either batchwise or continuously.

After completion of the reaction, the catalyst is separated from the reaction solution by filtration or decantation, and then the solvent and the product are recovered by distillation under normal pressure or reduced pressure. The reduction catalyst separated at this time can be reused for the next reaction as it is or after a simple treatment such as washing with an alcohol solvent.

[0019]

EXAMPLES The constitution and effects of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 A 200 ml autoclave equipped with an induction stirrer, a temperature detector, a pressure gauge, a safety valve and a hydrogen introducing pipe was charged with 10 g of acrylonitrile, 48 g of liquid ammonia and 48 g of isopropanol and heated to 120 ° C. The mixture was heated and reacted for a minute. After cooling while removing and collecting excess ammonia, 0.5 g of Raney nickel catalyst (NDHT-90 manufactured by Kawaken Fine Chemicals Co., Ltd.) and 0.04 g of sodium hydroxide were added, and then the reaction temperature was 100 ° C. and the pressure was 7 ° C.
The reduction reaction is carried out while hydrogen gas is being injected under pressure so as to maintain the pressure at 0 kg / cm ² . Absorption of hydrogen ends in about 1 hour. After the reaction was completed, the catalyst was separated from the colorless and transparent reaction liquid and analyzed by gas chromatography. As a result, 11.7 g of 1,
Formation of 3-diaminopropane was confirmed. The reaction yield was 83.6%. Next, the same operation was repeated except that the separated and recovered used catalyst was sequentially reused, and the results of trying to reuse the catalyst are shown below. Number of catalyst recyclings 1,3-diaminopropane production (g) Reaction yield (%) ────────────────────────────── 1 11.8 84.3 2 11.5 82.1 3 11.6 82.9 4 11.3 80.7

Comparative Example 1 The same operation as in Example 1 was repeated except that isopropanol as a reaction solvent was not used. The amount of 1,3-diaminopropane produced was 6.5 g, and the reaction yield was 46.4%. The results of recycling the recovered catalyst were as follows. Number of catalyst recyclings 1,3-diaminopropane production (g) Reaction yield (%) ────────────────────────────── 1 4.6 32.9 2 3.2 22.9 3 1.8 12.9 4 0.4 2.9

Examples 2 to 8 The reaction solvent was methanol, ethanol, butanol, second
The same operation as in Example 1 was repeated except that the butanol, propanol, methoxyethanol, and isopropoxyisopropanol were replaced. The amount of 1,3-diaminopropane produced and the reaction yield at this time were as follows. Examples Reaction solvent 1,3-diaminopropane production (g) Reaction yield (%) ────────────────────────────── ───── 2 Methanol 10.9 77.9 3 Ethanol 11.2 80.0 4 Butanol 11.5 82.1 5 Secondary butanol 11.8 84.3 6 Propanol 9.6 68.6 7 Methoxy Ethanol 10.3 73.6 8 Isopropoxyisopropanol 11.1 79.3

Example 9 Acrylonitrile 20 was placed in the same reactor as in Example 1.
g, liquid ammonia 48g, secondary butanol 48g and Raney nickel catalyst (Kawaken Fine Chemicals, N
After charging 0.5 g of DHT-90) and reacting for 10 minutes at a reaction temperature of 100 ° C., a reaction temperature of 100 ° C. and a pressure of 90 k
The reduction reaction was carried out while introducing hydrogen gas under pressure so as to maintain g / cm ² . Absorption of hydrogen ends in about 1 hour. After completion of the reaction, the catalyst was separated from the colorless and transparent reaction liquid and analyzed by gas chromatography, whereupon formation of 20.6 g of 1,3-diaminopropane was confirmed. Reaction yield is 7
It was 3.6%. Next, the completely same operation was repeated except that the separated and recovered used catalyst was sequentially reused, and the result of trying to reuse the catalyst is shown below. Number of catalyst recyclings 1,3-diaminopropane production (g) Reaction yield (%) ────────────────────────────── 1 20.1 71.8 2 20.5 73.2 3 19.8 70.7 4 18.8 67.1

Comparative Example 2 The same operation as in Example 9 was repeated except that secondary butanol as a reaction solvent was not used. The amount of 1,3-diaminopropane produced was 10.4 g, and the reaction yield was 37.1%.
Met. The results of recycling the recovered catalyst were as follows. Number of catalyst recyclings 1,3-diaminopropane production (g) Reaction yield (%) ────────────────────────────── 1 3.6 12.9 2 0.4 1.4 3 0 0

[0025]

According to the method of the present invention, 1,3-diaminopropane can be obtained in a high yield by the integrated production method from acrylonitrile. Further, the present invention has the following advantages. (1) The reaction rate is improved and the reaction time is shortened. (2) Generation of high boiling by-products is suppressed. (3) The yield of the desired product is improved. (4) Purification is easy because there are few by-products. (5) Less deactivation of the catalyst. (6) The recovered catalyst can be reused as it is or by a simple treatment. (7) Since it is an integrated manufacturing, the number of steps can be greatly shortened, which is economically advantageous. (8) Waste is greatly reduced.

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Claims (2)

(57) [Claims] 1. When producing 1,3-diaminopropane by heating and reacting ammonia with acrylonitrile and then catalytically reducing the reaction product, these reactions are carried out in an alcohol solvent. Do 1,3
-Method for producing diaminopropane. 2. The alcohol solvent is methanol, ethanol, propanol, isopropanol, butanol,
The process according to claim 1, which is one or more of secondary butanol, isobutanol, tertiary butanol, methoxyethanol, ethoxyethanol, isopropoxyethanol, methoxyisopropanol, ethoxyisopropanol and isopropoxyisopropanol.