JP4101352B2 - Production method of diamine - Google Patents

Description

【００３３】
比較例７
特開平５−１７４１３号公報の実施例１に従い下記の手順で触媒の繰り替えし使用試験を行った。
電磁攪拌機付き５００ｍｌオートクレーブにメタノール７５ｇ、ラネーニッケル７．５ｇおよびアンモニア５９．５ｇを仕込み、さらに水素を導入して１５ｋｇ／ｃｍ^２にした後昇温を行った。オートクレーブの内温が１２０℃に達した後さらに水素を導入して内圧を４０ｋｇ／ｃｍ^２にした。次に、１，９−ノナンジアール２７．３ｇおよび２−メチル−１，８−オクタンジアール１１．７ｇをメタノール８０ｇに溶解させて得られたメタノール溶液１１９ｇを３時間かけて高圧定量ポンプにてオートクレーブ内に供給した。当該メタノール溶液の供給中オートクレーブ内を１２０℃に保った。反応の進行と共に水素が消費されるので逐次水素を追加し圧力を一定に保った。当該メタノール溶液の供給を止めると同時に水素の消費も止まり反応は終了した。反応液を冷却し、触媒を濾別した後、濾液をガスクロマトグラフィーで分析したところ、１，９−ノナンジアミンと２−メチル−１，８−オクタンジアミンの混合物が３５．６ｇ得られていることが分かった。仕込みジアルデヒドの合計に対する取得ジアミンの収率は９０％と計算された。
ラネーニッケル７．５ｇの代わりに濾別回収した触媒を用いた以外は、上記と同様の操作を繰り返し、反応収率の変化を調べた。結果を下に示す。
１回目反応 ジアミン収率 ９０％
２回目反応 〃 ８５％
３回目反応 〃 ７８％
４回目反応 〃 ６５％
５回目反応 〃 ４８％
ラネーニッケル触媒を用いた触媒の回収再使用試験では、反応後の活性が著しく低下した。
【００３４】
【発明の効果】
本発明により、ジアルデヒドからジアミンを製造する方法において、溶媒としてアルコール溶媒を用い、反応液中の水濃度が５〜１５重量％の範囲で反応を行うことにより、触媒の劣化を抑制しつつ良好な収率でジアミンを製造できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a diamine useful as a raw material for various polyamides or polyurethanes.
[0002]
[Prior art]
A solution obtained by dissolving a dialdehyde in a solvent is supplied to a reactor in which a hydrogenation catalyst, a solvent, ammonia and hydrogen are present, and the dialdehyde is reductively aminated to produce a corresponding diamine. 1) a method in which dialdehyde is introduced into a reductive amination reactor at a rate not substantially greater than the conversion rate of dialdehyde (see US Pat. No. 2,636,051), (2) dialdehyde is an alcohol solvent And a method of introducing this solution into a reductive amination reactor (see JP-A-5-17413), and (3) when dialdehyde is mixed with a diluent such as alcohol. A method in which a mixture prepared by suppressing the formation of hemiacetal by limiting the temperature to a maximum of 5 ° C. is added to a reductive amination reactor (JP-A-7-69). See 99 No.) is known.
In addition, one of the inventors of the present invention (4) by using a nickel catalyst supported on an inorganic oxide as a hydrogenation catalyst, a solution obtained by dissolving dialdehyde in a solvent, A method for reusing a catalyst in the reductive amination reaction of the dialdehyde fed to a reactor in which solvent, ammonia and hydrogen are present, and finding a method for producing a diamine in a single step, in a high yield and at a low cost. An application was made (see Japanese Patent Application Laid-Open No. 7-196586).
[0003]
The above method (1) discloses an example using water as a solvent and Raney nickel as a catalyst, but the yield of diamine is as low as 40% or less. I can not say.
The method (2) discloses an example using methanol or ethanol as a solvent and Raney nickel as a catalyst. Although the yield of diamine is as high as about 90%, according to the results of a further test by the present inventors (Comparative Example 7 of the present application), Raney nickel used in the reaction has a markedly reduced catalytic activity after the reaction, and the recovered catalyst can be reused. It was found that there was a problem. Therefore, this method cannot be said to be an economical production method in consideration of catalyst costs.
The method (3) requires temperature control to suppress the formation of hemiacetal, and therefore requires cooling with a refrigerant, which is not industrially preferable.
Although the method (4) discloses the reaction results when the catalyst is reused in Example 10, the number of times the catalyst is reused is only one, and the reaction results and catalyst when the catalyst is repeatedly reused. There is no mention of the reaction results when using. The present inventor examined the case where the catalyst was repeatedly reused by the method (4) (Comparative Example 1 of the present application). As a result, it was found that the diamine yield upon repeated reuse decreased from 92% for the first time to 91% for the second time to 82% for the fifth time. Therefore, this method has a problem as an industrial diamine production method in which the catalyst is continuously used when the catalyst is repeatedly reused, resulting in a decrease in the diamine yield.
[0004]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a method for producing diamine from dialdehyde in one step, in a high yield, and at a lower cost than conventional methods.
In the reductive amination reaction, since water is normally produced as a by-product, water coexists in the reaction system. In the above-mentioned prior literature, reference to this by-product water is disclosed in JP-A-7-69999 (3). It is only a gazette. Moreover, in Example 1, there is only a description that “the formed reaction water is distilled” during the post-treatment operation of the reaction, and it is considered that water is recognized as affecting the reaction results. I can't. Although there is no description regarding the water concentration at the time of reaction in this specification, it is estimated that the maximum concentration is 3.3% by weight from the description regarding the reaction conditions.
In US Pat. No. 2,636,051 of (1), there is no description regarding by-product water, as is clear from the fact that all of the examples use water as a solvent. In (2) Japanese Patent Laid-Open No. 5-17413, the amount of water by-product calculated from the reaction conditions described in Example 1 is 3.4% by weight, and in (4) Japanese Patent Laid-Open No. 7-196586. In the publication, the amount of water by-product is calculated as 2.30% by weight from the reaction conditions described in Example 1.
Therefore, it is clear that none of the above-mentioned prior art documents focuses on the influence of by-product water on the reductive amination reaction, and even more consciously does not refer to the control of the water concentration in the reaction solution. .
[0005]
[Means for Solving the Problems]
As a result of intensive studies on the influence of the water concentration in the reductive amination reaction solution on the reaction results, the present inventors have found that, according to the present invention, dialdehyde or a solution obtained by dissolving dialdehyde in a solvent is hydrogenated. In a method for producing a corresponding diamine by reductive amination of the dialdehyde by supplying it to a reactor in which a catalyst, a solvent, ammonia and hydrogen are present, an alcohol solvent is used as the solvent, and the water concentration in the reaction solution is 5 to 5. By finding a method characterized by carrying out the reaction in the range of 15% by weight, the above object could be achieved.
[0006]
According to the method of the present invention, since the activity of the catalyst during the reductive amination reaction can be further suppressed, diamine can be produced at low cost. It is an unprecedented finding that the decrease in catalyst activity can be suppressed by carrying out the reaction in the range of 5 to 15% by weight of water in the reaction solution using an alcohol solvent as the solvent, which is completely unexpected. Was that. In a method for producing expensive diamines, a decrease in diamine yield due to a decrease in catalytic activity greatly affects the production cost of diamines and lowers industrial value. In addition, frequent renewal of the catalyst accompanying a decrease in catalyst activity in an industrial continuous diamine production method requires complicated operations and reduces industrial value. Since the present invention can suppress a decrease in the activity of the catalyst, it is superior to the conventional method in that both of these industrial problems can be solved.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The dialdehyde used in the present invention is a linear aliphatic, branched aliphatic, alicyclic or aromatic skeleton having 4 to 20 carbon atoms, preferably 6 to 16 carbon atoms, more preferably 8 to 12 carbon atoms. The dialdehyde which has is mentioned. For example, linear aliphatic dialdehydes such as butane dial, hexane dial, octane dial, nonane dial, decandial, undecandial, dodecandial, tetradecandial, hexadecandial, octadecandial, eicosandial; Branched chain aliphatic dialdehydes such as methyloctane dial, 2-methylnonane dial, 2,7-dimethyloctane dial; 1,3-cyclohexanedicarbaldehyde, 1,4-cyclohexanedicarbaldehyde, 3 (4 ), 8 (9) -tricyclo [5.2.1.0] decandicarbaldehyde, 2 (3), 5 (6) -bicyclo [2.2.1] heptanedicarbaldehyde and the like. Aldehydes; or fragrances such as terephthalaldehyde and isophthalaldehyde Dialdehyde; is exemplified. These dialdehydes can be easily and inexpensively synthesized, for example, by an oxo reaction of an unsaturated aldehyde having one fewer carbon atoms or a diolefin having two fewer carbon atoms. It can also be obtained by ozonolysis of cyclic olefins having the same carbon number and subsequent reduction, oxidation of aromatic hydrocarbons having the same carbon number, reduction of dicarboxylic acids having the same carbon number, and the like.
The concentration of the dialdehyde is generally preferably in the range of 5 to 25% by weight with respect to the total reaction solution. If it is 5% by weight or less, the amount of ammonia and solvent recovered in the diamine separation and purification process will increase, and the industrial value will be small. If it is 25% by weight or more, the amount of polymer produced will increase and the yield of diamine will decrease. The deterioration of the catalyst is increased.
[0008]
Using the above dialdehydes as raw materials, linear aliphatic diamines such as butanediamine, hexanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tetradecanediamine, hexadecanediamine, octadecanediamine, eicosanediamine, etc. Branched-chain aliphatic diamines such as 2-methyloctanediamine, 2-methylnonanediamine and 2,7-dimethyloctanediamine; 1,3-cyclohexanedimethanamine, 1,4-cyclohexanedimethanamine, 3 (4) , 8 (9) -tricyclo [5.2.1.0] decanedimethanamine, 2 (3), 5 (6) -bicyclo [2.2.1] heptanedimethanamine and other alicyclic diamines; or p-xylylenediamine, m-xylylenediamine Etc. Any aromatic diamine; is produced.
[0009]
Examples of the alcohol solvent used in the present invention include alcohols, diols and polyols. Examples of the alcohol include aliphatic alcohols, alicyclic alcohols, and aromatic alcohols. The alcohol solvent preferably has 10 or less carbon atoms, and specific examples thereof include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, sec-butyl alcohol, tert- Butyl alcohol, n-amyl alcohol, i-amyl alcohol, sec-amyl alcohol, t-amyl alcohol, n-hexanol, n-heptanol, n-octanol, n-decanol, 2-ethylhexanol, 2-octanol, 3- Aliphatic alcohols such as octanol; Alicyclic alcohols such as cyclohexanol, cyclohexylmethanol, 2-cyclohexylethanol, 1-cyclohexylethanol; Aromatics such as benzyl alcohol and 2-phenylethanol Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 2-methyl-1, Examples include diols such as 4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, and diethylene glycol; polyols such as glycerin and pentaerythritol. Among these alcohol solvents having 10 or less carbon atoms, aliphatic alcohols having 5 or less carbon atoms are particularly preferable in terms of good distillation separation from the generated diamine. These alcohol solvents can be used alone or in a suitable mixture of two or more.
When an alcohol solvent having 11 or more carbon atoms is used, the solubility of water and ammonia in the solvent itself becomes small and the reaction cannot be performed in a uniform state, and the solvent becomes expensive and the industrial value is lowered.
Although there is no restriction | limiting in particular about the usage-amount of an alcohol solvent, It is 0.5-20 weight times with respect to this dialdehyde, Preferably it is the range of 1-10 weight times. If the amount of the alcohol solvent is too large, it is practically disadvantageous if the recovery and reuse of the solvent is taken into consideration. If the amount is too small, the yield of the diamine is lowered and the deterioration of the catalyst is increased.
[0010]
The water concentration in the reaction solution in the present invention is in the range of 5 to 15% by weight, preferably in the range of 7 to 12% by weight, based on the entire reaction solution. In the method for producing a diamine for reductive amination of a dialdehyde, as described above, it is known that water up to about 3.4% by weight is produced by the condensation of dialdehyde and ammonia. The concentration of water in the reductive amination reaction solution is maintained in a concentration range of 5 to 15% by weight by adding water from outside the system as necessary. When the water concentration is less than 5% by weight, the effect of suppressing the adhesion of the high boiling point component causing the catalyst deterioration to the catalyst surface is not recognized. On the other hand, if it exceeds 15% by weight, the amount of by-products in which the aldehyde group of the raw material dialdehyde is partially hydrogenated increases, so that the selectivity is lowered and the amount of high-boiling components produced is increased. Deactivation of the catalyst occurs due to this, which also leads to a decrease in yield.
[0011]
The amount of ammonia used in the reductive amination reaction is 5 to 50 times, preferably 10 to 30 times the amount of the raw material dialdehyde as the amount of ammonia in the reaction solution. If the amount of ammonia is too small, the yield decreases, and if it is too large, it is practically disadvantageous.
[0012]
The reductive amination reaction for producing diamine from dialdehyde can be carried out by a known method. Examples of hydrogenation catalysts include Raney catalysts such as Raney nickel, Raney cobalt, and Raney copper; metals that have hydrogenation activity such as nickel, cobalt, platinum, palladium, rhodium, ruthenium, and copper are diatomaceous earth, silica, alumina, silica alumina, and clay. , Supported catalysts such as titania, zirconia, magnesia, calcia, lanthanum oxide, niobium oxide, and carbon can be used. In particular, a nickel catalyst supported on an inorganic oxide or a nickel catalyst such as Raney nickel is preferable. The carrier may contain an alkali metal, an alkaline earth metal, a phosphorus oxide, or a mixture thereof. The main catalyst metal is nickel, but it may be nickel alone, modified with one or more metals such as cobalt, iron, copper, chromium, manganese, silver, molybdenum, rhenium, palladium, rhodium, ruthenium, platinum. Also good. The usage-amount of a nickel catalyst can be changed according to the desired reaction rate, and is chosen from the range of 0.01-30 weight% with respect to a reaction mixture, Preferably, it is 0.1-10 weight%. The catalyst may be suspended in the reaction liquid phase or used as a fixed bed.
[0013]
The reaction temperature is 40 to 200 ° C, preferably 80 to 160 ° C, particularly preferably 100 to 140 ° C. When the reaction temperature is lower than 40 ° C., the reaction does not proceed at a practically possible rate. When the reaction temperature is higher than 200 ° C., by-products increase, resulting in a decrease in yield.
[0014]
Although there is no restriction | limiting in particular in reaction pressure, Usually, it is the range of 40-200 atmospheres. Note that hydrogen may be added so as to replenish the hydrogen consumed in the reaction, or the reaction may be performed while always circulating hydrogen.
[0015]
For the reaction, a batch system, a continuous system, or the like is used. Preferably, a method in which dialdehyde is fed to the reactor at a rate slower than the hydrogenation rate is recommended. That is, in the case of a batch reactor, there is a method in which a reaction in which dialdehyde or a solution of dialdehyde is dissolved in a solvent is fed to a reactor filled with a catalyst, a solvent, ammonia and hydrogen while feeding at a rate slower than the hydrogenation rate. preferable. In the case of a continuous type, a method in which ammonia, a solvent and a dialdehyde are fed into a reactor filled with a catalyst, a solvent and hydrogen at a rate slower than the hydrogenation rate is preferable.
[0016]
The catalyst is separated from the reaction liquid containing the catalyst extracted from the reactor by a method similar to these by extracting only the reaction liquid from the reactor by filtration or centrifugal separation, and the catalyst component. The catalyst component can be reused by returning it to the reactor.
[0017]
The diamine thus obtained can be purified by a general purification method, that is, distillation or recrystallization after distilling off ammonia and the solvent from the reaction solution from which the catalyst has been separated. A pure diamine can be obtained.
[0018]
【Example】
Next, the method of the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
[0019]
Example 1
After adding 1.5 g of nickel catalyst and 70.0 g of n-butanol to a 500 ml autoclave with a magnetic stirrer, 10 kg / cm ² The inside of the autoclave was replaced three times with a hydrogen pressure of Next, 62.5 g of ammonia was added and hydrogen was 50 kg / cm. ² Then, the autoclave was heated to 140 ° C. Total pressure 100kg / cm ² After adjusting the pressure with hydrogen to be 37.5 g of a mixture of 1,9-nonanediar / 2-methyl-1,8-octanediar = 80/20 (molar ratio), 70.0 g of n-butanol and A mixed solution of 10.0 g of water was fed into the autoclave over 1 hour, followed by reaction for 2 hours. At this time, the total pressure in the autoclave is 100 kg / cm. ² The reaction was carried out while replenishing hydrogen sequentially. The water concentration in the reaction solution is 7.5% by weight when the amount of water added with the condensed water of dialdehyde and ammonia is added. After the reaction, the autoclave was cooled, the unreacted ammonia was released, and the catalyst component was separated from the contents by filtration to obtain 136.2 g of a reaction solution containing diamine. When the composition of the reaction solution was analyzed by gas chromatography, 36.5 g of a mixture of 1,9-nonanediamine / 2-methyl-1,8-octanediamine = 80/20 (molar ratio) was formed, and a hydroxyl group was formed at one end. As a result, 0.2 g of an amine having a ratio was generated. The yield of diamine based on the charged dialdehyde is calculated as 96%.
Next, the reaction was performed in the same manner as described above using the catalyst separated by filtration. As a result of analyzing the reaction solution after separating the catalyst by gas chromatography, the yield of diamine with respect to the charged dialdehyde was 94%.
The third, fourth, and fifth reactions were performed in the same manner. The diamine yield in each test was 94%, 92%, and 91%.
In 5 repeated reactions, the decrease in diamine yield was 5%, and the degree of catalyst deterioration was extremely small.
[0020]
Comparative Example 1
With reference to Example 1 of JP-A-7-196586, a repeated use test of the catalyst was conducted according to the following procedure.
In a 300 ml electromagnetic stirring type autoclave, 1.15 g of nickel catalyst (nickel content 52%) supported on diatomaceous earth having a pore volume of about 10 to about 100 nm in diameter and 0.19 ml / g and 1-butanol 63. After adding 00 g and introducing 60 atm of hydrogen, the temperature was raised to 160 ° C., and catalytic reduction treatment was performed at this temperature for 20 minutes. The autoclave was cooled to room temperature and then the hydrogen was released. Next, 30.6 g of ammonia is charged and 160 atm. ℃ Raised the temperature to. While flowing hydrogen gas at a rate of 20 L / hr, a high-pressure metering pump was charged with a solution of 18.72 g of 1-butanol and 75.0 g of 1-butanol in a mixture of 1,9-nonanedial and 2-methyl-1,8-octanedial over 40 minutes. Was fed into the autoclave. 160 hours after the completion of the supply of the solution ℃ Then, hydrogen gas was passed under stirring.
The water concentration in the reaction solution is 2.3% by weight as condensed water of dialdehyde and ammonia. The charged dialdehyde concentration in the total reaction solution was 10 weight %.
The hydrogen flow was stopped, and the autoclave was returned to normal pressure after cooling. By removing the catalyst from the reaction solution by filtration and concentrating the filtrate. Crude product 18.8 g was obtained. Gas chromatograph In As a result of analysis, 17.5 g of a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine was contained, and the total yield of diamine was 92.3%.
Subsequently, using the catalyst separated by filtration, the same operation as described above was repeated 5 times, and the change in the reaction yield was examined. Results are shown below.
First reaction diamine yield 92%
Second reaction 〃 91%
3rd reaction 〃 89%
4th reaction ８６ 86%
5th reaction ８２ 82%
By repeating the reaction five times, the diamine yield decreased by 10% from 92% in the first reaction to 82%, and the degree of catalyst deterioration was larger than that in Example 1.
[0021]
Example 2
The same conditions as in Example 1 except that 70.0 g of methanol was used instead of 70.0 g of n-butanol charged together with the catalyst, and 70.0 g of methanol was used instead of 70.0 g of n-butanol in the mixed solution to be fed. Reaction was performed. The water concentration in the reaction solution at this time is 7.5% by weight when the amount of water added with the condensed water of dialdehyde and ammonia is added. The results of repeating the reaction 5 times in the same manner as in Example 1 are shown below.
In 5 repeated reactions, the decrease in diamine yield was 5%, and the degree of catalyst deterioration was extremely small.
First reaction diamine yield 95%
Second reaction 〃 94%
Third reaction 〃 92%
4th reaction ９２ 92%
5th reaction 〃 90%
[0022]
Example 3
The same as Example 1 except that 70.0 g of isoamyl alcohol was used instead of 70.0 g of n-butanol charged together with the catalyst, and 70.0 g of isoamyl alcohol was used instead of 70.0 g of n-butanol in the mixed solution to be fed. The reaction was conducted under conditions. The water concentration in the reaction solution at this time is 7.5% by weight when the amount of water added with the condensed water of dialdehyde and ammonia is added. The results of repeating the reaction 5 times in the same manner as in Example 1 are shown below.
In 5 repeated reactions, the decrease in diamine yield was 4%, and the degree of catalyst deterioration was extremely small.
First reaction diamine yield 95%
Second reaction 〃 95%
Third reaction 〃 93%
4th reaction ９２ 92%
5th reaction 〃 91%
[0023]
Example 4
The reaction was carried out under the same conditions as in Example 1 except that 70.0 g of n-butanol in the mixed solution to be fed was changed to 60.0 g and the amount of water to be added was changed to 10.0 g. The water concentration in the reaction solution at this time is 11.5% by weight when the amount of water added with the condensed water of dialdehyde and ammonia is added. The results of repeating the reaction 5 times in the same manner as in Example 1 are shown below.
In 5 repeated reactions, the decrease in diamine yield was 6%, and the degree of catalyst deterioration was extremely small.
First reaction diamine yield 94%
Second reaction 〃 93%
Third reaction 〃 92%
4th reaction ９０ 90%
5th reaction 〃 88%
[0024]
Comparative Example 2
The reaction was carried out under the same conditions as in Example 1 except that water was not added to the mixed solution to be fed and butanol in the mixed solution to be fed was changed to 80.0 g. The water concentration in the reaction solution is 3.5% by weight as condensed water of dialdehyde and ammonia. The results of repeating the reaction 5 times in the same manner as in Example 1 are shown below.
The decrease in diamine yield was 11% after 5 repeated reactions, and the degree of catalyst deterioration was greater than when water was added.
First reaction diamine yield 96%
Second reaction ９２ 92%
Third reaction 〃 91%
4th reaction 〃 88%
5th reaction ８５ 85%
[0025]
Comparative Example 3
70.0 g of n-butanol to be initially charged is changed to 50.0 g, 20.0 g of water is added, and 70.0 g of n-butanol of the mixed solution to be fed is changed to 60.0 g, and 10.0 g of water is changed to 20.0 g. The reaction was performed under the same conditions as in Example 1 except that. The water concentration in the reaction solution at this time is 19.5% by weight when the amount of water added with the condensed water of dialdehyde and ammonia is added. The results of repeating the reaction 5 times in the same manner as in Example 1 are shown below.
By repeating the reaction five times, the diamine yield was significantly reduced and a white polymer was produced. Compared with the case where a small amount of water was added, the degree of catalyst deterioration was increased.
1st reaction Diamine yield 84%
Second reaction 〃 76%
Third reaction 〃 62%
4th reaction 〃 48%
5th reaction ２３ 23%
[0026]
Comparative Example 4
Under the same conditions as in Example 1, except that 70.0 g of tetrahydrofuran was used instead of 70.0 g of n-butanol charged together with the catalyst, and 70.0 g of tetrahydrofuran was used instead of 70.0 g of n-butanol in the mixed solution to be fed. Reaction was performed. The water concentration in the reaction solution at this time is 7.5% by weight when the amount of water added with the condensed water of dialdehyde and ammonia is added. The results of repeating the reaction 5 times in the same manner as in Example 1 are shown below.
The decrease in the diamine yield was 21% after 5 repeated reactions, and the degree of catalyst deterioration was greater than when butanol was used as the solvent.
First reaction diamine yield 94%
Second reaction 〃 90%
Third reaction 〃 85%
4th reaction ８１ 81%
5th reaction ７３ 73%
[0027]
Example 5
Instead of 37.5 g of a mixture of 1,9-nonanediar / 2-methyl-1,8-octanediar = 80/20 (molar ratio), 3 (4), 8 (9) -tricyclo [5.2. 1.0] The reaction was carried out under the same conditions as in Example 1 except that 37.5 g of decandicarbaldehyde was used. The water concentration in the reaction solution at this time is 6.8% by weight when the amount of water added with the condensed water of dialdehyde and ammonia is added. The results of repeating the reaction 5 times in the same manner as in Example 1 are shown below.
In 5 repeated reactions, the decrease in diamine yield was 3%, and the degree of catalyst deterioration was extremely small.
First reaction diamine yield 96%
Second reaction 〃 95%
Third reaction 〃 95%
4th reaction ９３ 93%
5th reaction ９３ 93%
[0028]
Example 6
After adding 1.44 g of nickel catalyst, 21.0 g of n-butanol and 3.5 g of water to a 100 ml autoclave with a magnetic stirrer, 10 kg / cm ² The inside of the autoclave was replaced three times with a hydrogen pressure of Next, 10.5 g of ammonia was added and hydrogen was 50 kg / cm. ² Then, the autoclave was heated to 140 ° C. Total pressure 100kg / cm ² After adjusting the pressure with hydrogen so as to be, 8.75 g of a mixture of 1,9-nonanediar / 2-methyl-1,8-octanediar = 80/20 (molar ratio), 19.52 g of n-butanol, And water (36.63 g / hr), ammonia (13.13 g / hr), and hydrogen (10 L / hr) were fed into the reactor at the rate of 30.63 g / hr, and the same amount of reaction from a sampling port equipped with a mesh filter. A continuous reaction was carried out while keeping the amount of the reaction solution at 50 ml while extracting the solution. The water content in the reaction solution at this time becomes 10.0% by weight when the amount of water added with the condensed water from dialdehyde and ammonia is added. As a result of distilling off ammonia from the reaction solution flowing out every hour and analyzing by gas chromatography, the yield of diamine was changed as follows.
Although a yield reduction of 7% was observed after 20 hours, a good yield could be maintained. A total of 161.3 g of diamine was obtained for 20 hours. The average yield of diamine was 91%, and the amount of catalyst consumed per kg of diamine was 8.9 g.
1st hour Diamine yield 94%
2nd hour ９６ 96%
3rd hour ９３ 93%
4th hour ９３ 93%
5th hour ９４ 94%
10th hour ９２ 92%
15th hour ９０ 90%
20th hour ８７ 87%
[0029]
Comparative Example 5
The 21.0 g of n-butanol charged together with the catalyst was changed to 24.5 g, water was not added, and 19.52 g of the mixed solution fed to the reactor was changed to 26.58 g. A continuous reaction was carried out under the same conditions as in Example 6 except that was not added. The mixed solution was fed into the reactor at a rate of 30.63 g / hr as in Example 6. The water concentration in the reaction solution at this time is derived from the condensed water of dialdehyde and ammonia and is 4.0% by weight. Table 1 shows the reaction results when the reaction was carried out for 20 hours. A yield reduction of 23% was observed in the reaction for 20 hours.
[0030]
Comparative Example 6
The 21.0 g of n-butanol charged together with the catalyst was changed to 18.2 g, the water 3.5 g was changed to 5.86 g, and 19.52 g of n-butanol in the mixed solution fed to the reactor was changed to 16 The continuous reaction was carried out under the same conditions as in Example 6 except that the amount was changed to 0.02 g and water 2.36 g was changed to 5.86 g. The mixed solution was fed into the reactor at a rate of 30.63 g / hr as in Example 6. At this time, the water concentration in the reaction solution becomes 18.0% by weight by adding the amount derived from the condensed water of dialdehyde and ammonia. The reaction yield after 18 hours was 51%, and a 43% decrease in yield was observed after 18 hours.
[0031]
The reaction results of Example 6, Comparative Example 5 and Comparative Example 6 are compared and shown in Table 1.
[0032]
[Table 1]

[0033]
Comparative Example 7
In accordance with Example 1 of Japanese Patent Laid-Open No. 5-17413, the catalyst was repeated and used in the following procedure.
A 500 ml autoclave with a magnetic stirrer was charged with 75 g of methanol, 7.5 g of Raney nickel and 59.5 g of ammonia, and hydrogen was further introduced to give 15 kg / cm. ² Then, the temperature was raised. After the internal temperature of the autoclave reaches 120 ° C., hydrogen is further introduced to reduce the internal pressure to 40 kg / cm. ² I made it. Next, 119 g of a methanol solution obtained by dissolving 27.3 g of 1,9-nonane dial and 11.7 g of 2-methyl-1,8-octane dial in 80 g of methanol was determined at high pressure over 3 hours. At the pump It was fed into the autoclave. While supplying the methanol solution, the inside of the autoclave was kept at 120 ° C. Since hydrogen was consumed as the reaction proceeded, hydrogen was added successively to keep the pressure constant. At the same time as the supply of the methanol solution was stopped, the consumption of hydrogen was stopped and the reaction was completed. After cooling the reaction solution and filtering off the catalyst, the filtrate is gas chromatographed. I As a result, it was found that 35.6 g of a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine was obtained. The yield of diamine obtained relative to the total of charged dialdehyde was calculated to be 90%.
The same operation was repeated except that the catalyst recovered by filtration was used instead of 7.5 g of Raney nickel, and the change in reaction yield was examined. Results are shown below.
First reaction diamine yield 90%
Second reaction 〃 85%
Third reaction 〃 78%
4th reaction 〃 65%
5th reaction ４８ 48%
In the catalyst recovery and reuse test using Raney nickel catalyst, the activity after the reaction was significantly reduced.
[0034]
【The invention's effect】
According to the present invention, in the method for producing diamine from dialdehyde, an alcohol solvent is used as a solvent, and the reaction is carried out in a range of 5 to 15% by weight of water in the reaction solution, thereby suppressing deterioration of the catalyst. Diamine can be produced in a high yield.

Claims (4)

A method in which dialdehyde or a solution obtained by dissolving dialdehyde in a solvent is supplied to a reactor containing a hydrogenation catalyst, a solvent, ammonia and hydrogen, and the dialdehyde is reductively aminated to produce a corresponding diamine A process for producing diamine, wherein an alcohol solvent is used as a solvent and the reaction is carried out in a range of 5 to 15% by weight of water in the reaction solution. The method for producing a diamine according to claim 1, wherein the alcohol solvent is an alcohol, a diol or a polyol. The method for producing a diamine according to claim 1, wherein the alcohol solvent is an aliphatic alcohol having 5 or less carbon atoms. The method for producing a diamine according to any one of claims 1 to 3, wherein the dialdehyde is nonane dial, 2-methyloctane dial, or a mixture thereof.