JPH1192430A - Production of 1-amino-2,3-propanediol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress coloring and efficiently obtain the high-purity subject compound by arranging packing materials having small pressure loss in the upper and lower parts at feed position to distillation tower of a specific mixed liquid. SOLUTION: A mixed solution consisting essentially of (A) 1-amino 2,3- propanediol of formula I and further containing (B) a trace amount of 2- amino-1,3-propanediol of formula II and (C) a trace amount of water content and (D) a high boiling point material is separated in a distilling tower in which packing materials having small pressure loss are arranged in upper and lower parts at feed position of the mixed solution to provide the objective compound. For example, a crude product of synthetic reaction using starting materials of glycidol or an epihalohydrin and ammonia is used as the mixed solution. A polymerization ratio of the component A to the component B in mixed solution is preferably (99.5/0.5) to (<=99.7/0.3). A regular packing material is preferably used as the packing material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a specific aminodiol compound, 1-amino-2,3-propanediol, and to a method for producing 1-amino-2,3-propanediol having high purity and a method for producing the same. To provide.

[0002]

2. Description of the Related Art 1-Amino-2,3-propanediol is an industrially important compound, and has attracted attention as a useful raw material compound for an X-ray contrast agent, which has been growing in demand in recent years. Methods for producing 1-amino-2,3-propanediol are well known, and include, for example, a method of reacting glycidol with ammonia. Such 1-amino-
The method for producing 2,3-propanediol is described in, for example, L. K
norr et al. (Der. deutsch. chem. Ge.
s. Vol. 32.750.1899); Bau
m et al. (J. Org. Chem. Vol. 27.233)
1.1962) and disclosed in JP-A-56-16.
1355, JP-A-56-161356, JP-A-56-161357, JP-A-3-41056
JP, JP-A-3-41057, JP-A-3-63
251 and JP-A-3-86851 and JP-A-4
-352748, and JP-A-8-12628. Further, as a method of reacting 3-chloro-1,2-propanediol with ammonia, K.K. Baum et al. (J. Org. Chem. Vol. 27.2331.
1962) is known. At present, 1-amino-2,3-propanediol commercially available contains 2-amino-1,3-propanediol as an impurity in an amount of 0.3 to 0.1.
It contains 5% by weight. However, Japanese Patent Application Laid-Open No. 56-1613
No. 5, JP-A-56-16136, JP-A-56-16136
JP-A-16137, JP-A-3-41056, JP-A-3-41057, JP-A-3-63251 and JP-A-3-86851 disclose 2-amino-1,
There is no specific description about the separation of 3-propanediol. JP-A-4-352748 discloses that 1-amino-2,3-propanediol is more 2-
Amino-1,3-propanediol was found to have a higher boiling point, and 1-amino-2,3 was obtained by using a packed tower having a low pressure loss and a thin film evaporator or a scraping type thin film evaporator.
Although the method for continuously distilling a crude liquid of propanediol is shown, it is not considered that 2-amino-1,3-propanediol is efficiently separated on the apparatus. Further, Japanese Patent Application Laid-Open No. 8-12828 proposes that distillation is performed using a batch distillation apparatus while passing an inert gas. However, 1-amino-2,3-propanediol and its impurities are not distilled. Since it is unstable to heat, using a batch-type apparatus having a longer residence time than a continuous type is not considered to be superior in terms of equipment. From these circumstances, it was found that 2% in 1-amino-2,3-propanediol products
It has been desired to develop a production method that efficiently suppresses the content of -amino-1,3-propanediol to 0.3% by weight or less.

[0003]

SUMMARY OF THE INVENTION The object of the present invention is to
Provided is a method for producing 1-amino-2,3-propanediol such that the content of 2-amino-1,3-propanediol in an amino-2,3-propanediol product is 0.3% by weight or less. Is to do.

[0004]

Means for Solving the Problems The present inventors have developed a trace amount of 2
-When a mixed solution containing amino-1,3-propanediol and water and containing a high-boiling substance is separated by a distillation column to produce 1-amino-2,3-propanediol, the mixture is supplied to the distillation column. The inventors have found that 1-amino-2,3-propanediol can be suppressed from coloring and can be separated efficiently with high purity by using a filler having a small pressure loss above and below the mouth, thereby completing the present invention.

That is, the present invention relates to 1-amino-2,3-
A mixture containing propanediol, a trace amount of 2-amino-1,3-propanediol and a trace amount of water and containing a high-boiling substance is separated in a distillation column to give 1-amino-2,3-.
A method for producing 1-amino-2,3-propanediol, wherein when obtaining propanediol as a distillate, packing materials having a small pressure loss are arranged above and below a position where the mixed solution is supplied to the distillation column. I will provide a. The present invention relates to a method for producing 1-amino-2,3-propanediol and 2-amino-1,3-propane in a mixed solution which is a crude product of a synthesis reaction starting from glycidol or epihalohydrin and ammonia in the above production method. The weight ratio with the diol is 99.
5 / 0.5 to 99.7 / 0.3
-Amino-2,3-propanediol is provided. Further, the present invention provides a crude 1-amino-2,3-amino-1,3-propanediol having a weight ratio of 99.7 / 0.3 or less to 1-amino-2,3-propanediol.
When 1,2-propanediol is separated by a distillation column to obtain purified 1-amino-2,3-propanediol as a distillate, the packing having a small pressure loss is disposed. -Amino-2,3-propanediol is provided.

Hereinafter, the present invention will be described in detail. The mixed liquid used in the present invention is a mixed liquid containing 1-amino-2,3-propanediol, a trace amount of 2-amino-1,3-propanediol, water and a high-boiling substance, and contains glycidol, ammonia This is a name that includes the reaction product (crude reaction product), the mixed solution obtained by removing the low-boiling substances from the reaction product, and the mere mixture of the above substances. In the present invention, the crude reaction product used is obtained as follows.
That is, 1-amino-2,3-propanediol is produced by the reaction between glycidol and ammonia as shown in reaction formula (1). It is considered that as a reaction mechanism, the electron pair of the nitrogen atom of ammonia nucleophilically attacks the electron-deficient carbon atom of the epoxy group, causing a ring-opening addition reaction to the epoxy group. As a side reaction, ammonia does not attack the terminal carbon of the epoxy group of glycidol, but attacks the second carbon from the terminal, whereby 2 of the formula (2) can be obtained.
-Amino-1,3-propanediol is formed. It is difficult to avoid this side reaction due to the nature of the reaction.

[0007]

Embedded image

Further, even when epichlorohydrin, which is a kind of epihalohydrin, is reacted with ammonia,
Epichlorohydrin is hydrolyzed with water to give 3-chloro-1,2-propanediol as shown in the following reaction formula (2). Under an ammonia atmosphere, this causes a dehydrochlorination reaction and cyclization to form glycidol,
Further, by reacting with ammonia, 1-amino-
It is believed that 2,3-propanediol is produced. Therefore, even if epichlorohydrin is used, it will be via glycidol, and during the reaction, 2-amino-1,3
-Propanediol will be by-produced.

[0009]

Embedded image

Therefore, 1-amino-2,3- is reacted by reacting ammonia with glycidol or epichlorohydrin.
In the method for producing propanediol, 2-amino-1,3-propanediol is always produced as a by-product. Further, commercially available 1-amino acid containing about 0.3 to 0.5% by weight or more of 2-amino-1,3-propanediol.
Amino-2,3-propanediol is also a starting material in the present invention.

As a method for analyzing the content of 2-amino-1,3-propanediol in 1-amino-2,3-propanediol described in the present invention, 2-amino-1,3-propanediol is used.
Since propanediol and 1-amino-2,3-propanediol have similar structures as they are, it is difficult to separate them. Therefore, 1-amino-2,3-propanediol containing 2-amino-1,3-propanediol is subjected to acetylation treatment to facilitate separation, and then analyzed by gas chromatography (hereinafter abbreviated as GC). It is calculated from the peak area ratio. The calculation formula is shown below.

C [2-A-1,3-PDA] = P [2-A-1,3-PDA] × 100 / P [1-A-2,3-PDA] C [2-A-1 , 3-PDA]: 2-amino-1,3-propanediol content (%) (vs. 1-amino-2,3-propanediol) P [2-A-1,3-PDA]: 2-amino GC peak area of -1,3-propanediol P [1-A-2,3-PDA]: GC peak area of 1-amino-2,3-propanediol

The GC analysis is preferably performed by the following measuring method. Column packing material: ULBON R-1701 (Fused sillica capilary) Column: length; 25 m, inner diameter; 0.2 mm, film thickness: 0.25 μm Column temperature: 140 ° C. at start, 220 ° C. at the end, 5 ° C. heating rate / Min Detector: Flame ionization detector Injection temperature: 250 ° C Detection temperature: 250 ° C Carrier gas: helium Gas flow rate: 1.14 ml / min Split value: 1: 65.14 Sample: 1-amino-2,3- Propanediol derivative (sample treated with acetylating agent) Sample volume: 1.0 μl Range: 10 Calculation: area percentage

1-amino-2,3-propanediol and 2-amino-1,3-propanediol have a small difference in boiling point, and the number of theoretical plates required for separation in an ordinary distillation column increases. Inevitably, the pressure loss of the entire distillation column becomes large, and the pressure at the bottom of the column rises. 1
The high-boiling components contained in -amino-2,3-propanediol and 1-amino-2,3-propanediol are unstable to heat, and the decomposition reaction proceeds depending on the temperature and residence time, and It is also known that 1-amino-2,3-propanediol is colored. However, as a result of the study, the present inventors have found that by using a packing having a small pressure loss above and below the inlet to the distillation column, 1-amino-2,3
-It has been found that propanediol is efficiently separated without coloring.

The packing having a small pressure loss described in the present invention means that the pressure loss per theoretical plate is small, not the pressure loss per unit height such as per meter. Specifically, a packing having a small pressure loss means that the pressure loss per theoretical plate is 0.5 Torr.
r or less. Usually, pressure loss can be easily measured as "pressure loss per unit height".
That is, "pressure loss per theoretical plate" which defines the pressure loss of the packed tower used in the production method of the present invention.
In order to obtain the value, "the number of theoretical plates per unit height" is required. This "theoretical plate number per unit height" has, for example, a substantially constant specific volatility in a wide concentration range,
That is, if a total reflux test is performed using a binary system (chlorobenzene / ethylbenzene system, transdecalin / cisdecalin system, etc.) that is close to the ideal system, it can be easily obtained from the Fenke equation. ("Chemical Engineering Handbook, Revised 4
Edition "P598, 1978, Maruzen Co., Ltd.).

As a material satisfying such a condition, a commercially available product of Sumitomo Heavy Industries, Ltd.
Representative examples are "through packer BX and CY type", "Sumitomo / Mera Pack", "Techno Pack 100MD and 50MS" manufactured by Mitsui & Co., and "MC Pack" manufactured by Mitsubishi Corporation. Each of these packings has a pressure loss per theoretical plate of 0.5 Torr or less in a normal use range. For example, in the case of a general old-show distillation column, usually two to four stages correspond to one theoretical stage. Further, since the gas always passes through the liquid portion, a pressure loss corresponding to the liquid height per actual stage occurs. On the other hand, in the case of a packed column, since such a phenomenon does not generally occur, the pressure loss is small. Further, the packing specifically exemplified above is designed so that the pressure loss is particularly small.

The required theoretical plate number of the distillation column used in the production method of the present invention depends on the content of 2-amino-1,3-propanediol in the starting material and the content of target 2-amino-1,3-propanediol in the product. It varies depending on the amount, target yield of 1-amino-2,3-propanediol, reflux ratio and the like, but is usually in the range of 3 to 100 stages, preferably 5 to 30 stages.
The position of supply to the distillation column is 2 counting from the bottom of the distillation column.
It is preferable to supply in 80 to 80 stages, preferably in 2 to 24 stages. When the supply position is too low, for example, when an evaporator is connected to the bottom of the distillation column, separation of 1-amino-2,3-propanediol and 2-amino-1,3-propanediol having a small difference in boiling point occurs. Insufficient and high-boiling components, 2-amino-1,3-propanediol, are distilled out and will be mixed into the product 1-amino-2,3-propanediol. This is because there is no 1-amino-2,3-propanediol recovery section in the packed tower.

On the other hand, if the supply position is too high, 2-amino-1,3-propanediol entrained in 1-amino-2,3-propanediol and the like which distills out increases more than the separation efficiency. And will be mixed into the product 1-amino-2,3-propanediol. Therefore,
By appropriately setting the supply position to the packed tower, it is possible to efficiently separate 1-amino-2,3-propanediol and 2-amino-1,3-propanediol having a small difference in boiling point. The liquid temperature and pressure in the evaporator section installed in the distillation column are as follows: the concentration of the high boiling component in the crude 1-amino-2,3-propanediol solution, the target yield of 1-amino-2,3-propanediol, the distillation Although the temperature varies depending on the number of theoretical plates in the column and the pressure loss, the temperature of the liquid in the evaporator is usually 80 to 2
Distillation is performed at a temperature of 00 ° C. and a pressure in the range of 0.1 to 30 Torr.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. (Example 1) Into a 5-liter glass separable reactor equipped with a stirrer and a jacket, 2200 g of a 28% by weight aqueous ammonia solution was charged, and 182 g of glycidol was charged over 6 hours, followed by aging for 3 hours. The reaction temperature was controlled at 15 ° C. The 1-amino-2,3-propanediol concentration in the reaction crude liquid thus obtained was 6.
It was 5% by weight. The reaction crude liquid was subjected to 160 distillation using a distillation apparatus (distillation unit: 40 mmφ × 1200 mmH) equipped with a demister on the upper part of a stainless steel falling liquid film evaporator.
It was charged at 0 g / H, heated at a temperature of 106 ° C., distilled at a top pressure of 760 mmHg, and the bottoms were placed on a stainless steel falling film evaporator at the top of a regular packing (“through” manufactured by Sumitomo Heavy Industries, Ltd.). Zarabo Packing ": Specific surface area = 1
700 m ² / m ³ ) was charged into a distillation apparatus equipped with a vacuum jacket-type packed tower (50 mmφ × 110 mmH) filled with evaporator at a temperature of 152 ° C. and a top pressure of 20 mmHg.
Was performed to remove excess ammonia and water.
The composition of the crude liquid obtained by removing the low boiling point was 1-amino-2,
72.0% by weight of 3-propanediol and 0.9% of water
%, And other components were 27.1% by weight.

Subsequently, a stirred liquid film type evaporator having a steam heating part of a stainless steel jacket is filled with a regular packing ("Surzer Lab Packing" manufactured by Sumitomo Heavy Industries, Ltd .: specific surface area = 1700 m ² / m ³ ). Vacuum-packed packed tower (50 mmφ x 385 mmH, 38
The crude liquid obtained above was charged at a rate of 300 g / H into a distillation apparatus equipped with a liquid filled to 5 mmH, and the bottom liquid had a 1-amino-2,3-propanediol concentration of 40% by weight. The temperature of the evaporator was kept constant as described above, and distillation was performed at a top pressure of 2 mmHg and a reflux ratio of 1. The supply position was 275 mmH from the bottom of the packed tower. The quality of the obtained product is 30 by APHA and 1-amino-2,3
-The content of propanediol was 99.5%.

(Comparative Example 1) The procedure was carried out in the same manner as in Example 1 until the boiling point was removed, and in the commercialization step, the process was carried out in the same manner as in Example 1 except that the supply position to the packed column was from the bottom of the column. The quality obtained is described in Table 1.

Example 2 The same procedure as in Example 1 was carried out until the low boiling point was reached. In the production process, the packed column was supplied at a position of 330 mmH from below the packed tower. The quality obtained is described in Table 1.

Example 3 Commercially available 1-amino-2,3
-Purification was carried out using propanediol. In the commercialization process, the supply position of the packed tower was supplied at a position of 275 mmH from below the packed tower. The quality obtained is described in Table 1.

[0024]

[Table 1]

[0025]

As described above, in the case where a mixture comprising a crude reaction product containing glycidol and ammonia as starting materials and containing a trace amount of 2-amino-1,3-propanediol is purified by distillation, the mixture of By arranging the packing having a small pressure loss above and below the supply position, it is possible to obtain high-purity 1-amino-2,3-propanediol having a small amount of trace components.

Claims (5)

[Claims] 1. A 1-amino-2,3-propanediol represented by the following formula (1), and a trace amount of 2-amino-
When a mixed solution containing 1,3-propanediol and a trace amount of water and containing a high boiling point is separated by a distillation column to obtain 1-amino-2,3-propanediol as a distillate, the mixed solution is used. Wherein a packing having a small pressure loss is arranged above and below a supply position to the distillation column. 1-Amino-2,3-propanediol. Embedded image 2. The method according to claim 1, wherein the mixture comprises a crude product of a synthesis reaction using glycidol or epihalohydrin and ammonia as starting materials.
For the production of -amino-2,3-propanediol 3. A mixture of 1-amino-2,3-propanediol and 2-amino-1,3-propanediol of the formula (2).
The weight ratio with propanediol is 99.5 / 0.5 to 9
The method for producing 1-amino-2,3-propanediol according to claim 1 or 2, wherein the ratio is 9.7 / 0.3. Embedded image 4. The method for producing 1-amino-2,3-propanediol according to claim 1, wherein the packing having a small pressure loss is an ordered packing. 5. A crude 1-amino-amino compound in which the weight ratio of 1-amino-2,3-propanediol to 2-amino-1,3-propanediol is 99.7 / 0.3 (weight ratio) or less. When 1,2-propanediol is separated by a distillation column to obtain purified 1-amino-2,3-propanediol as a distillate, the packing having a small pressure loss is disposed. A method for producing amino-2,3-propanediol.