JPS63115854A - Method for producing aminoethyl sulfonic acid - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention deals with the production of aminoethyl sulfonic acid by reacting chloroethylamine hydrochloride with sodium sulfite, inorganic salts mixed into the synthesis solution, In particular, it relates to a method for effectively removing sodium chloride, sodium sulfate, etc. and producing highly pure aminoethyl sulfonic acid.

Aminoethyl sulfonic acid is a compound known as taurine, and is known to have preventive and curative effects against myocardial infarction, arteriosclerosis, liver dysfunction, and the like.

[Prior art] When separating organic substances from inorganic salts, an extremely common method is to separate the organic substances from the inorganic salts by cooling and crystallizing the organic substances by utilizing the solubility difference between the organic substances and the inorganic salts. be. However, when using this method to separate aminoethylsulfonic acid from sodium chloride and sodium sulfate present in the synthesis solution, for example, the synthesis solution is cooled to below 10°C, and aminoethylsulfonic acid is crystallized and separated. When performing this, a large amount of the above inorganic salt is mixed into the crystal, and the above inorganic salt cannot be easily removed even if the aminoethyl sulfonic acid is purified by the commonly used recrystallization method. As a method for obtaining highly pure aminoethyl sulfonic acid that does not contain the above-mentioned inorganic salts, a method using electrodialysis was proposed in Japanese Patent Application No. 164893/1983. If electrodialysis is performed, a considerable amount of aminoethyl sulfonic acid flows out from the condensate side.

[Problems to be Solved by the Invention] The problems to be solved by the present invention are to recover aminoethylsulfonic acid flowing out in the electrodialysis method of the above-mentioned prior art and efficiently produce highly purified aminoethylsulfonic acid. It is to be manufactured in

[Means for Solving the Problems] As a result of intensive studies to overcome the above drawbacks, the present inventors have discovered that the above problems can be solved by adopting a two-stage electrodialysis method, and have developed the present invention. I ended up completing it. In the two-stage electrodialysis method of the present invention, in the first stage electrodialysis, a reaction solution obtained by synthesizing aminoethyl sulfonic acid with chloroethylamine hydrochloride and sodium sulfite is combined with an anion exchange membrane and a cation exchange membrane as a dialysis membrane. The first desalted solution is then supplied to a first electrodialysis device configured to perform first-stage electrodialysis, and divided into a first desalted solution from which inorganic salts have been removed and a first concentrated solution containing inorganic salts. In addition to effectively separating aminoethylsulfonic acid from the desalted solution, the first concentrated solution is subjected to a second electrodialysis device similar to the first electrodialysis device described above, and a second stage of electrodialysis is performed to obtain the second desalted solution. and the second a condensed phase liquid, the second desalted liquid is recycled to the aminoethyl sulfonic acid synthesis system or electrodialysis system, and the aminoethyl sulfonic acid leaked into the first concentrated liquid is recovered. be.

That is, the present invention provides anion exchange membrane and cation exchange using a synthetic solution containing inorganic salts mainly consisting of sodium chloride and sodium sulfate as a dialysis membrane when producing aminoethyl sulfonic acid by reacting chloroethylamine hydrochloride and sodium sulfite. The first stage of electrodialysis is performed by supplying it to a first electrodialysis device configured by combining membranes,
The synthesis solution containing the inorganic salt is divided into a first desalination solution from which the inorganic salt has been removed and a first concentrated solution containing the inorganic salt, and aminoethyl sulfonic acid is separated from the first desalination solution. A second stage of electrodialysis is performed by applying the first concentrated solution to a second electrodialysis device similar to the first electrodialysis device described above, and the second desalted solution is divided into a second desalted solution and a second concentrated solution. This is a method for producing aminoethylsulfonic acid which is recycled to an aminoethylsulfonic acid synthesis system or an electrodialysis system.

[Operation and Effects of the Invention] According to the method of the present invention, aminoethyl sulfonic acid can be effectively separated from a synthetic liquid containing inorganic salts such as sodium chloride and sodium sulfate by a relatively simple operation. Aminoethyl sulfonic acid leaked during dialysis can also be effectively recovered.Moreover, during electrodialysis, part of the water is removed along with the above inorganic salt, and aminoethyl sulfonic acid is purified and concentrated at the same time. This is much more advantageous in terms of sulfonic acid recovery operation.

Next, the method of the present invention will be specifically explained with reference to FIG. The apparatus shown in FIG. 1 is merely an example of the first electrodialysis apparatus used in the method of the present invention, and various changes may be made as necessary without departing from the spirit of the present invention. Of course, it's Chino. Also, the second electrodialysis device is shown similarly to the first electrodialysis device. In FIG. 1, reference numeral 1 denotes a first electrodialysis tank, the interior of which is divided into a plurality of chambers by ion exchange membranes consisting of cation exchange membranes C and anion exchange membranes A, which are provided alternately. An electrode (+) 4 is provided at the other end, and an electrode (-) 5 is provided at the other end. These ion exchange membranes are not necessarily limited to specific ones, and various types such as condensed type, polymerized type, homogeneous type, and heterogeneous type can be used. For example, as a cation exchange membrane, Neo Sebuta CM-2 (manufactured by Tokuyama Soda Co., Ltd.),
Examples of the anion exchange membrane include Neosebuku CL-25T (manufactured by Tokuyama Soda Co., Ltd.), Neocepta AM-3 (manufactured by Tokuyama Soda Co., Ltd.), and Neocepta ACH-457 (manufactured by Tokuyama Soda Co., Ltd.).

Therefore, among the plurality of chambers mentioned above, the first desalination liquid chamber 2 is partitioned with an anion exchange membrane A on the anode side and a cation exchange MC on the cathode side. An aminoethyl sulfonic acid synthesis solution 6 containing salt impurities is supplied, while an electrolyte solution 7, preferably an aqueous solution of sodium chloride, which is the main inorganic salt to be removed, is supplied to the first concentrated liquid chamber 3 to form an anode 4 and a cathode. 5
More direct current passes through the current. The cations in the first desalted liquid chamber 2 pass through the cation exchange membrane C and move to the adjacent first condensing liquid chamber 3, and the anions pass through the anion exchange membrane A and move to the adjacent first concentrated liquid chamber 3. Therefore, the inorganic salt in the first desalting solution is unilaterally separated from the aminoethyl sulfonic acid and moves to the first iawi solution, and if electrodialysis is performed for an appropriate time, it will be removed from the first desalting solution chamber 2. A first desalination solution 8 containing almost no inorganic salts is obtained. Moreover, as the ions move, some water also moves from the first desalinated liquid chamber 2 to the first concentrated liquid chamber 3, so that the first desalted liquid 8 that has been amped before electrodialysis is
is obtained. In addition, a part of the first desalted liquid 8 or the second concentrated liquid chamber is extracted from the first desalted liquid chamber 2 or the first concentrated liquid chamber 3, respectively, as needed, or the liquid composition is adjusted. Afterwards, it may be circulated again to the original chambers, or it may be processed by passing through each chamber continuously without circulation.

In addition, when performing the first stage electrodialysis, 7-aminoethylsulfonic acid leaks from the first desalination liquid chamber 2 to the first concentrated liquid chamber 3 due to electrophoresis and concentration difference diffusion of aminoethylsulfonic acid. In order to recover the aminoethyl sulfonic acid obtained, the first 'a preliquid is supplied to a second electrodialysis apparatus similar to the first electrodialysis apparatus as a feed liquid for the second stage electrodialysis,
Electrodialysis treatment similar to the first stage electrodialysis is performed. Similar to the first-stage electrodialysis, the inorganic salts in the second desalting solution are unilaterally separated from the aminoethyl sulfonic acid and transferred to the second concentrated solution. A second desalting solution containing almost no inorganic salts is obtained from the desalting solution chamber. Moreover, as the ions move, a portion of the water also moves from the second desalted liquid chamber to the second concentrated liquid chamber, so that a second desalted liquid that is more concentrated than before electrodialysis is obtained. Further, a portion of the second desalted liquid or the second concentrated liquid is extracted from the second desalted liquid chamber or the second m-phase liquid chamber, respectively, as necessary.
It may be circulated as it is or after adjusting the liquid composition to the original chambers, or it may be processed without being circulated (it may be continuously passed through each chamber for treatment).

From the first desalted solution in which the inorganic salts are separated and the aminoethylsulfonic acid is concentrated, the desired highly purified aminoethylsulfonic acid can be obtained by known means such as cooling crystallization. In addition, the second desalination solution is the recovered aminoethylsulfonic acid that leaked during the first stage electrodialysis, and because the concentration of aminoethylsulfonic acid is low, it is difficult to separate it by means such as cooling crystallization. However, the second desalination solution from which the inorganic salts have been separated is recycled and used as part of the water for dissolving sodium sulfite in the aminoethyl sulfonic acid synthesis system. The recovery of aminoethyl sulfonic acid is carried out as follows.

There is no particular limit to the concentration of aminoethylsulfonic acid in the synthesis solution subjected to first-stage electrodialysis, but since water moves during electrodialysis and aminoethylsulfonic acid is concentrated, the solubility of aminoethylsulfonic acid at the electrodialysis temperature is When the temperature exceeds 100%, crystal precipitation occurs. Therefore, it is necessary to maintain the first stage electrodialysis temperature and aminoethyl sulfonic acid concentration appropriately so that crystals of aminoethyl sulfonic acid do not precipitate in the first electrodialysis tank during the first stage electrodialysis. The first stage electrodialysis temperature is about 50℃, and the concentration of aminoethylsulfonic acid in the first desalination solution after electrodialysis is 1
It is preferable to set it to 7 to 19%.

The first stage electrodialysis temperature is within the usable temperature range of the ion exchange membrane, preferably between room temperature and 55°C, preferably between 45 and 53°C. This is undesirable because it exceeds the operating temperature range of the ion exchange membrane, and when the temperature is low, aminoethylsulfonic acid crystals precipitate, making it impossible to increase the concentration of aminoethylsulfonic acid, which is undesirable.

After the first stage electrodialysis, the concentration of aminoethyl sulfonic acid in the first desalination solution was adjusted to 17 to 19%.

The solubility of aminoethylsulfonic acid in water at °C is 18%, and if the concentration becomes higher than this, aminoethylsulfonic acid will precipitate in the electrodialysis tank and damage the ion exchange membrane. If the temperature is low, the yield will be low and the efficiency will be poor.

In order to make the concentration of aminoethyl sulfonic acid in the first desalination solution 17 to 19% after the completion of the first stage electrodialysis, the amount of water transferred in the first stage electrodialysis and the aminoethyl sulfonic acid in the synthesis solution are Although it depends on the concentration, inorganic salt concentration, etc., the aminoethyl sulfonic acid concentration at the start of the first stage electrodialysis is 10 to 14%.
6 If the concentration of aminoethyl sulfonic acid in the synthesis solution is high, the synthesis solution should be diluted with water to adjust the concentration.At this time, the second desalination solution from which the inorganic salts have been separated is It is recovered from aminoethylsulfonic acid that leaked during dialysis, and the concentration of aminoethylsulfonic acid is low.
Because separation is difficult or has little effect depending on the method such as cooling crystallization, the second desalting solution from which the inorganic salt has been separated is cooled and crystallized from the first desalting solution to remove the crystals. It is possible to mix the aminoethyl sulfonic acid in the synthesis solution with the filtrate after the reaction and use it in the electrodialysis system instead of water.As a result, the aminoethyl sulfonic acid can be recovered. be exposed.

The electrodialysis treatment conditions are: electrodialysis temperature is 55°C or lower, and current density is 4.5A per 1 d+n” of ion exchange membrane.
It is appropriate to choose the following.

Incidentally, by providing a large number of the above-mentioned anion exchange membranes A and cation exchange membranes C in both the first and second stage electrodialysis tanks, the electrodialysis treatment of the reaction product liquid can be significantly streamlined.

Purified aminoethyl sulfonic acid that passes the specifications of the Japanese Pharmacopoeia (8th revision) can be obtained by subjecting the first desalted solution that has been subjected to the first-stage electrodialysis treatment to normal cooling crystallization.

The manufacturing method of the present invention is a method in which a chloroethylamine hydrochloride aqueous solution is added to an aqueous sodium sulfite solution and heated. That is, when chloroethylamine hydrochloride is reacted with 1-1.3 times the mole of sodium sulfite at a temperature ranging from room temperature to the boiling point, a synthetic liquid containing aminoethyl sulfonic acid is obtained. The synthetic solution produced by this method contains 5 to 30% by weight of aminoethylsulfonic acid, 1 to 28% by weight of sodium chloride, and 1 to 1% by weight of sodium sulfate.
Sodium chloride and sodium sulfate in the synthetic solution are separated by two-stage electrodialysis treatment of the synthetic solution containing 0%, and the first desalted solution obtained by the first-stage electrodialysis is When cooling crystallization is performed using a normal method such as external cooling with stirring, aminoethyl sulfonic acid precipitates, so it is separated by an appropriate method such as centrifugation.
By washing the separated crystals with washing water in an amount of 0.5 to 5 times the weight of the crystals, the sodium chloride and sodium sulfate contents in aminoethyl sulfonic acid are adjusted to the values specified in the Japanese Pharmacopoeia (8th revision). Crystals of aminoethyl sulfonic acid that meet the standard values are obtained. Further, the second desalted solution obtained by the second stage electrodialysis is mixed with the filtrate and recycled for use in the aminoethyl sulfonic acid synthesis system, that is, as part of the water for dissolving sodium sulfite, or By recycling the aminoethylsulfonic acid in the synthesis solution into the electrodialysis system as a substitute for water for concentration adjustment, the aminoethylsulfonic acid leaked into the first concentrated solution during the first stage electrodialysis is recovered. .

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but these are merely illustrative, and it goes without saying that the present invention is not limited to these Examples.

Example 1 30 with stirrer, thermometer, addition funnel and cooling tube
20.00 kg of water was heated to 35°C with nitrogen bubbling in two flasks, and 4 ml of sodium sulfite was added to it.
．． A sodium sulfite aqueous solution was prepared by dissolving 93 kg (purity 94.0%, containing 6% sodium sulfate). To this, 80% chloroethylamine hydrochloride aqueous solution 5.0
8 kg was gradually dropped over 6 hours at 53-56°C, and then kept at 55°C for 3 hours.Then, the temperature was raised to 65°C.
2 hours at °C, 2 hours at 80°C, 2 hours at 90°C,
The reaction was carried out at the boiling point for 1 hour to obtain an aminoethylsulfonic acid synthesis solution. All reactions of 0 or more were carried out under a nitrogen blanket.

This synthetic solution contained 4.09 kg of aminoethyl sulfonic acid.
(13.6% by weight), sodium chloride 3.96kg
(13.2% by weight), sodium sulfate 0.30kg (1
, 0% by weight), and the conversion rate to aminoethylsulfonic acid in this synthesis was 93.4 mol%.

6 kg of this synthetic solution (aminoethyl sulfonic acid 816.
0g, sodium chloride 792.0g, sodium sulfate 6
0.0g) was added to adjust the aminoethyl sulfonic acid concentration to 11.2% by adding 1,300g of water to the mixture and supplying it to the first desalination liquid chamber, and 2.5k of a 7.8% sodium chloride aqueous solution
g (195.0 g of sodium chloride)] i? i
A solution was prepared to be supplied to the liquid chamber and subjected to the first stage electrodialysis.

These solutions were mixed with a membrane spacing of 0 using Neocepta AM-3 (anion exchange membrane, manufactured by Tokuyama Soda Co., Ltd.) and Neocepta CM-2 (cation exchange membrane, manufactured by Tokuyama Soda Co., Ltd.) with an effective membrane area of 2 dn+" per membrane. .75+am, IQ
Using a first electrodialyzer as shown in FIG. 1, which is configured in pairs, an aminoethylsulfonic acid synthesis solution is supplied to the first desalination solution chamber, and the first 'a1i! A 7.8% sodium chloride aqueous solution was supplied to the liquid chamber to perform the first stage of electrodialysis. !
Temperature during gas dialysis: 50℃, current density: 4.5A/dm”
Treat aminoethylsulfonic acid synthesis solution with Wk0.061
/ ) Ir-dm” for 4.5 hours.

The composition of the first desalinated solution obtained by the first stage electrodialysis was 18.2% by weight of aminoethylsulfonic acid (797.2g
), sodium chloride 0.2% by weight (7.9g), and sodium sulfate 0.6% by weight (27.0g).

Sodium chloride in aminoethyl sulfonic acid is 99.0
% by weight was separated by dialysis, and 55.2% by weight of sodium sulfate was separated by dialysis. Furthermore, the leakage of aminoethylsulfonic acid into the first concentrated liquid was 2.3% by weight.

The first desalted solution was cooled to 3''C, and aminoethylsulfonic acid was crystallized and separated.Washing was performed using the same amount of washing water as the weight of crystallized crystals.Aminoethyl with a purity of 99.9% or more 558 g of sulfonic acid was obtained, with 26 ppm of sodium chloride and 20 ppm of sodium sulfate in the aminoethyl sulfonic acid.

Example 2 The first stage electrodialysis was performed in the same manner as in Example 1, and the first concentrated liquid obtained in Example 1 was supplied to the second desalination liquid chamber, and 7.8% sodium chloride was water? The 8 liquid was supplied to the second concentrate chamber, and second-stage electrodialysis was performed using a first electrodialyzer similar to the first electrodialyzer.

Aminoethylsulfonic acid 18.
Sodium chloride 0.2% (7.9g), Sodium sulfate 0.6% (2% by weight)
A first desalination solution with a composition of 7.0 g) was obtained, and in the second stage electrodialysis, 1.0% by weight of aminoethylsulfonic acid (18
,7g), sodium chloride 0.4% by weight (7.5g),
A second desalination solution was obtained having a composition of 0.8% by weight (14.9 g) of sodium sulfate.

In the first stage electrodialysis, 99.0 ffi1% sodium chloride and 55.2 wt% sodium sulfate were separated, and in the second stage electrodialysis, 99.2 ffi1% sodium chloride and 54.8 ffi1% sodium sulfate were separated. % of sodium sulfate was isolated. In addition, the leakage of aminoethylsulfonic acid to the first concentrated liquid was 2.3% by weight, and the leakage of aminoethylsulfonic acid to the second concentrated liquid was 1.6% by weight. The loss was less than 0.1% by weight.

Example 3 The first desalted liquid obtained in Example 2 was cooled and crystallized, and the filtrate from which aminoethylsulfonic acid was separated was mixed with the second desalted liquid to obtain a recycled liquid.

Aminoethylsulfonic acid was synthesized in the same manner as in Example 1, except that 26.0kg of the recycled liquid was used instead of water for dissolving sodium sulfite, and 5.15kg (14.3% by weight) of aminoethylsulfonic acid, chloride A synthetic solution containing 4.02 kg (11.2% by weight) of sodium and 0.32 kg (0.9% by weight) of sodium sulfate was obtained.

The conversion rate to aminoethylsulfonic acid in this synthesis was 93
．． It was 1 mol%. Furthermore, instead of water for diluting 5.00 kg of the synthetic liquid supplied to the first desalination liquid chamber, 2.50 kg of the recycled liquid was used to adjust the aminoethyl sulfonic acid concentration to 10.9%. Example 2 except for these operations
The same operation was performed.

Aminoethylsulfonic acid 18.
5% by weight (798.4g), sodium chloride 0.13
Weight% (5.6g), sodium sulfate 0.56% by weight
A first desalination solution with a composition of (24.0 g) was obtained, and the second stage electrodialysis was carried out to obtain 1.0% by weight of aminoethylsulfonic acid (
18.7g), sodium chloride 0.3% by weight (5.4g
), sulfuric acid) A second desalination solution having a composition of 0.8% by weight (14.2 g) of IJum was obtained.

The first stage electrodialysis separated 99.0% by weight of sodium chloride and 53.0% by weight of sodium sulfate, and the second stage electrodialysis separated 99.4% by weight of sodium chloride and 57.0% by weight. % of sodium sulfate was isolated. In addition, the leakage of aminoethylsulfonic acid to the first i4M solution was 2.4% by weight, and the leakage of aminoethylsulfonic acid to the second concentrated solution was 1.6% by weight. The substantial loss was less than 0.1% by weight.

The first desalted solution was cooled to 3°C, and aminoethylsulfonic acid was crystallized and separated. Washing was performed using the same amount of washing water as the weight of crystals separated by crystallization. 551 g of aminoethylsulfonic acid with a purity of 99.9% or more was obtained, and the sodium chloride in the aminoethylsulfonic acid was 211)l)Ill, and the sodium sulfate was 19ppm.

[Brief explanation of the drawing]

FIG. 1 shows an embodiment of the first electrodialyzer. In the figure, each symbol has the following meaning. A: Anion exchange membrane, C: Cation exchange membrane, 1: First electrodialysis tank, 2: First desalination liquid chamber, 3: First concentrated liquid chamber, 4:
Anode, 5: Cathode, 6: Synthetic solution, 7: Electrolyte solution, 8: First desalination solution, 9: First concentrated solution, 10: Anolyte, 11: Cathode solution Patent applicant Mitsui Toatsu Chemical Co., Ltd. Drawings 1st V

Claims (1)

[Claims] (1) When producing aminoethyl sulfonic acid by reacting chloroethylamine hydrochloride and sodium sulfite,
A synthetic solution containing inorganic salts mainly consisting of sodium chloride and sodium sulfate is supplied as a dialysis membrane to a first electrodialysis device configured by combining an anion exchange membrane and a cation exchange membrane to perform first-stage electrodialysis. , dividing the synthetic solution containing the inorganic salt into a first desalting solution from which the inorganic salt has been removed and a first concentrated solution containing the inorganic salt, and separating aminoethyl sulfonic acid from the first desalting solution; , a second stage of electrodialysis is performed by applying the first concentrated liquid to a second electrodialyzer similar to the first electrodialyzer, and the second desalted liquid is divided into a second desalted liquid and a second concentrated liquid. 1. A method for producing aminoethylsulfonic acid, which comprises recycling it to an aminoethylsulfonic acid synthesis system or an electrodialysis system.