JPH0532599A - Method for separating and purifying amino acid - Google Patents

Abstract

PURPOSE:To efficiently separate and purify an amino acid useful as foods, feeds, medicines, etc., in high purity by bringing a metallic ion-coordinated fine resin having a specific average particle diameter with an aqueous solution of an amino acid, adsorbing the amino acid on the resin and then eluting the adsorbed amino acid. CONSTITUTION:Diethylenetriamine and water are added to chloromethylstyrene- divinylbezene copolymer having <=200mum average grain diameter and 4mol% crosslinking decree, and reacted at 120-250 deg.C for 6hr. The resultant product is then washed with water to provide an aminated resin, which is subsequently reacted with acrylic acid. The prepared product is washed with water to afford a chelating resin having polyaminocarboxylate group. An aqueous solution of copper sulfate is then reacted with the chelating resin to prepare a chelated resin having coordinated metallic ions. An aqueous solution containing an amino acid (e.g. cysteine) is subsequently added to adsorb the amino acid on the resin, which is then separated by filtration and washed with water. The adsorbed amino acid is subsequently eluted with 5N aqueous ammonia, etc., to efficiently separate and purify the objective amino acid in high purity.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for separating and purifying amino acids, and more particularly to a method for separating and purifying amino acids using a resin having a functional group coordinated with a metal ion.

[0002]

2. Description of the Related Art Amino acids are used for foods, feeds, pharmaceuticals,
It is used in a wide range of fields such as cosmetics and industrial products.

Amino acids are produced by any of the fermentation method, the synthetic method, and the extraction method, and usually, by-products and raw materials contained as impurities are then separated and purified. As a method for separating and purifying a target amino acid from by-products such as other amino acids and a raw material, a crystallization method utilizing a difference in solubility is generally adopted. Since the solubility of amino acids in general organic solvents is low, the crystallization method using an aqueous solution is usually used. In this case, the solubilities of multiple amino acids present in the aqueous solution are often similar, so in order to separate the target amino acid from other amino acids to obtain a highly pure product, the crystallization method is repeated. It requires complicated operations.

Particularly, in the case of amino acids which are structural isomers such as leucine and isoleucine, the two cannot be separated by a usual crystallization method. Therefore, for example, β-naphthalenesulfonic acid or 2-bromo-5 as described in “Fine Chemical” March 15, 1982, p.
-A complicated method such as adding a third component such as toluenesulfonic acid to form an amino acid as a salt with the third component and separating them by utilizing the difference in solubility thereof has to be used.

Thus, in the conventional amino acid production process,
Separation and purification of amino acids which cannot be separated by ordinary crystallization means, such as repeated crystallization or particularly leucine and isoleucine, require the extremely complicated treatment as described above. Therefore, the manufacturing time is long, a large number of processing devices are required, and the construction cost and the operating cost are large.

[0006] As a purification method by mutual separation of amino acids, which improves the above-mentioned drawbacks of the conventional method, the present inventors have previously described in Japanese Patent Laid-Open No. 1-258652, an aminocarboxylic acid type or an aminophosphonic acid coordinated with a metal ion. A method has been disclosed in which a resin having an acid-type chelating functional group is brought into contact with an amino acid aqueous solution to adsorb the amino acid on the resin, and then the adsorbed amino acid is eluted. The method disclosed in this publication exerts an unprecedented effect in the separation and purification of amino acids having similar properties. However, it is not always sufficiently satisfactory in terms of separating and recovering the target amino acid with high purity.

[0007]

In view of such circumstances, the inventors of the present invention have conducted intensive studies to find a method for efficiently separating and purifying a highly pure amino acid, and as a result, completed the present invention.

[0008]

Means for Solving the Problems That is, according to the present invention, when a resin having metal ions coordinated is brought into contact with an aqueous amino acid solution, the resin having an average particle size of 200 μm or less is used to separate the amino acids to be separated and purified. The present invention provides a method for separating and purifying amino acids by adsorbing them on a resin and then eluting the adsorbed amino acids.

In the present invention, by using a fine resin having a metal ion coordinated and an average particle size of 200 μm or less,
Amino acids to be separated and purified can be efficiently adsorbed. More preferably, a resin having an average particle size of 150 μm or less is used.

The resin used in the present invention has a functional group that coordinates with a metal ion, such as a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, and an amino group, to which a metal ion is coordinated. Any resin that coordinates such a metal ion and that adsorbs an amino acid to be separated can be used in the present invention. The resin substrate is not particularly limited, and insoluble polymers such as styrene-based, acryl-based, and phenol-based resins that are commonly used for ion exchange resins and chelate resins can be used.

In the present invention, the compound has a functional group that coordinates with a metal ion and has an average particle size of 200 μm or less, preferably 1
A resin of 50 μm or less can be used, and metal ions can be coordinated thereto. The average particle size can be reduced to 200 μm or less, preferably 150 μm or less by pulverizing and classifying a resin having a relatively large particle size in which metal ions are coordinated.

When a resin having an average particle diameter of 200 μm or less and having a chelating functional group for coordinating a metal ion is used, a commercially available ion exchange resin or chelate resin is crushed and classified for use. Alternatively, a fine resin produced by a known method can be used. Preferred specific examples of the resin having a functional group that coordinates with a metal ion that can be used in the present invention are shown below.

(1) Carboxylic acid group-type chelating resin: Amino resin or polyamino resin may be used as monochloroacetic acid, monobromoacetic acid, monochloropropionic acid, monobromopropionic acid, or an alkali metal salt or alkaline earth metal salt thereof. A resin obtained by reacting a halogenated alkylcarboxylic acid compound. The amino resin used herein has a primary or secondary amino group, and includes, for example, a nitrile group, a chloromethyl group, a sulfonyl chloride group, an isocyanate group, a carbonyl chloride group, an epoxy group, an aldehyde group, or chlorine, It is obtained by reacting a polymer having an amine reactive group such as a halogen atom such as bromine or iodine with ammonia, methylamine or ethylamine. A polyamino resin is a functional group containing two or more primary or secondary groups.
A polymer having a primary amino group, for example, a polymer having an amine reactive group as described above, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, octamethylenediamine, nonamethylenediamine, diethylenetriamine, triethylene. It is obtained by reacting a polyamine such as tetramine, tetraethylenepentamine, hydrazine and guanidine.

Acrylic acid, methacrylic acid, acetylenedicarboxylic acid, maleic acid, alkali metal salts or alkaline earth metal salts of these acids, or methyl ester can be added to the above amino resin or polyamino resin.
A resin obtained by reacting an ethyl ester or the like (hereinafter referred to as an acrylic acid-based compound) and, if an ester is used, then performing hydrolysis.

Obtained by reacting the above-mentioned polymer having an amine-reactive group with an amino acid compound such as glycine, alanine, β-alanine, iminodiacetic acid, iminodipropionic acid, ethylenediaminediacetic acid, and ethylenediaminetriacetic acid. resin.

Commercially available Sumichelate MC-30, MC-75,
MC-76, MC-77, MC-78, Sumisepare AS-13, AS-23
[Made by Sumitomo Chemical Co., Ltd.], Duolite C-464,
C-466 [Made by Duolite International Co., Ltd.],
Diaion WK-10, WK-20, CR-10 [Made by Mitsubishi Kasei Co., Ltd.], Uniselec UR-10, UR-20, UR-30, UR-4
Chelating resin such as 0, UR-50 (all manufactured by Unitika Ltd.).

These carboxylic acid group type chelate resins are
According to the present invention, it is usually pulverized to be used so that the average particle diameter is 200 μm or less. In addition, if the resin base before introducing the functional group is fine, the particle size of the resin will not increase too much by the introduction of the functional group after that, so such a fine raw material resin is used to introduce the functional group. In such a case, the chelate resin having an average particle diameter of 200 μm or less is usually used as it is.

(2) Phosphonic acid group-type chelate resin: In addition to the above amino resin or polyamino resin,
Alkyl phosphorylating agents such as chloromethyl phosphoric acid and chloroethyl phosphoric acid, or alkyleneizing agents such as formaldehyde, and phosphorylating agents such as phosphorous trichloride, phosphorous acid, methyl phosphite and ethyl phosphite, and acidic catalysts such as hydrochloric acid and sulfuric acid. Resin obtained by reacting below.

Commercially available Sumichelate MC-95, Sumisepare AS-14, AS-24 (all manufactured by Sumitomo Chemical Co., Ltd.), Duolite C-467 (manufactured by Duolite International), Uniselec UR-3300 (Unitika (stock) ) Made chelate resin.

These phosphonic acid group type chelate resins are also
According to the present invention, it is usually pulverized to be used so that the average particle diameter is 200 μm or less. In addition, if the resin base before introducing the functional group is fine, the particle size of the resin will not increase too much by the introduction of the functional group after that, so such a fine raw material resin is used to introduce the functional group. In such a case, the chelate resin having an average particle diameter of 200 μm or less is usually used as it is.

(3) Resin having sulfonic acid group: commercially available Sumikaion KC-470 (manufactured by Sumitomo Chemical Co., Ltd.), Duolite C-20, C-26 (manufactured by Duolite International Co., Ltd.), Diaion SK1B [Mitsubishi Kasei Co., Ltd.
Made] resin.

These resins having sulfonic acid groups are also usually pulverized and used according to the present invention so that the average particle diameter becomes 200 μm or less.

In the present invention, a resin having a chelating functional group such as aminocarboxylic acid or aminophosphonic acid is preferably used, and more preferably, a polyamino resin is a halogenated alkylcarboxylic acid compound,
Resins obtained by reacting acrylic acid compounds, amino acid compounds, alkyl phosphorylating agents, or alkyleneizing agents with phosphorylating agents, that is, carboxylic acid groups or phosphonic acids that bond to the polymer main chain via polyalkylene polyamino groups A so-called polyaminocarboxylic acid type or polyaminophosphonic acid type chelate resin having a group in the side chain is used. When such a polyaminocarboxylic acid type or polyaminophosphonic acid type chelate resin is used, leakage of metal ions coordinated to a functional group to an amino acid after separation and purification is small, and a high separation and purification effect is obtained. To be

By finely classifying the fine resin having a functional group as described above, or by classifying it as necessary,
Those having an average particle size of 200 μm or less can be used separately.

The metal ion to be coordinated with the resin is not particularly limited as long as the amino acid for the purpose of separation and purification can be coordinated with the metal ion coordinated with the resin. However, transition metal ions are generally preferred. In particular, each of the ions of iron, cobalt, nickel, copper, and zinc, which are the 4th periodic element of the periodic table, is preferably used in terms of production cost and the amount of metal leaked to the purified amino acid side in the separation and purification step. To be Of these, copper ions and cobalt ions are more preferable.

In order to coordinate such a metal ion to the resin having the functional group, an aqueous solution containing the metal ion may be brought into contact with the resin. For example, a method of passing an aqueous solution in which the metal ions are dissolved in a tower filled with a resin in advance or a method of introducing the resin into an aqueous solution of metal ions and stirring and contacting them for a predetermined time can be employed.

The amount of the metal ion coordinated to the resin having the functional group is not particularly limited, but the amount of the coordinating metal ion decreases, the amount of the amino acid separation and purification process decreases, and thus the resin 1 is generally used. It is preferred to coordinate up to about 0.1 gram atom per liter of metal ions up to the saturation capacity.

The conditions for contacting the aqueous solution in which the metal ion is dissolved with the resin having the functional group differ depending on the type and concentration of the metal ion, the contact temperature, and the type and amount of the resin having the functional group, so preliminary experiments are conducted as appropriate. It is decided by. Generally, 1 to 100 liters of an aqueous solution of a metal mineral salt having a concentration of about 0.01 to 0.5 mol / L is added to 1 liter of the resin having the functional group at room temperature for 0.1 to 24 liters.
A method of contacting for a time is adopted.

The resin having the functional group with the metal ion coordinated in this way is brought into contact with the amino acid aqueous solution to be separated and purified as it is or after washing with water as necessary. If a resin with a large particle size is used at the stage of coordinating the metal ions, and if the particle size of the resin with the coordinating metal ions is large, then the particles are crushed and classified to obtain the average particle size. To 200 μm or less, and if necessary, after washing with water, it is brought into contact with the aqueous solution of the amino acid to be separated and purified.

The aqueous solution of an amino acid to be treated in the present invention contains an amino acid having an affinity for a resin coordinated with a metal ion, and another amino acid and / or another amino acid having an affinity different from the affinity of the amino acid for the resin. Any substance containing an impurity compound may be used. Such amino acids and impurity compounds include asparagine, aspartic acid, glutamine, glutamic acid, methionine,
Amino acids such as cystine, cysteine, tyrosine, valine, phenylalanine, alanine, tryptophan, proline, serine, ornithine, citrulline, lysine, aminobutyric acid, leucine, isoleucine, and anthranilic acid, 2-hydroxy-4-methyl-thiobutyric acid, 2 −
Examples include amino acid fermentation raw materials such as hydroxy-3-phenylpropionic acid. An amino acid aqueous solution containing at least one kind of these amino acids and one or more kinds of other amino acids or impurity compounds is to be treated. Typically, an aqueous solution containing two or more kinds of amino acids, that is, an aqueous solution containing one or more kinds of other amino acids in addition to the amino acid to be separated and purified is treated.

The method of the present invention is particularly effective when an aqueous solution in which the content of the amino acid to be separated and purified is equimolar or more to the metal ion coordinated to the resin to be contacted is treated. Show. Above all, it is excellent in separation and purification of aspartic acid, glutamic acid, serine, ornithine, lysine, phenylalanine, cysteine or leucine. Particularly, an excellent effect is recognized in the separation and purification of leucine containing isoleucine, methionine and the like as impurities produced by precipitation by neutralizing acid hydrolysates such as casein, keratin and hemoglobin with an alkali.

In contacting the resin having metal ions coordinated with the amino acid aqueous solution according to the present invention, the pH of the amino acid aqueous solution is preferably in the range of about 2 to about 12, and particularly pH.
More preferably, it is carried out in the range of about 3 to about 10. If the pH of the amino acid aqueous solution deviates from this range and becomes less than about 2 or more than about 12, the purification efficiency is lowered, which is not preferable.

The contact of the resin having metal ions coordinated with the aqueous solution of amino acid is preferably carried out by adding the resin to the aqueous solution of amino acid and immersing the resin therein. Then, the resin is separated by filtration. Further, both can be brought into contact with each other by filling the inside of the tower with the resin and passing an amino acid aqueous solution through the tower.

The contact temperature between the amino acid aqueous solution and the resin is not particularly limited, and it is carried out at any temperature between about 0 ° C and about 100 ° C. The contact time is also not particularly limited.
The preferable contact time and contact temperature can be set by appropriately performing preliminary experiments according to the type and concentration of amino acid, the type and amount of resin, and the like. Also, the amount of the resin to which the metal ions are coordinated can be set by appropriately performing preliminary experiments.

In the method of the present invention, the resin having the functional group to which a metal ion is coordinated is brought into contact with an amino acid aqueous solution, and the amino acid for the purpose of separation and purification is adsorbed on the resin. The resin is washed as it is, or after washing with water as required, the adsorbed amino acid is eluted with a separating eluent. As such a separating and eluting agent, water, aqueous ammonia, mineral acid, an aqueous solution of an alkali metal hydroxide or an alkaline earth metal hydroxide is preferably used from the viewpoint of ease of recovering amino acids, etc. Or in appropriate combination.

The aqueous solution in which the amino acid is eluted in this manner can be made into a purified amino acid by subjecting to a known method such as concentration and precipitation treatment and drying. Further, the resin after elution of the amino acid can be used as it is, or can be repeatedly used for separation and purification of the amino acid aqueous solution after coordinating metal ions again as necessary.

[0037]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following examples, the purity of the amino acid to be purified is expressed on the basis of weight calculated according to the following formula. Purity of target amino acid (%) = (weight of target amino acid / weight of all amino acids including target amino acid) x 100

Example 1 To 500 g of a chloromethylstyrene-divinylbenzene copolymer having an average particle size of 50 μm and a cross-linking degree of 4 mol%, 5150 g of diethylenetriamine and 1300 g of water were added.
After reacting at 20 to 125 ° C. for 6 hours, the mixture was filtered and washed with water to obtain 2200 g (undried) of aminated resin a. Using 300 g of this aminated resin a, acrylic acid 1
50 g and 100 g of water were added, and the mixture was reacted at 40 to 60 ° C. for 6 hours, then filtered and washed with water to obtain a chelate resin having a polyaminocarboxylic acid group. On the other hand, 0.05 mol of copper sulfate and 0.5 mol of ammonia were added to 1 liter of water,
A copper sulfate aqueous solution was prepared. This copper sulfate aqueous solution (500 ml) and the previously obtained chelate resin (50 ml) are contacted with each other at room temperature for 5 hours, and then filtered and washed with water to obtain 2.1 g of copper ion-coordinated chelate resin A (average particle diameter: 120 μm).
Obtained 50 ml. Using 10 ml of this chelate resin A, an aqueous solution containing 0.5 g of methionine and 0.5 g of cysteine 20
The mixture was added to 0 ml, stirred for 30 minutes, filtered, washed with 10 ml of water, and the adsorbed amino acid was eluted with 30 ml of 5N aqueous ammonia. The amino acid in the obtained eluent was 0.4 g of cysteine and 0.02 g of methionine, and the purity of cysteine was 95.2%.

Example 2 Using 250 g of the aminated resin a obtained in the first half of Example 1, 200 g of monochloroacetic acid and 1.2 liter of a 2N sodium hydroxide aqueous solution were added thereto, and the reaction was carried out at 50-60 ° C. for 4 hours. After filtration and washing with water, 410 g (undried) of polyaminocarboxylic acid type chelate resin was obtained. This resin was contacted with an aqueous solution of copper sulfate in the same manner as in Example 1,
50 ml of chelate resin B (average particle diameter: 95 μm) coordinated with 2.5 g of copper ion was obtained. When this chelate resin B was used to treat an aqueous amino acid solution in the same manner as in Example 1, cysteine was found to be present in the amino acids in the obtained eluent.
The content of 0.43 g and methionine was 0.022 g, and the purity of cysteine was 95.1%.

Comparative Example 1 The same operation as in Example 1 was repeated except that a chloromethylstyrene-divinylbenzene copolymer having an average particle size of 360 μm was used, and 2.0 g of copper ion was added. Coordinated chelate resin C (average particle size 510 μm) 50
I got ml. When an aqueous amino acid solution was treated in the same manner as in Example 1 using this chelate resin C, the amino acids in the obtained eluent were 0.40 g of cysteine and 0.030 g of methionine, and the purity of cysteine was 93.0. %Met.

Comparative Example 2 The same operation as in Example 2 was repeated except that a chloromethylstyrene-divinylbenzene copolymer having an average particle diameter of 360 μm was used, and 2.2 g of copper ion was added. Coordinated chelate resin D (average particle size 490 μm) 50
I got ml. When this chelate resin D was used to treat an aqueous amino acid solution in the same manner as in Example 1, the resulting amino acid in the eluent was 0.41 g of cysteine and 0.037 g of methionine, and the purity of cysteine was 91.7. %Met.

Examples 3 to 7 and Comparative Examples 3 to 7 Various chelate resins were synthesized as follows.

Chelate resin E: 2060 g of diethylenetriamine and 515 g of water were added to 300 g of an acrylonitrile-divinylbenzene copolymer having a crosslinking degree of 4 mol% and an average particle size of 52 μm, and the mixture was reacted at 110 to 125 ° C. for 6 hours and then filtered, After washing with water, 1200 g (undried) of aminated resin b was obtained. Using 200 g of this aminated resin b, 100 g of acrylic acid and 100 g of water were added thereto and reacted at 40 to 50 ° C. for 6 hours. Then, filtration and washing with water are performed to obtain the polyaminocarboxylic acid type chelate resin 41.
0 g (undried) was obtained. On the other hand, 0.05 mol of copper sulfate and 0.5 mol of ammonia were added to 1 liter of water to prepare a copper sulfate aqueous solution, and 500 ml of this copper sulfate aqueous solution was brought into contact with 50 ml of the chelate resin obtained above at room temperature for 5 hours. By filtration and washing with water, 50 ml of chelate resin E (average particle size 98 μm) coordinated with 2.3 g of copper ions was obtained.

Chelate resin F: 2 parts of the amination resin b
00g, and sodium monochloroacetate 466 there
40 g of caustic soda and 720 g of water
The reaction was carried out at 50 ° C for 6 hours. Then, filtration and washing with water were performed to obtain 450 g (undried) of polyaminocarboxylic acid type chelate resin. On the other hand, 0.05 mol of copper sulfate and 0.5 mol of ammonia were added to 1 liter of water to prepare a copper sulfate aqueous solution, and 500 ml of this copper sulfate aqueous solution was brought into contact with 50 ml of the chelate resin obtained above at room temperature for 5 hours. filtration,
By washing with water, 50 ml of chelate resin F (average particle size 96 μm) coordinated with 2.2 g of copper ions was obtained.

Chelate resin G: Diethylenetriamine and acrylic acid were reacted in the same manner as in the synthesis of the chelate resin E except that an acrylonitrile-divinylbenzene copolymer having a crosslinking degree of 4 mol% and an average particle diameter of 310 μm was used. Further, copper ions were adsorbed. As a result, 2.0
chelate resin G (average particle size 54
50 .mu.m) was obtained.

Chelate resin H: Diethylenetriamine and monochloroacetic acid were reacted in the same manner as in the synthesis of the chelate resin F except that an acrylonitrile-divinylbenzene copolymer having a crosslinking degree of 4 mol% and an average particle diameter of 310 μm was used. Further, copper ions were adsorbed. as a result,
50 ml of chelate resin H (average particle size 520 μm) coordinated with 2.1 g of copper ions was obtained.

Chelating Resins I and J: Commercially Available Chelating Resin Sumicepar AS-13 Having Aminocarboxylic Acid Group
A chelate resin I having 2.0 g of copper ions coordinated was prepared using [Sumitomo Chemical Co., Ltd., average particle size of 520 μm] and subjected to the same treatment as the contact with the aqueous solution of copper sulfate in Example 1.
50 ml (average particle size 530 μm) were obtained. Next, 30 ml of this chelating resin I was crushed to obtain 325 mesh and 10
Classification was carried out using a 0 mesh sieve. As a result, 0.75 g
Chelate resin J (average particle size 120)
20 μm) was obtained.

Chelating Resins K and L: Commercially Available Chelating Resin Sumisepare AS-14 Having Aminophosphonic Acid Group
A chelate resin K in which 2.0 g of copper ion was coordinated was prepared by using [Sumitomo Chemical Co., Ltd., average particle size: 530 μm] and performing the same treatment as the contact with the copper sulfate aqueous solution in Example 1.
50 ml (average particle size 530 μm) were obtained. Next, 30 ml of this chelating resin K was crushed to obtain 325 mesh and 10
Classification was carried out using a 0 mesh sieve. As a result, 0.8 g of copper ion coordinated chelate resin L (average particle size 100 μm
m) 20 ml was obtained.

Chelating Resins M and N: Commercially available chelating resin skimylate having a sulfonic acid group KC-470 [manufactured by Sumitomo Chemical Co., Ltd., average particle size: 520 μm] was used, and contact with the aqueous solution of copper sulfate in Example 1 was performed. The same process was performed. As a result, 50 ml of a chelate resin M (average particle size: 520 μm) coordinated with 1.9 g of copper ion was obtained. Next, 30 ml of this chelate resin M was pulverized and classified using a 325 mesh and a 100 mesh screen. As a result, 0.8
Chelate resin N (average particle size 95
20 μm) was obtained.

Chelating resin E obtained as described above
.About.N, the contact treatment with the amino acid aqueous solution was performed in the same manner as in Example 1. The results are shown in Table 1.

[0051]

[Table 1]

Example 8 Using 10 ml of the chelate resin A obtained in Example 1, 100 ml of an amino acid aqueous solution containing 1 g of leucine and 1 g of isoleucine was added, and after stirring for 10 minutes, the resin was filtered. After washing with 20 ml of water, the adsorbed amino acid was eluted with 50 ml of 5N ammonia water. The amino acids contained in the eluent were 0.79 g of leucine and 0.0081 g of isoleucine, and the purity of leucine was 99.0%.

Comparative Example 8 Using the chelate resin C obtained in Comparative Example 1, the same treatment as in Example 8 was performed. The amino acid in the obtained eluent is
0.69 g of leucine and 0.013 g of isoleucine,
The leucine purity was 98.2%.

Examples 9 to 14 and Comparative Examples 9 to 14 Using chelate resins B and D to N, contact treatment with an aqueous amino acid solution and elution of amino acids were carried out in the same manner as in Example 8. The results are shown in Table 2.

[0055]

[Table 2]

Example 15 Using 10 ml of the chelate resin A obtained in Example 1, 200 ml of an amino acid aqueous solution containing 1 g of aspartic acid and 1 g of asparagine was added, and after stirring for 30 minutes, the resin was filtered. After washing with 20 ml of water, the adsorbed amino acid was eluted with 50 ml of 5N ammonia water. The amino acids contained in the eluent were 0.67 g of aspartic acid and asparagine.
It was 0.0093 g and the purity of aspartic acid was 98.6%.

Comparative Example 15 Using the chelate resin C obtained in Comparative Example 1, Example 1 was used.
The same process as 5 was performed. The amino acids in the obtained eluent were 0.54 g of aspartic acid and 0.015 g of asparagine.
The purity of aspartic acid was 97.2%.

Example 16 Using 10 ml of the chelate resin A obtained in Example 1, 100 ml of an amino acid aqueous solution containing 2 g of ornithine and 2 g of citrulline was added, and the resin was filtered after stirring for 30 minutes. Next, after washing with 20 ml of water, 50 ml of 5N ammonia water
The adsorbed amino acid was eluted with. Regarding the amino acids contained in the eluent, ornithine was 0.83 g and citrulline was 0.010 g, and the purity of ornithine was 98.8%.

Comparative Example 16 Using the chelate resin C obtained in Comparative Example 1, Example 1 was used.
The same process as 6 was performed. The amino acid in the obtained eluent was 0.68 g of ornithine and 0.022 g of citrulline, and the purity of ornithine was 96.9%.

[0060]

INDUSTRIAL APPLICABILITY According to the present invention, a highly pure amino acid can be easily obtained, so that its industrial value is extremely high.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C07C 229/24 8930-4H 229/26 8930-4H 323/58 7419-4H

Claims (5)

[Claims] 1. The average particle size of metal ions coordinated is 200 μm.
A method for separating and purifying an amino acid, which comprises contacting a resin having a size of m or less with an aqueous amino acid solution to adsorb the amino acid on the resin, and then eluting the adsorbed amino acid. 2. The method according to claim 1, wherein the amino acid aqueous solution contains a plurality of amino acids capable of coordinating with metal ions. 3. The method according to claim 1, wherein the resin having a metal ion coordinated therein is a chelate resin having an aminocarboxylic acid type or aminophosphonic acid type chelating functional group. 4. The functional group in the chelate resin is bound to the resin substrate via a polyalkylene polyamine.
The method described. 5. The method according to claim 1, wherein the metal ion is a copper ion or a cobalt ion.