JP2870192B2 - Crystallization of amino acids - Google Patents

Crystallization of amino acids

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Publication number
JP2870192B2
JP2870192B2 JP50336890A JP50336890A JP2870192B2 JP 2870192 B2 JP2870192 B2 JP 2870192B2 JP 50336890 A JP50336890 A JP 50336890A JP 50336890 A JP50336890 A JP 50336890A JP 2870192 B2 JP2870192 B2 JP 2870192B2
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JP
Japan
Prior art keywords
amino acid
crystallization
crystals
amino acids
concentration
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP50336890A
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Japanese (ja)
Inventor
欣他 城下
龍太 豊増
賢 佐伯
Original Assignee
味の素株式会社
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Filing date
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Priority to JP1-33369 priority Critical
Priority to JP3336989 priority
Application filed by 味の素株式会社 filed Critical 味の素株式会社
Priority to JP50336890A priority patent/JP2870192B2/en
Application granted granted Critical
Publication of JP2870192B2 publication Critical patent/JP2870192B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Description

【発明の詳細な説明】 技術分野 本発明はアミノ酸の精製方法、詳しくはアミノ酸の晶
析法、更に詳しくはアミノ酸の晶析操作による結晶形態
の改善方法に関するものである。
Description: TECHNICAL FIELD The present invention relates to a method for purifying an amino acid, more particularly, to a method for crystallizing an amino acid, and more particularly to a method for improving a crystal form by a crystallization operation of an amino acid.
背景技術 一般的なアミノ酸の晶析法としては、アミノ酸水溶液
を減圧濃縮して晶析させる方法、中和して晶析させる方
法、あるいは水溶液に低級アルコールまたはケトンを大
量に添加しながら溶剤晶析させる方法等が提案されてい
る(特開昭59−39857号公報,特開昭59−45898号公報参
照)。
BACKGROUND ART As a general method for crystallizing an amino acid, a method of concentrating an amino acid aqueous solution under reduced pressure for crystallization, a method of neutralizing and crystallizing, or a method of solvent crystallization while adding a large amount of a lower alcohol or ketone to an aqueous solution. There has been proposed a method for causing the above to occur (see JP-A-59-39857 and JP-A-59-45898).
これらの方法のうち、減圧濃縮して晶析させる方法は
析出した微細なアミノ酸結晶が気泡を巻き込み易く突沸
するため濃縮操作に注意を要する。また、中和して晶析
させる方法は結晶が溶液上層に浮き易く、また結晶があ
まり大きく成長しないため、固液分離操作に手間どるこ
とが多い。一方、低級アルコールやケトンを添加してア
ミノ酸を晶析させる方法は別に有機溶媒の回収設備が必
要であり、製造プロセスが複雑化するだけでなく、さら
に溶媒を完全に回収することは不可能であるため、経済
的に成り立ちにくい面がある。
Of these methods, the method of concentrating under reduced pressure for crystallization requires careful attention to the concentration operation because the precipitated fine amino acid crystals are likely to entrap air bubbles and bump. In the method of crystallization by neutralization, the crystal tends to float in the upper layer of the solution, and the crystal does not grow so large. Therefore, the solid-liquid separation operation is often troublesome. On the other hand, the method of crystallizing amino acids by adding a lower alcohol or ketone requires a separate organic solvent recovery facility, which not only complicates the manufacturing process but also makes it impossible to completely recover the solvent. As a result, there are aspects that are not economically viable.
従って、簡便な操作・設備を用いて高純度のアミノ酸
結晶を取得する晶析法を提供することは当該分野におい
て意義のあることである。
Therefore, it is significant in the art to provide a crystallization method for obtaining high-purity amino acid crystals using simple operations and equipment.
発明の開示 本発明は、アミノ酸の晶析に際し、アミノ酸溶液に界
面活性剤及び/又はアルコールを存在せしめることを特
徴とするアミノ酸の晶析法に関する。
DISCLOSURE OF THE INVENTION The present invention relates to a method for crystallizing an amino acid, which comprises causing a surfactant and / or an alcohol to be present in an amino acid solution when crystallizing the amino acid.
発明を実施するための形態 本発明の対象となるアミノ酸は特に限定されないが、
好ましくはフェニルアラニン、トリプトファン、セリ
ン、イソロイシン、バリン、スレオニン、ロイシンが挙
げられる。これらのアミノ酸の製造法については特に制
限はなく、発酵法、化学合成法、酵素法、その他の方法
で製造されたいずれのものでもよい。また、一般にL−
アミノ酸の晶析に使用されるが、D−あるいはDL−アミ
ノ酸に使用してもよいし、アミノ酸誘導体に用いてもさ
しつかえない。
Modes for Carrying Out the Invention Amino acids targeted by the present invention are not particularly limited,
Preferable examples include phenylalanine, tryptophan, serine, isoleucine, valine, threonine, and leucine. The method for producing these amino acids is not particularly limited, and any of those produced by a fermentation method, a chemical synthesis method, an enzymatic method, or other methods may be used. In general, L-
It is used for crystallization of amino acids, but it may be used for D- or DL-amino acids or may be used for amino acid derivatives.
本発明に用いられる界面活性剤及びアルコール類は次
の通りである。
The surfactants and alcohols used in the present invention are as follows.
アニオン性界面活性剤としては脂肪酸塩系、硫酸エス
テル塩系、アルキルアリルスルホン塩酸系、りん酸エス
テル塩系が有効であり、具体的な例としてオレイン酸ナ
トリウム、ラウリル硫酸ナトリウム、ドテシルベンゼン
スルホン酸ナトリウム、レシチン等が挙げられる。
As the anionic surfactant, a fatty acid salt type, a sulfate ester type, an alkyl allyl sulfonate hydrochloride type and a phosphate ester type are effective, and specific examples thereof include sodium oleate, sodium lauryl sulfate, dodecylbenzene sulfonic acid. Sodium, lecithin and the like.
カチオン性界面活性剤としては第四アンモニウム塩
類、脂肪族アミン系、ピリジニウム系が有効であり、具
体的な例として、サニゾール(花王(株)製)、ラウリ
ルアミン、硫酸水素ラウリルピリジニウム等が挙げられ
る。
As the cationic surfactant, quaternary ammonium salts, aliphatic amines and pyridiniums are effective, and specific examples thereof include sanizole (manufactured by Kao Corporation), laurylamine, laurylpyridinium hydrogen sulfate and the like. .
非イオン性界面活性剤としてはポリオキシエチレンエ
ーテル系、ソルビタンアルキルエステル系、多価アルコ
ールと脂肪酸のエステル類、脂肪酸エタノールアミド系
が有効であり、具体的な例として、Brij(Atlas社
製)、Tween(Atlas社製)、モノステアリン酸グリセロ
ール等が挙げられる。
As nonionic surfactants, polyoxyethylene ethers, sorbitan alkyl esters, esters of polyhydric alcohols and fatty acids, and fatty acid ethanolamides are effective. Specific examples are Brij (manufactured by Atlas), Tween (manufactured by Atlas), glycerol monostearate and the like.
アルコール類としては多価アルコールが有効であり、
具体的な例としてエチレングリコール、プロピレングリ
コール等が挙げられる。
Polyhydric alcohols are effective as alcohols,
Specific examples include ethylene glycol and propylene glycol.
本発明を実施するに際しては、アミノ酸の酸あるいは
アルカリ溶解液に上記の添加剤を溶解した後、アルカリ
または酸を添加して中和晶析を行うか、アミノ酸水溶液
に上記の添加剤を溶解した後、濃縮してアミノ酸を晶析
させることにより行うことができる。ただしこの場合、
添加剤によって発泡性があるものでもあるので、あまり
発泡しない添加剤、例えば、モノステアリン酸グリセロ
ール、プロピレングリコールなどを使用する。また、上
記の添加剤を溶解したアミノ酸水溶液をそのまま冷却し
て晶析させてもよい。このように、本発明はアミノ酸の
晶析方法の如何にかかわらず適用することが可能であ
る。また、その際のアミノ酸濃度は結晶が析出する濃度
であればいずれでもよい。又、アミノ酸組成も特に限定
されるものではなく、その他の不純物を含んだ系であっ
てもよい。
In carrying out the present invention, after dissolving the above-mentioned additive in an acid or alkali solution of an amino acid, neutralization crystallization is performed by adding an alkali or an acid, or the above-mentioned additive is dissolved in an aqueous amino acid solution. Thereafter, it can be carried out by concentrating and crystallizing the amino acid. However, in this case,
Since some additives have foaming properties, additives that do not foam much, such as glycerol monostearate and propylene glycol, are used. Alternatively, the aqueous solution of the amino acid in which the above additive is dissolved may be cooled and crystallized. As described above, the present invention can be applied regardless of the method of crystallizing amino acids. The amino acid concentration at this time may be any concentration as long as crystals are precipitated. Also, the amino acid composition is not particularly limited, and a system containing other impurities may be used.
本発明における添加剤の濃度であるが、これは結晶形
に対し大きな影響を与え、場合によっては結晶成長を阻
害することも考えられるため、予め実験を行って最適濃
度を検定した。通常は溶液中のアミノ酸重量に対し10−
50000ppmであり、より好ましくは500−5000ppmである。
The concentration of the additive in the present invention has a great effect on the crystal form and may possibly inhibit the crystal growth. Therefore, the optimum concentration was determined by conducting experiments in advance. Usually, 10-
50,000 ppm, more preferably 500-5000 ppm.
このようにして本発明を用いると、アミノ酸の結晶表
面の疎水性が改善され、結晶が水溶液から分離すること
なく安定した懸濁状態となり、溶液中の基質が結晶表面
に連続して供給される為、余分な微細晶が発生せずに結
晶が大きく成長する。これにより、また水溶液表面にも
浮きにくくなる為、泡を巻き込み発泡することもなく速
やかに濃縮することができる。更に結晶が大きくなるた
め、固溶分離操作も容易となり付着母液量を減らすこと
ができる。その際の結晶形は、添加剤の種類や濃度、及
び晶析法によって多様に変化するが、概ね、濃縮晶析で
は集合した結晶になり易く、中和あるいは冷却晶析の場
合は単一結晶のまま成長する傾向にある。このようにし
て、界面活性剤の添加によって高純度のアミノ酸結晶を
得る晶析技術を確立した。
By using the present invention in this way, the hydrophobicity of the amino acid crystal surface is improved, the crystals are in a stable suspension without separation from the aqueous solution, and the substrate in the solution is continuously supplied to the crystal surface. Therefore, the crystals grow large without generating extra fine crystals. This makes it difficult to float on the surface of the aqueous solution, so that it is possible to concentrate quickly without involving bubbles and foaming. Further, since the crystals become larger, the solid solution separation operation is also facilitated, and the amount of the attached mother liquor can be reduced. The crystal form at that time varies depending on the type and concentration of the additive and the crystallization method, but in general, it tends to be aggregated crystals in concentrated crystallization, and a single crystal in neutralization or cooling crystallization. It tends to grow as it is. Thus, a crystallization technique for obtaining high-purity amino acid crystals by adding a surfactant was established.
以下、本発明を実施例で具体的に説明する。 Hereinafter, the present invention will be described specifically with reference to Examples.
実施例1 L−フェニルアラニン(L−Phe)を150g/の濃度で
含有するpH1.5の粗製溶液1に第1表に示す添加剤を
各1000ppm(対L−Phe重量)添加し、60℃でpH6.0まで
中和して結晶を析出させた後、40℃まで冷却して結晶を
成長させた。得られた結晶は卓上式遠心分離機で一定条
件下で分離して評価した。また、比較の為、添加剤無添
加の場合も上記と同様の操作をした。その結果は第1表
の通りであった。
Example 1 To each of the crude solutions 1 containing L-phenylalanine (L-Phe) at a concentration of 150 g / and having a pH of 1.5, the additives shown in Table 1 were added in an amount of 1000 ppm (based on L-Phe weight). After neutralization to pH 6.0 to precipitate crystals, the crystals were cooled to 40 ° C. to grow crystals. The obtained crystals were separated and evaluated under a certain condition using a table-top centrifuge. For comparison, the same operation as described above was performed in the case where no additive was added. The results are as shown in Table 1.
実施例2 発酵法より得られたL−トリプトファン(L−Trp)
を6g/の濃度で含有する水溶液5に第5表に示す添
加剤を各2000ppm(対し−Trp重量)添加し、エバポレー
ターで60℃、減圧下濃縮しその後40℃まで冷却してL−
Trp結晶を析出させた。結晶は卓上式遠心分離機で一定
条件下で分離して評価した。また、比較の為、添加剤無
添加の場合も上記と同様の操作をした。その際の結晶形
と懸濁状態は第2表の通りであった。
Example 2 L-tryptophan (L-Trp) obtained by a fermentation method
Was added to an aqueous solution 5 containing 6g / at a concentration of 2000 ppm (in each case -Trp weight), and concentrated under reduced pressure at 60 ° C by an evaporator, then cooled to 40 ° C and L-
Trp crystals were precipitated. The crystals were separated and evaluated under a certain condition using a tabletop centrifuge. For comparison, the same operation as described above was performed in the case where no additive was added. Table 2 shows the crystal form and suspension state.
実施例3 L−イソロイシン(L−Ile)の粗結晶を250g/の濃
度で50℃溶解した酸性溶液2に第3表に示す添加剤を
各500ppm(対L−Ile重量)添加し十分に溶解した後、6
N−NaOH水溶液を滴下して中和し、再結晶化を行った。
結晶は一定条件下で過分離を行い評価した。なお、無
添加の場合も同様の操作を行った。その際の結晶形と付
着水分は第3表の通りであった。
Example 3 Addition of the additives shown in Table 3 to each acidic solution 2 in which crude crystals of L-isoleucine (L-Ile) were dissolved at 50 ° C. at a concentration of 250 g / 500 ppm (by weight relative to L-Ile) and sufficiently dissolved. After that, 6
N-NaOH aqueous solution was added dropwise to neutralize and recrystallize.
The crystals were over-separated under certain conditions and evaluated. In addition, the same operation was performed in the case of no addition. At this time, the crystal form and the attached moisture are as shown in Table 3.
産業上の利用可能性 本発明によれば、アミノ酸結晶の分離操作性が改善さ
れると同時に、より高純度の結晶を取得できる安価な晶
析方法であることから、工業レベルでの実施が期待され
る。
Industrial Applicability According to the present invention, the separation operability of amino acid crystals is improved, and at the same time, it is an inexpensive crystallization method capable of obtaining higher purity crystals. Is done.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭60−237054(JP,A) 特開 昭49−20119(JP,A) 特公 昭46−19610(JP,B1) (58)調査した分野(Int.Cl.6,DB名) C07C 229/36 C07C 227/42 WPI(DIALOG)──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-60-237054 (JP, A) JP-A-49-20119 (JP, A) JP-B-46-19610 (JP, B1) (58) Field (Int. Cl. 6 , DB name) C07C 229/36 C07C 227/42 WPI (DIALOG)

Claims (1)

    (57)【特許請求の範囲】(57) [Claims]
  1. 【請求項1】フェニルアラニン、トリプトファン、セリ
    ン、イソロイシン、バリン、スレオニン及びロイシンよ
    りなる群の中から選ばれるアミノ酸の晶析において、晶
    析時に脂肪酸塩系、硫酸エステル塩系、アルキルアリル
    スルホン酸塩系もしくはりん酸エステル塩系のアニオン
    性界面活性剤、第4アンモニウム塩系、脂肪族アミン系
    もしくはピリジニウム系のカチオン性界面活性剤及びポ
    リオキシエチレンエーテル系、ソルビタンアルキルエス
    テル系、多価アルコールと脂肪酸のエステル類もしくは
    脂肪酸エタノールアミド系の非イオン性界面活性剤より
    なる群の中から選ばれる界面活性剤を該アミノ酸に対し
    て500〜5000ppmの濃度で存在せしめることを特徴とする
    アミノ酸の晶析法。
    1. In the crystallization of an amino acid selected from the group consisting of phenylalanine, tryptophan, serine, isoleucine, valine, threonine and leucine, at the time of crystallization, a fatty acid salt, a sulfate ester, an alkylallyl sulfonate is used. Or phosphate ester-based anionic surfactant, quaternary ammonium salt-based, aliphatic amine-based or pyridinium-based cationic surfactant, and polyoxyethylene ether-based, sorbitan alkyl ester-based, polyhydric alcohol and fatty acid A method for crystallizing an amino acid, wherein a surfactant selected from the group consisting of esters or fatty acid ethanolamide-based nonionic surfactants is present at a concentration of 500 to 5000 ppm based on the amino acid.
JP50336890A 1989-02-13 1990-02-09 Crystallization of amino acids Expired - Fee Related JP2870192B2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP1-33369 1989-02-13
JP3336989 1989-02-13
JP50336890A JP2870192B2 (en) 1989-02-13 1990-02-09 Crystallization of amino acids

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP50336890A JP2870192B2 (en) 1989-02-13 1990-02-09 Crystallization of amino acids

Publications (1)

Publication Number Publication Date
JP2870192B2 true JP2870192B2 (en) 1999-03-10

Family

ID=26372049

Family Applications (1)

Application Number Title Priority Date Filing Date
JP50336890A Expired - Fee Related JP2870192B2 (en) 1989-02-13 1990-02-09 Crystallization of amino acids

Country Status (1)

Country Link
JP (1) JP2870192B2 (en)

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