JP3243891B2 - Purification method of pyruvate - Google Patents
Purification method of pyruvateInfo
- Publication number
- JP3243891B2 JP3243891B2 JP14205393A JP14205393A JP3243891B2 JP 3243891 B2 JP3243891 B2 JP 3243891B2 JP 14205393 A JP14205393 A JP 14205393A JP 14205393 A JP14205393 A JP 14205393A JP 3243891 B2 JP3243891 B2 JP 3243891B2
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- JP
- Japan
- Prior art keywords
- pyruvic acid
- purity
- pyruvate
- effluent
- acid
- Prior art date
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Description
【０００１】[0001]
【産業上の利用分野】本発明はピルビン酸の精製方法に
関する。ピルビン酸は工業的にはアラニン、チロシン、
トリプトファンなどの各種アミノ酸の製造原料としてさ
らに種々の医薬製造の中間原料として広い用途を有して
いる。従って安価に製造し得れば種々の合成原料とし
て、また代謝促進物質として極めて有用である。The present invention relates to a method for purifying pyruvic acid. Pyruvate is industrially alanine, tyrosine,
It has a wide range of uses as a raw material for producing various amino acids such as tryptophan and also as an intermediate raw material for producing various pharmaceuticals. Therefore, if it can be produced at low cost, it is extremely useful as various synthetic raw materials and as a metabolism promoting substance.
【０００２】安価に高純度のピルビン酸水溶液が得られ
れば、その塩を得るにはそのまま塩化反応を行った後、
濃縮・晶析などの常法により容易に目的物を得ることが
でき、また、ピルビン酸水溶液を常法による濃縮後、エ
ステル化原料にしてもよいし、Ｌ−チロシン、Ｌ−トリ
プトファンを酵素反応から製造する原料としても有用で
ある。If a high-purity pyruvic acid aqueous solution can be obtained at low cost, the salt can be obtained by directly performing a salification reaction.
The target substance can be easily obtained by a conventional method such as concentration and crystallization, and the pyruvic acid aqueous solution may be concentrated by a conventional method and then used as an esterification raw material, or L-tyrosine and L-tryptophan may be subjected to an enzymatic reaction. It is also useful as a raw material produced from.
【０００３】[0003]
【従来の技術】従来、ピルビン酸またはその塩を含む水
溶液からピルビン酸またはその塩を精製する方法として
は、ピルビン酸塩を含む水溶液からの分離法は、強酸性
陽イオン交換樹脂により陽イオン成分を除去した後、強
塩基性陰イオン交換樹脂による吸着・クロマト分離によ
る精製（実験化学講座ｖｏｌ１２＆２５）を行い、(a)
有機酸として得る場合には蒸留精製するか、または、
(b) ピルビン酸塩として得る場合には塩化反応を行った
後、濃縮・晶析あるいは、有機溶媒による晶析などの精
製を行う（特開昭５４−１３２５２２号公報、特公昭５
８−４２８５５号公報）方法が知られている。2. Description of the Related Art Conventionally, as a method for purifying pyruvic acid or a salt thereof from an aqueous solution containing pyruvic acid or a salt thereof, a method of separating pyruvic acid or a salt thereof from an aqueous solution containing pyruvate has been known. After removal of, purification by adsorption and chromatographic separation with a strongly basic anion exchange resin (Experimental Chemistry Lecture vol. 12 & 25) was performed, and (a)
When obtained as an organic acid, it is purified by distillation, or
(b) In the case of obtaining pyruvate, after performing a salification reaction, purification such as concentration and crystallization or crystallization with an organic solvent is performed (Japanese Patent Application Laid-Open No. 54-132522, Japanese Patent Publication No.
A method is known.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら従来の方
法では、不安定なピルビン酸またはその塩を安価に収率
よく純度よく得るには不十分であり、特に不純物を多く
混入した発酵生産されたピルビン酸またはその塩、ある
いは濃縮・晶析によって目的物を取得した後の不純物を
多く混入した母液から安価に収率よく回収精製する方法
が望まれた。しかしながら、従来の方法（実験化学講座
第１２および２５巻）記載の強塩基性陰イオン交換樹脂
（四級アンモニウム基を交換基とする）では、溶出剤お
よび不純物の混入が著しく、収率よく回収精製するには
不十分であった。However, the conventional method is not sufficient for obtaining unstable pyruvic acid or a salt thereof inexpensively and with good purity, and particularly, pyruvic acid produced by fermentation containing a large amount of impurities. There has been a demand for a method of recovering and purifying an acid or a salt thereof, or a mother liquor containing a large amount of impurities after obtaining a target substance by concentration and crystallization at low cost and with good yield. However, in the strongly basic anion exchange resin (using a quaternary ammonium group as an exchange group) described in the conventional method (Experimental Chemistry Course, Vol. It was not enough for purification.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、ピルビン
酸を含有する混合液から、不純物を分離除去しピルビン
酸を精製する方法について鋭意研究を続けてきた結果、
三級アミンを交換基とする弱塩基性陰イオン交換体が純
度も収率もともに優れ効果的に精製できることを見い出
し本発明を完成させるに至った。Means for Solving the Problems The present inventors have conducted intensive studies on a method for purifying pyruvic acid by separating and removing impurities from a mixture containing pyruvic acid.
The present inventors have found that a weakly basic anion exchanger having a tertiary amine as an exchange group can be effectively purified with excellent purity and yield, and completed the present invention.
【０００６】すなわち、本発明は、ピルビン酸を含む水
溶液を、三級アミンを交換基とする弱塩基性陰イオン交
換体と接触させることを特徴とするピルビン酸の精製方
法である。That is, the present invention is a method for purifying pyruvic acid, which comprises contacting an aqueous solution containing pyruvic acid with a weakly basic anion exchanger having a tertiary amine as an exchange group.
【０００７】以下本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
【０００８】本発明によれば、ピルビン酸を含む水溶液
を三級アミンを交換基とする弱塩基性陰イオン交換体と
接触させることにより、ピルビン酸を該樹脂に吸着さ
せ、しかるのちに溶出することによりピルビン酸を精製
することができる。According to the present invention, pyruvic acid is adsorbed on the resin by contacting an aqueous solution containing pyruvic acid with a weakly basic anion exchanger having a tertiary amine as an exchange group, and then eluted. Thus, pyruvic acid can be purified.
【０００９】本発明において用いるピルビン酸を含む水
溶液は、たとえば発酵生産された培養液およびそれらの
処理物、ピルビン酸塩類の濃縮・晶析母液の処理液、ま
たは化学合成法で製造されたピルビン酸を含む処理液で
あってもよいし、ピルビン酸を含む蒸留精製残渣であっ
てもよい。ピルビン酸塩類の精製にあっては、まず強酸
性陽イオン交換体に通液し、陽イオン成分を除去し、し
かる後に前記イオン交換体により精製を行う。主な不純
物としてはパラピルビン酸、酢酸などの有機酸などが挙
げられる。The aqueous solution containing pyruvic acid used in the present invention may be, for example, a fermentation-produced culture solution and a treated product thereof, a treatment solution of a mother liquor for concentrating and crystallizing pyruvates, or pyruvic acid produced by a chemical synthesis method. Or a distillation purification residue containing pyruvic acid. In the purification of pyruvates, the solution is first passed through a strongly acidic cation exchanger to remove cation components, and then purified by the ion exchanger. The main impurities include organic acids such as parapyruvic acid and acetic acid.
【００１０】本発明に用いる弱塩基性陰イオン交換体
は、三級アミンを交換基とする弱塩基性陰イオン交換体
であって、ここで三級アミンとは、例えば、The weakly basic anion exchanger used in the present invention is a weakly basic anion exchanger having a tertiary amine as an exchange group, wherein the tertiary amine is, for example,
【化１】 であり、Ｐは高分子基を示し、Ｒ1 およびＲ2 は同種ま
たは異種のアルキル基を示す。形状は任意であり短繊維
状、解砕物、あるいはビーズ状樹脂を示す。たとえば本
発明で用いるイオン交換体を商品名で示せば“ダウェッ
クス”ＮＷＡ−１；“ダイアイオン”ＷＡ−３０、ＷＡ
−１０、ＷＡ−１１；“デュオライト”Ａ−６、Ａ−３
０８、ＫＡ−８００、ＫＡ−９００；“アンバーライ
ト”ＩＲＡ−９３、ＩＲＡ−９４、ＩＲＡ−６８、ＸＥ
−２７５；“レバチット”ＭＰ−６０などが挙げられ
る。Embedded image Wherein P represents a polymer group, and R 1 and R 2 represent the same or different alkyl groups. The shape is arbitrary and indicates a short fiber, a crushed product, or a beaded resin. For example, if the ion exchanger used in the present invention is indicated by a trade name, "Dowex"NWA-1;"Diaion" WA-30, WA
-10, WA-11; "Duolite" A-6, A-3
08, KA-800, KA-900; "Amberlite" IRA-93, IRA-94, IRA-68, XE
-275; "Levatit" MP-60 and the like.
【００１１】本発明において用いる溶出剤としては硫
酸、塩酸などの鉱酸でよく、また、濃度は０．１Ｎ〜２
Ｎの一般的濃度でよく、あまり濃度を高くすると目的物
中に溶出剤が混入し純度を下げるし、また溶出剤濃度を
下げると目的物の濃度が希薄となるため、好ましくは
０．３Ｎ〜１Ｎである。The eluent used in the present invention may be a mineral acid such as sulfuric acid, hydrochloric acid or the like, and the concentration thereof is 0.1N to 2N.
A general concentration of N may be used. If the concentration is too high, the eluent is mixed into the target substance to lower the purity, and if the concentration of the eluent is lowered, the concentration of the target substance becomes thin. 1N.
【００１２】また、溶出剤の通液速度ＳＶは０．１〜２
と一般的な速度でよいが目的物を純度よく溶出させるに
はＳＶ０．３〜１．０が好ましい。操作温度については
特に規定されず常温で収率よく純度よく目的物が得られ
る。In addition, the flow rate SV of the eluent is 0.1 to 2
At a general rate, SV of 0.3 to 1.0 is preferable for eluting the target substance with high purity. The operating temperature is not particularly limited, and the desired product can be obtained at normal temperature and with high yield.
【００１３】本発明の精製操作は常法で実施できる。The purification operation of the present invention can be carried out by a conventional method.
【００１４】[0014]
【実施例】以下、実施例により本発明を具体的に説明す
る。The present invention will be described below in detail with reference to examples.
【００１５】実施例１ 純度４１％のピルビン酸含量２４％のピルビン酸ナトリ
ウム晶析母液を、強酸性陽イオン交換樹脂“レバチッ
ト”Ｓ−１００（Ｈ＋）（西独バイエル社製）に通液
し、得られた流出液を、１．５Ｎの苛性ソーダで再生し
た三級アミンを交換基とする弱塩基性陰イオン交換樹脂
“ダイヤイオン”ＷＡ−３０（三菱化成工業（株）
製）、７００mlを充填した４０mmφ塔に通液・吸着し
た。十分に水洗を行った後、０．５Ｎ硫酸を溶出剤と
し、ＳＶ＝０．５で通液・脱着した。流出液を３５０ml
ずつ区分し、ピルビン酸濃度を液体クロマトグラフィー
で定量し、同時にまた液中の酸成分の定量を中和滴定で
行い、次式に従ってピルビン酸純度を求めた。Example 1 A sodium pyruvate crystallization mother liquor having a purity of 41% and a pyruvate content of 24% was passed through a strongly acidic cation exchange resin "LEVATIT" S-100 (H + ) (manufactured by Bayer AG, West Germany). The resulting effluent was weakly anion-exchange resin "Diaion" WA-30 having a tertiary amine exchange group regenerated with 1.5N caustic soda (Mitsubishi Kasei Kogyo Co., Ltd.)
And adsorbed to a 40 mmφ column filled with 700 ml. After sufficiently washing with water, the solution was passed through and desorbed at an SV of 0.5 using 0.5N sulfuric acid as an eluent. 350 ml of effluent
The pyruvate concentration was quantified by liquid chromatography, and the acid component in the liquid was simultaneously quantified by neutralization titration to determine the pyruvate purity according to the following equation.
【００１６】[0016]
【式１】 (Equation 1)
【００１７】それによるとピルビン酸純度９３．１％の
流出液が７２％の収率で得られた。得られたピルビン酸
水溶液を苛性ソーダ水溶液で中和した後、濃縮・晶析・
脱水を繰返し、ピルビン酸ナトリウムの結晶を７５％の
収率で得た。得られた乾燥結晶を酵素法乳酸デヒドロゲ
ナーゼによる定量をした結果、純度９９．１％であっ
た。This gave an effluent with a pyruvate purity of 93.1% in a yield of 72%. After neutralizing the obtained pyruvic acid aqueous solution with caustic soda aqueous solution, concentration, crystallization,
Dehydration was repeated to obtain sodium pyruvate crystals in a yield of 75%. The obtained dried crystals were quantified by an enzymatic lactate dehydrogenase, and as a result, the purity was 99.1%.
【００１８】実施例２ 純度６１％、濃度６．４％のピルビン酸を含有する培養
液３．７リットルを強酸性陽イオン交換樹脂“レバチッ
ト”Ｓ−１００（Ｈ＋）（西独バイエル社製）２リット
ルに通液し得られた流出液を、アルカリ水溶液で再生し
た“ダイヤイオン”ＷＡ−３０（ＯＨ−型）（三菱化成
工業（株）製）３．２リットルを充填した７０mmφの塔
に通液吸着させ、十分に水洗を行った後０．５Ｎの硫酸
を溶出剤としＳＶ０．８で通液・脱着した。流出液を
２．５リットルずつに区分し、ピルビン酸濃度を液体ク
ロマトグラフィーで定量し、同時にまた液中の酸成分の
定量を中和滴定で行い、ピルビン酸純度を求めた。それ
によると９４．１％純度の流出液を７８％の収率で得
た。Example 2 3.7 liters of a culture solution containing pyruvate having a purity of 61% and a concentration of 6.4% was applied to a strongly acidic cation exchange resin "LEVATIT" S-100 (H + ) (manufactured by Bayer AG, West Germany). The effluent obtained by passing through 2 liters was passed through a 70 mmφ column filled with 3.2 liters of “Diaion” WA-30 (OH - type) (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) regenerated with an aqueous alkali solution. After passing through and adsorbing and thoroughly washing with water, the solution was passed through and desorbed with SV 0.8 using 0.5N sulfuric acid as an eluent. The effluent was divided into 2.5 liter portions, and the concentration of pyruvate was determined by liquid chromatography, and at the same time, the acid component in the solution was determined by neutralization titration to determine the purity of pyruvate. The result was a 94.1% pure effluent in 78% yield.
【００１９】実施例３ 実施例２と同様に、硫酸の溶出剤濃度を０．５Ｎから
１．０Ｎに変え、溶出液速度ＳＶ０．８から０．６に変
えた以外は変えることなく、同様の操作を行った。Example 3 In the same manner as in Example 2, except that the concentration of the eluent for sulfuric acid was changed from 0.5N to 1.0N and the eluate speed SV was changed from 0.8 to 0.6, the same procedure was repeated. The operation was performed.
【００２０】その結果、ピルビン酸純度９４．７％の流
出液を７１．５％の収率で得た。As a result, an effluent having a pyruvate purity of 94.7% was obtained in a yield of 71.5%.
【００２１】実施例４ 実施例２と同様に三級アミンを交換基とする弱塩基性陰
イオン交換樹脂“アンバーライト”ＩＲＡ−９３（米国
ロームアンドハース社製）を、１．５Ｎ苛性ソーダで再
生した後、内径４０mmφの塔に３５０ml充填し、純度６
２％、濃度２．６％のピルビン酸水溶液を通液・吸着さ
せた。十分に水洗を行った後、０．５Ｎの硫酸を溶出剤
としＳＶ０．８３で通液・吸着した。流出液を２００ml
ずつ区分し、実施例１と同様に分析・定量した。その結
果、純度９３．０％の流出液を７２．３％の収率で得
た。Example 4 In the same manner as in Example 2, a weakly basic anion exchange resin "Amberlite" IRA-93 (trade name, manufactured by Rohm and Haas Company, USA) having a tertiary amine as an exchange group was regenerated with 1.5N sodium hydroxide. After that, packed into a tower with an inner diameter of 40 mmφ by 350 ml,
A 2%, 2.6% pyruvic acid aqueous solution was passed and adsorbed. After sufficiently washing with water, the solution was passed and adsorbed with SV 0.83 using 0.5N sulfuric acid as an eluent. 200 ml of effluent
Each sample was analyzed and quantified in the same manner as in Example 1. As a result, an effluent having a purity of 93.0% was obtained at a yield of 72.3%.
【００２２】実施例５ 実施例２と同様に三級アミンを交換基とする弱塩基性イ
オン交換樹脂“デュオライト”ＫＡ−９００（米国ダイ
アモンドシャムロック社製）を、２Ｎ苛性ソーダで再生
した後、内径３６mmφの塔に１８０ml充填し、実施例４
と同純度、濃度のピルビン酸を含有する水溶液を通液・
吸着させた。十分に水洗を行った後、０．５Ｎの硫酸を
溶出剤としＳＶ０．７で通液・脱着した。流出液を１３
０mlずつ区分し実施例１と同様に分析・定量した。その
結果、純度９６．８％の流出液を７３．８％の収率で得
た。Example 5 A weakly basic ion exchange resin "Duolite" KA-900 (manufactured by Diamond Shamrock, USA) having a tertiary amine as an exchange group was regenerated with 2N sodium hydroxide in the same manner as in Example 2. Example 4 A tower with an inner diameter of 36 mmφ was packed with 180 ml,
Aqueous solution containing pyruvic acid of the same purity and concentration as
Adsorbed. After sufficiently washing with water, the solution was passed and desorbed with SV 0.7 using 0.5 N sulfuric acid as an eluent. 13 effluents
The sample was divided into 0 ml portions and analyzed and quantified in the same manner as in Example 1. As a result, an effluent having a purity of 96.8% was obtained in a yield of 73.8%.
【００２３】比較例１ 実施例２と同培養液を同法により処理した流出液を使用
して、同法で再生した四級アンモニウム基を交換基とす
る強塩基性陰イオン交換樹脂“ダイヤイオン”ＰＡ４１
２（三菱化成工業（株）製）７２０mlに通液・吸着さ
せ、０．５Ｎ硫酸を溶出剤としＳＶ０．５で通液・脱着
した。流出液を３６０mlずつに区分し、同法により分析
定量したところ、９３．７％純度の流出液を５６％の収
率で得た。Comparative Example 1 Using an effluent obtained by treating the same culture solution as in Example 2 by the same method, a strongly basic anion exchange resin "Diaion" having a quaternary ammonium group as an exchange group was regenerated by the same method. "PA41
The solution was passed through and adsorbed to 720 ml of 2 (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.), and passed through and desorbed with 0.5N SV using 0.5N sulfuric acid as an eluent. The effluent was divided into 360 ml portions and analyzed and quantified by the same method. As a result, an effluent having a purity of 93.7% was obtained in a yield of 56%.
【００２４】比較例２ 実施例１と同様に、弱塩基性イオン交換樹脂“ダイヤイ
オン”ＷＡ−３０を四級アンモニウム基を交換基とする
強塩基性イオン交換樹脂“ダイヤイオン”ＰＡ−３１６
（三菱化成工業（株）製）に変えた以外は、変えること
なく操作を行った。その結果、ピルビン酸純度８９．６
％の流出液を４８．５％の収率で得た。Comparative Example 2 In the same manner as in Example 1, a weakly basic ion exchange resin "Diaion" WA-30 was replaced with a strongly basic ion exchange resin "Diaion" PA-316 having a quaternary ammonium group as an exchange group.
(Mitsubishi Kasei Kogyo Co., Ltd.). As a result, pyruvate purity was 89.6.
% Effluent was obtained in a 48.5% yield.
【００２５】比較例３ 実施例１と同様に、弱塩基性イオン交換樹脂“ダイヤイ
オン”ＷＡ−３０を四級アンモニウム基を交換基とする
強塩基性イオン交換樹脂“レバチット”ＭＰ−５００
（西独バイエル社製）に変えた以外は、変えることなく
操作を行った。その結果、ピルビン酸純度８７．６％の
流出液を２０．８％の収率で得た。Comparative Example 3 In the same manner as in Example 1, a weakly basic ion-exchange resin "Diaion" WA-30 was replaced with a strongly basic ion-exchange resin "Levatit" MP-500 using a quaternary ammonium group as an exchange group.
(Bayer, West Germany), except for the operation. As a result, an effluent having a pyruvic acid purity of 87.6% was obtained in a yield of 20.8%.
【００２６】比較例４ 実施例２と同培養液を同法により処理した流出液を使用
して、同法で再生した一、二級アミンを交換基とする弱
塩基性陰イオン交換樹脂“アンバーライト”ＩＲ−４５
（ロームアンドハース社製）３５０mlを充填した４０mm
φの塔に通液・吸着させた。十分に水洗を行った後、
０．４Ｎの硫酸を溶出剤としＳＶ＝０．５で通液・脱着
した。流出液を１７５mlずつ区分し、実施例１と同様に
分析・定量した。その結果、最高ピルビン酸純度４７％
の流出液を９％の収率で得た。Comparative Example 4 Using an effluent obtained by treating the same culture solution as in Example 2 by the same method, and regenerating by the same method, a weakly basic anion exchange resin having a primary or secondary amine as an exchange group, "Amber" Light "IR-45"
(Rohm and Haas Company) 40mm filled with 350ml
The liquid was passed and adsorbed through the φ tower. After washing thoroughly with water,
The solution was passed and desorbed at SV = 0.5 using 0.4N sulfuric acid as an eluent. The effluent was divided into 175 ml portions and analyzed and quantified in the same manner as in Example 1. As a result, the highest pyruvic acid purity 47%
Was obtained in a yield of 9%.
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【発明の効果】本発明によれば、一操作で一挙にピルビ
ン酸の純度を向上させることができ、高純度の精製品を
得ることができる。また、その後の精製の負荷を下げ、
工業的に安価にピルビン酸を精製することが可能とな
る。According to the present invention, the purity of pyruvic acid can be improved all at once by one operation, and a purified product of high purity can be obtained. In addition, the load of subsequent purification was reduced,
It becomes possible to purify pyruvic acid industrially at low cost.
【００２９】さらに、本発明によればピルビン酸を高回
収率でかつ高純度に精製することが可能となる。Further, according to the present invention, it is possible to purify pyruvic acid with high recovery and high purity.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 51/487 C07C 51/47 C07C 59/19 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. 7 , DB name) C07C 51/487 C07C 51/47 C07C 59/19
Claims (1)
交換基とする弱塩基性陰イオン交換体と接触させること
を特徴とするピルビン酸の精製方法。1. A method for purifying pyruvic acid, comprising contacting an aqueous solution containing pyruvic acid with a weakly basic anion exchanger having a tertiary amine as an exchange group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14205393A JP3243891B2 (en) | 1993-06-14 | 1993-06-14 | Purification method of pyruvate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14205393A JP3243891B2 (en) | 1993-06-14 | 1993-06-14 | Purification method of pyruvate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06345683A JPH06345683A (en) | 1994-12-20 |
| JP3243891B2 true JP3243891B2 (en) | 2002-01-07 |
Family
ID=15306319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14205393A Expired - Fee Related JP3243891B2 (en) | 1993-06-14 | 1993-06-14 | Purification method of pyruvate |
Country Status (1)
| Country | Link |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103331C (en) * | 2000-01-21 | 2003-03-19 | 无锡轻工大学 | Process for extracting pyruvic acid from fermented liquid of pyruvic acid and preparing sodium pyrouvate |
| PL2330209T3 (en) | 2008-09-30 | 2017-12-29 | Toray Industries, Inc. | Method and apparatus for producing a chemical and continuous culture system |
| US9365876B2 (en) | 2010-12-09 | 2016-06-14 | Toray Industries, Inc. | Method for producing chemical by continuous fermentation |
| JP6201753B2 (en) | 2012-03-30 | 2017-09-27 | 東レ株式会社 | Process for producing chemicals by continuous fermentation and continuous fermentation apparatus |
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1993
- 1993-06-14 JP JP14205393A patent/JP3243891B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH06345683A (en) | 1994-12-20 |
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