KR101711638B1 - Method for Recovering and Purifying of Monoethylamine from Enzyme Reaction Solution for Theanine - Google Patents

Method for Recovering and Purifying of Monoethylamine from Enzyme Reaction Solution for Theanine Download PDF

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KR101711638B1
KR101711638B1 KR1020140188623A KR20140188623A KR101711638B1 KR 101711638 B1 KR101711638 B1 KR 101711638B1 KR 1020140188623 A KR1020140188623 A KR 1020140188623A KR 20140188623 A KR20140188623 A KR 20140188623A KR 101711638 B1 KR101711638 B1 KR 101711638B1
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ethylamine
theanine
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한민호
박동철
강기권
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대상 주식회사
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    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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Abstract

본 발명은 (a) 이온교환 공정을 거쳐 회수 분리된 에틸아민 및 양이온을 포함하는 재생액을 pH 3-6으로 조정하고 농축하는 단계; 및 (b) 상기 단계 (a)의 결과물을 냉각하여 양이온염으로 석출시키는 단계를 포함하는 미반응 에틸아민을 포함하는 테아닌 효소 반응액으로부터 에틸아민의 회수 정제 방법에 관한 것이다. 본 발명은 가열을 통한 증류 과정을 거쳐 목적 생성물인 테아닌을 분해하는 문제점 없이, 이온교환 공정을 거쳐 회수 분리된 재생액을 특정 pH로 조정하고 농축하며 냉각을 하여, 높은 회수율 및 순도를 가지는 에틸아민을 회수 정제할 수 있다. 이렇게 높은 회수율 및 순도로 회수 정제된 에틸아민은 차기 테아닌 효소 반응에 재활용이 가능하다.(A) adjusting and regulating a regeneration liquid containing ethylamine and a cation recovered and separated through an ion exchange process to a pH of 3-6; And (b) cooling the resultant product of step (a) to precipitate as a cation salt. The present invention relates to a process for the recovery and purification of ethylamine from a theanine enzyme reaction solution containing unreacted ethylamine. The present invention relates to a process for recovering and recovering a regenerated solution recovered through the ion exchange process without any problem of decomposition of theanine, which is a target product, through heating and distillation, Can be recovered and purified. This high recovery and purity recovered ethylamine can be recycled to the next theanine enzyme reaction.

Description

테아닌 효소 반응액으로부터 에틸아민의 회수 정제 방법{Method for Recovering and Purifying of Monoethylamine from Enzyme Reaction Solution for Theanine}(Method for Recovering and Purifying of Monoethylamine from Enzyme Reaction Solution for Theanine)

본 발명은 미반응 에틸아민을 포함하는 테아닌 효소 반응액으로부터 에틸아민의 회수 정제 방법에 관한 것이다.
The present invention relates to a process for the recovery and purification of ethylamine from a theanine enzyme reaction solution containing unreacted ethylamine.

테아닌은 녹차 맛의 주요성분으로서 알려져 있고, 차를 비롯한 식품의 향기성분으로서 중요한 물질이다. 테아닌을 포함하는 γ-글루타밀 유도체(γ-glutamyl derivative)는, 동물 및 식물체에 있어서 생리 활성 물질로서 작용한다고 알려져 있으며, 예를 들면 Ｃｈｅｍ．Ｐａｒｍ．Ｂｕｌｌ., 19(7) 1301-1307(1971)에는, 테아닌이나 L-글루타민(L-glutamine)이 카페인에 의해 유발되는 경련에 길항(拮抗)한다고 보고되어 있다.Theanine is known as a major component of green tea taste, and is important as a flavor component of tea and other foods. The γ-glutamyl derivative containing theanine is known to act as a physiologically active substance in animals and plants. For example, it is known that γ-glutamyl derivatives including theanine are known, for example, in Chem.Parm.Bull., 19 (7) 1301-1307 ), Theanine and L-glutamine have been reported to antagonize caffeine-induced seizures.

한편, 테아닌의 제조 방법으로 추출법 및 화학적 유기합성 방법이 알려져 있으나, 이는 수율이 낮으며, 특히 유기합성법은 합성물의 분리 정제 등에 있어서 번잡한 조작을 필요로 하는 문제점이 있었다.On the other hand, the extraction method and the chemical organic synthesis method are known as the production method of theanine, but the yield is low. In particular, the organic synthesis method has a problem in that complicated operation is required in the separation and purification of the synthesis.

이에, 공업적 생산방법으로서, 슈도모나스(Pseudomonas) 속 유래의 글루타미나아제(glutaminase)의 γ-글루타밀기 전이반응을 이용하여 L-글루타민과 에틸아민으로 부터 테아닌을 합성하는 효소법이 보고되어 있으며(일본 공개특허공보 특개평11-225789), 상기 효소를 담체(擔體)에 고정화한 효소법이 알려져 있다(일본국 공개특허공보 특개평5-328986). As an industrial production method, there has been reported an enzymatic method for synthesizing theanine from L-glutamine and ethylamine by using a? -Glutamyltransfer reaction of glutaminase derived from Pseudomonas sp . (Japanese Unexamined Patent Application Publication No. 11-225789), and an enzyme method in which the enzyme is immobilized on a carrier (JP-A-5-328986).

한편, 이러한 효소법에 의해 테아닌을 제조 공정 후에 잔류되는 미반응 에틸아민을 회수하는데 있어, 미국 특허등록 US 8211674에서는 테아닌 효소 반응 생성 후, 정제 공정에서 잔류 에틸 아민을 감압 농축에 의해 제거하는 내용이 개시되어 있으며, 미국 특허 등록 US 8211674에는 모노-, 디- 및 트리-에틸아민의 분별 증류에 의한 분리 과정이 개시되어 있다. On the other hand, US patent application US 8211674 discloses that, in order to recover unreacted ethylamine remaining after the theanine production process by such an enzymatic method, the residual ethylamine is removed by concentration under reduced pressure in the purification process after the theanine enzyme reaction is produced. And U.S. Patent No. 8211674 discloses a separation process by fractional distillation of mono-, di-, and tri-ethylamines.

그러나, 테아닌 효소반응액의 에틸아민을 증류하기 위해서는 열원(heat source)이 필요하며, 가열을 할 경우 테아닌이 분해되는 문제점이 있으며, 증류를 통해 에틸아민을 효소반응액으로부터 회수를 하고자 해도 증류 초반 발생하는 가스 상태의 에틸아민을 포집하기 어려워 에틸아민의 회수 수율이 낮으며 반응 부산물인 암모니아가 에틸아민보다 끓는 점이 낮고 증기압이 높기 때문에 일반적인 증류의 방법에서 분리가 어려워 회수된 에틸아민의 순도가 낮은 문제점이 있었다.
However, in order to distill ethylamine in the reaction solution of theanine enzyme, a heat source is required. When heated, there is a problem that theanine is decomposed. In order to recover ethylamine from the reaction solution by distillation, It is difficult to collect the ethylamine in the gaseous state and the recovery yield of ethylamine is low. Since the reaction byproduct, ammonia, has a lower boiling point than ethylamine and has a high vapor pressure, separation in the general distillation method is difficult and the purity of recovered ethylamine is low There was a problem.

본 명세서 전체에 걸쳐 다수의 논문 및 특허문헌이 참조되고 그 인용이 표시되어 있다. 인용된 논문 및 특허문헌의 개시 내용은 그 전체로서 본 명세서에 참조로 삽입되어 본 발명이 속하는 기술 분야의 수준 및 본 발명의 내용이 보다 명확하게 설명된다.Numerous papers and patent documents are referenced and cited throughout this specification. The disclosures of the cited papers and patent documents are incorporated herein by reference in their entirety to better understand the state of the art to which the present invention pertains and the content of the present invention.

본 발명자들은 테아닌 효소 반응 후 잔류되는 에틸아민을 가열 하여 테아닌을 분해하지 않고, 차기 반응에 재활용이 가능한 순도로 회수 정제하는 방법을 개발하고자 예의 노력하였다. 그 결과, 이온교환 공정을 거쳐 회수 분리된 재생액을 특정 pH로 조정하고 농축하며 냉각을 한 결과, 가열을 통한 증류 과정을 거치는 경우 보다, 높은 회수율 및 순도를 가지는 에틸아민을 회수 정제할 수 있음을 확인함으로써, 본 발명을 완성하게 되었다.
The present inventors have made efforts to develop a method of recovering and purifying ethylamine remaining after the theanine enzyme reaction at a purity permitting recycling in the next reaction without decomposing theanine. As a result, the regenerated solution recovered and recovered through the ion exchange process was adjusted to a specific pH and concentrated and cooled. As a result, ethylamine having a high recovery and purity can be recovered and purified as compared with distillation through heating Thereby completing the present invention.

따라서 본 발명의 목적은 미반응 에틸아민을 포함하는 테아닌 효소 반응액으로부터 에틸아민의 회수 정제 방법을 제공하는 데 있다.
Accordingly, an object of the present invention is to provide a process for the recovery and purification of ethylamine from a theanine enzyme reaction solution containing unreacted ethylamine.

본 발명의 다른 목적 및 이점은 하기의 발명의 상세한 설명 및 청구범위에 의해 보다 명확하게 된다.Other objects and advantages of the present invention will become more apparent from the following detailed description of the invention and claims.

본 발명의 일 양태에 따르면, 본 발명은 다음의 단계를 포함하며 미반응 에틸아민을 포함하는 테아닌 효소 반응액으로부터 에틸아민의 회수 정제 방법을 제공한다: (a) 이온교환 공정을 거쳐 회수 분리된 에틸아민 및 양이온을 포함하는 재생액을 pH 3-6으로 조정하고 농축하는 단계; 및 (b) 상기 단계 (a)의 결과물을 냉각하여 양이온염으로 석출시키는 단계.
According to one aspect of the present invention, the present invention provides a process for the recovery and purification of ethylamine from a theanine enzyme reaction solution comprising unreacted ethylamine, comprising the steps of: (a) recovering the recovered Adjusting the regeneration liquid containing ethylamine and cations to pH 3-6 and concentrating; And (b) cooling the resultant of step (a) to precipitate as a cation salt.

본 발명자들은 테아닌 효소 반응 후 잔류되는 에틸아민을 가열 하여 테아닌을 분해하지 않고, 차기 반응에 재활용이 가능한 순도로 회수 정제하는 방법을 개발하고자 예의 노력하였다. 그 결과, 이온교환 공정을 거쳐 회수 분리된 재생액을 특정 pH로 조정하고 농축하며 냉각을 한 결과, 가열을 통한 증류 과정을 거치는 경우 보다, 높은 회수율 및 순도를 가지는 에틸아민을 회수 정제할 수 있음을 확인하였다.
The present inventors have made efforts to develop a method of recovering and purifying ethylamine remaining after the theanine enzyme reaction at a purity permitting recycling in the next reaction without decomposing theanine. As a result, the regenerated solution recovered and recovered through the ion exchange process was adjusted to a specific pH and concentrated and cooled. As a result, ethylamine having a high recovery and purity can be recovered and purified as compared with distillation through heating Respectively.

본 명세서에서 용어 "효소반응액"은 당업계에 공지된 다양한 효소를 이용하여 테아닌을 제조하는 데 있어 반응액을 의미하며, 상기 테아닌 효소반응액에는 테아닌, 아미노산류, 에틸아민 및 양이온이 포함되어 있다.
As used herein, the term "enzyme reaction solution" means a reaction solution for preparing theanine using various enzymes known in the art, and the theanine enzyme reaction solution contains theanine, amino acids, ethylamine and cations have.

이하, 미반응 에틸아민을 포함하는 테아닌 효소반응액으로부터 에틸아민을 회수 정제하기 위한 본 발명의 방법을 단계별로 상세하게 설명하면 다음과 같다:Hereinafter, the method of the present invention for recovering and purifying ethylamine from a theanine enzyme reaction solution containing unreacted ethylamine will be described in detail as follows:

(a) 이온교환 공정을 거쳐 회수 분리된 재생액의 pH 조정 및 농축 (a) pH adjustment and concentration of regenerant recovered and recovered through an ion exchange process

우선, 본 발명의 방법은 (a) 이온교환 공정을 거쳐 회수 분리된 에틸아민 및 양이온을 포함하는 재생액을 pH 3-6으로 조정하고 농축하는 단계를 포함한다.First, the method of the present invention comprises the steps of (a) adjusting and regulating a regeneration liquid containing ethylamine and cations recovered and separated through an ion exchange process to a pH of 3-6.

본 발명의 일 구현예에 따르면, 상기 단계 (a)의 양이온은 암모늄 이온, 나트륨 이온, 칼륨 이온, 칼슘 이온 및 마그네슘 이온으로 구성된 군으로부터 선택되는 양이온이고, 가장 바람직하게는 암모늄 이온 및 나트륨 이온이다.According to one embodiment of the present invention, the cation of step (a) is a cation selected from the group consisting of ammonium ion, sodium ion, potassium ion, calcium ion and magnesium ion, most preferably ammonium ion and sodium ion .

상기 단계 (a)의 pH 조정은 당업계에 공지된 다양한 염기(base)를 이용하여 실시할 수 있으며, 보다 바람직하게는 상기 염기(base)는 수산화나트륨 또는 암모니아이다.The pH of the step (a) may be adjusted by using various bases known in the art. More preferably, the base is sodium hydroxide or ammonia.

상기 단계 (a)의 pH 조정은 염기를 이용하여 회수 분리된 재생액을 중화시키되, 바람직하게는 pH 3-6, 보다 바람직하게는 pH 4-6으로 조정한다.The pH of the step (a) is adjusted by neutralizing the regenerated solution recovered and separated using a base, preferably pH 3-6, more preferably pH 4-6.

본 발명에서 상기 pH 범위로 조정을 하는 이유는 강산성의 재생액을 농축 하기 위해 내산 설비를 사용해야 하는 제약을 극복하고 농축 시 산증기 발생을 방지하기 위함이며 재생액에 포함되어 있는 에틸아민 및 양이온염의 용해도를 낮추어 후술하는 양이온염의 석출 과정을 용이하게 하기 위함이다.In the present invention, the pH is adjusted to the above range in order to overcome the restriction of using an acidic facility to concentrate the strongly acidic regenerant solution and to prevent the generation of acid vapor during concentration, and the concentration of ethylamine and cationic salt So as to facilitate the precipitation process of the cation salt to be described later by lowering the solubility.

본 발명의 다른 구현예에 따르면, 상기 단계 (a)의 농축은 재생액 부피를 기준으로 하여 에틸아민 20-30 (w/v)% 농도로 실시한다.
According to another embodiment of the present invention, the concentration of the step (a) is carried out at a concentration of 20-30 (w / v)% ethylamine based on the volume of the regeneration liquid.

(b) 상기 단계 (a)의 결과물의 냉각 및 양이온염의 석출 (b) cooling the product of step (a) and precipitating the cation salt

마지막으로, 본 발명의 방법은 (b) 상기 단계 (a)의 결과물을 냉각하여 양이온염으로 석출시키는 단계를 포함한다. Finally, the process of the present invention comprises (b) cooling the product of step (a) to precipitate out into a cationic salt.

본 발명의 또 다른 구현예에 따르면, 상기 단계 (b)의 냉각은 온도 20℃ 이하로 실시하며, 보다 바람직하게는 온도 0-25℃, 보다 더 바람직하게는 온도 10-20℃로 실시한다.According to another embodiment of the present invention, the cooling of step (b) is carried out at a temperature of 20 ° C or lower, more preferably at a temperature of 0-25 ° C, and more preferably at a temperature of 10-20 ° C.

본 발명의 다른 구현예에 따르면, 상기 단계 (b)의 양이온염은 염화암모늄(염안) 및 염화나트륨(식염)이다. According to another embodiment of the present invention, the cationic salt of step (b) is ammonium chloride (saline) and sodium chloride (salt).

본 발명의 또 다른 구현예에 따르면, 상기 방법은 상기 단계 (b) 이후에, (c) 상기 단계 (b)의 결과물을 여과하여 석출된 양이온염을 제거하여 에틸아민을 수득하는 단계를 추가적으로 포함한다.
According to another embodiment of the present invention, the method further comprises the step of (c) after the step (b), filtering the resultant of step (b) to remove the precipitated cation salt to obtain ethylamine do.

이러한 방법으로 테아닌 효소반응액으로부터 에틸아민을 회수 정제할 수 있다.
In this way, ethylamine can be recovered and purified from the theanine enzyme reaction solution.

본 발명의 다른 구현예에 따르면, 상기 회수 정제된 에틸아민은 회수율 97% 이상 및 순도 99% 이상이다.According to another embodiment of the present invention, the recovered purified ethylamine has a recovery of 97% or more and a purity of 99% or more.

본 발명의 또 다른 구현예에 따르면, 상기 회수 정제된 에틸아민은 에틸아민-염산염 형태이다. According to another embodiment of the present invention, the recovered ethylamine is in the form of ethylamine hydrochloride.

본 발명의 다른 구현예에 따르면, 상기 단계 (a)의 이온교환 공정은 다음의 단계를 포함하는 방법으로 실시된다: (i) 테아닌 효소반응액의 테아닌, 아미노산, 에틸아민 및 양이온을 양이온 교환 수지에 흡착시키는 단계; 및 (ii) 상기 단계 (i)의 결과물인 흡착물을 재생하여 에틸아민 및 양이온을 포함하는 재생액을 회수 분리하는 단계.
According to another embodiment of the present invention, the ion exchange process of step (a) is carried out by a method comprising the steps of: (i) contacting the theanine, amino acid, ethylamine and cations of the theanine enzyme reaction liquid with a cation exchange resin ; And (ii) regenerating the adsorbate as a result of the step (i) to recover and separate the regenerant solution containing ethylamine and cations.

(i) 테아닌 효소반응액의 테아닌, 아미노산, 에틸아민 및 양이온을 양이온 교환 수지에 흡착 (i) Theanine, amino acid, ethylamine and cations of the theanine enzyme reaction solution are adsorbed on a cation exchange resin

본 발명에 이용되는 이온교환 공정은 우선, (i) 테아닌 효소 반응액의 테아닌, 아미노산, 에틸아민 및 양이온을 양이온 교환 수지에 흡착시키는 단계를 거친다.In the ion exchange process used in the present invention, first, (i) a step of adsorbing the theanine, amino acid, ethylamine and cations of the theanine enzyme reaction solution to the cation exchange resin is carried out.

보다 바람직하게는, 상기 단계 (i)의 테아닌 효소반응액은 양이온 교환 수지에 대하여 교환용량(exchange capacity) 1.5-2.0 eq/L로 통액되고, 보다 더 바람직하게는 1.7-1.9 eq/L로 통액된다.
More preferably, the theanine enzyme reaction solution of step (i) is passed through the cation exchange resin at an exchange capacity of 1.5-2.0 eq / L, more preferably 1.7-1.9 eq / L, do.

본 발명의 보다 다른 구현예에 따르면, 상기 방법은 단계 (i) 및 (ii) 사이에, (i-1) 상기 단계 (i)의 결과물인 흡착물을 용리하여 테아닌 및 아미노산을 회수 분리하는 단계를 추가적으로 포함한다.According to a further embodiment of the present invention, the method comprises the steps of: (i-1) recovering the anion and the amino acid by eluting the adsorbate resulting from said step (i) between steps (i) and .

보다 더 바람직하게는, 상기 단계 (i-1)의 용리는 용리제인 수산화암모늄으로 실시한다.
Even more preferably, the elution of step (i-1) is carried out with ammonium hydroxide, which is an eluent.

(ii) 상기 단계 (i)의 결과물인 흡착물을 재생하여 에틸아민 및 양이온을 포함하는 재생액의 회수 분리 (ii) regenerating the adsorbate resulting from step (i) to recover and recover the regenerant solution containing ethylamine and cations

그리고, 본 발명에 이용되는 이온교환 공정은 (ii) 상기 단계 (i)의 결과물인 흡착물을 재생하여 에틸아민 및 양이온을 포함하는 재생액을 회수 분리하는 단계를 포함한다.And, the ion exchange process used in the present invention includes (ii) regenerating the adsorbate as a result of the step (i) and recovering and separating the regenerant solution containing ethylamine and cations.

보다 바람직하게는, 상기 단계 (ii)의 재생은 재생제인 산(acid)으로 실시하며, 보다 더 바람직하게는 상기 재생제인 산(acid)은 무기산이며, 보다 더 바람직하게는 염산 또는 황산이다.
More preferably, the regeneration of step (ii) is carried out with an acid as a regenerant, more preferably the acid as the regenerant is an inorganic acid, more preferably hydrochloric acid or sulfuric acid.

본 발명의 특징 및 이점을 요약하면 다음과 같다:The features and advantages of the present invention are summarized as follows:

(ⅰ) 본 발명은 미반응 에틸아민을 포함하는 테아닌 효소 반응액으로부터 에틸아민의 회수 정제 방법을 제공한다.(I) The present invention provides a method for the recovery and purification of ethylamine from a theanine enzyme reaction solution containing unreacted ethylamine.

(ii) 본 발명은 가열을 통한 증류 과정을 거치지 않기 때문에 목적 생성물인 테아닌을 분해하는 문제점 없이, 이온교환 공정을 거쳐 회수 분리된 재생액을 특정 pH로 조정하고 농축하며 냉각을 하여, 높은 회수율 및 순도를 가지는 에틸아민을 회수 정제할 수 있다. (ii) Since the present invention does not involve distillation through heating, the recovered liquid recovered through the ion exchange process is adjusted to a specific pH, concentrated, and cooled without problems of decomposing theanine, which is a target product, Purity ethylamine can be recovered and purified.

(iii) 이렇게 높은 회수율 및 순도로 회수 정제된 에틸아민은 차기 테아닌 효소 반응에 재활용이 가능하다.
(iii) The ethylamine thus recovered and recovered at such a high recovery and purity can be recycled to the next theanine enzyme reaction.

이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 요지에 따라 본 발명의 범위가 이들 실시예에 의해 제한되지 않는다는 것은 당업계에서 통상의 지식을 가진 자에 있어서 자명할 것이다.
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .

실시예Example

실시예 1(비교예): 미반응 에틸아민 증류 회수Example 1 (Comparative Example): Unreacted ethylamine distillation recovery

에틸아민 증류 회수 시 암모니아 분리 가능성 및 수율을 확인하기 위해서, 테아닌 효소 반응액을 양이온 교환수지에 1.8 eq/L 통액하여 테아닌 및 아미노산류, 미반응 에틸아민과 반응 부산물 암모니아를 흡착시켰다. 1.8% NH4OH 용리제로 용리하여 테아닌과 아미노산류를 회수한 후 5% HCl 재생제로 재생하여 재생액을 회수하였다.In order to confirm the possibility of separation and yield of ammonia during the distillation recovery of ethylamine, theanine enzyme reaction liquid was passed through 1.8 eq / L to the cation exchange resin to adsorb the theanine and amino acids, unreacted ethylamine and reaction byproduct ammonia. The theanine and amino acids were recovered by elution with 1.8% NH 4 OH eluent and regenerated with 5% HCl regenerant to recover the regenerated solution.

재생액은 pH 6으로 조정하여 brix 30으로 농축하고 0℃로 냉각하였다. 냉각한 농축액을 pH 13으로 조정하고 서서히 가열하여 에틸아민을 기화하였다. 기화된 에틸아민은 0℃ 응축관에서 응축되어 회수하였다. The regeneration solution was adjusted to pH 6, concentrated to brix 30, and cooled to 0 占 폚. The cooled concentrate was adjusted to pH 13 and slowly heated to vaporize ethylamine. The vaporized ethylamine was condensed and recovered in a 0 ° C condensing tube.

증류법distillation NaNa NH3 NH 3 EtNH2 EtNH 2 NH3/
EtNH2 NH 3 /
EtNH 2 %% gg %% gg %% gg 재생액Recycled amount 0.8%0.8% 3.23.2 0.8%0.8% 3.43.4 18.8%18.8% 75.275.2 11.3%11.3% 증류distillation 0.0%0.0% 0.00.0 1.3%1.3% 1.51.5 58.5%58.5% 66.366.3 5.5%5.5%

상기 표 1에서 볼 수 있듯이, 증류 회수의 경우 에틸아민의 회수율은 88%이였으며, NH3/EtNH2 몰 정제비가 2배임을 확인할 수 있었다.
As can be seen from Table 1, the recovery rate of ethylamine in the distillation recovery was 88%, and it was confirmed that the refining ratio of NH 3 / EtNH 2 mol was 2 times.

실시예 2: 미반응 에틸아민 농축 및 염 제거Example 2 Concentration of Unreacted Ethyl Amine and Salt Removal

재생액 중화 및 농축 시 염 제거 가능성을 확인하기 위하여, 테아닌 효소 반응액을 양이온교환수지에 1.8 eq/L 통액하여 테아닌 및 아미노산류, 미반응 에틸아민과 반응 부산물 암모니아를 흡착시켰다. 1.8% NH4OH 용리제로 용리하여 테아닌과 아미노산류를 회수한 후 5% HCl 재생제로 재생하여 재생액을 회수하였다.The theanine enzyme reaction solution was passed through 1.8 eq / L of the cation exchange resin to adsorb the theanine and amino acids, the unreacted ethylamine and the reaction by-product ammonia in order to confirm the possibility of salt removal in the regeneration liquid neutralization and concentration. The theanine and amino acids were recovered by elution with 1.8% NH 4 OH eluent and regenerated with 5% HCl regenerant to recover the regenerated solution.

재생액은 pH 6으로 조정하여 에틸아민 기준 20~30%으로 농축하고 20℃로 냉각하였다. 냉각한 농축액을 여과하여 염안과 식염을 제거하였다.The regenerated solution was adjusted to pH 6, concentrated to 20 to 30% based on ethylamine, and cooled to 20 캜. The cooled concentrate was filtered to remove salts and salts.

-- pH 가성소다 조절pH caustic soda control pH 암모니아 조절pH ammonia control 농축농도Concentration concentration EtNH2, %EtNH 2 , % EtNH2,gEtNH 2 , g Na/
EtNH2 Na /
EtNH 2 NH3/
EtNH2 NH 3 /
EtNH 2 EtNH2, %EtNH 2 , % EtNH2,gEtNH 2 , g NH3/
EtNH2 NH 3 /
EtNH 2 원액Undiluted solution 3.4%3.4% 109109 6.1%6.1% 16.1%16.1% 3.5%3.5% 109109 21.0%21.0% 22%
(모액)22%
(Mother liquor) 23.9%23.9% 108108 3.2%3.2% 5.1%5.1% 22.3%22.3% 108108 6.3%6.3% 30%
(모액)30%
(Mother liquor) 38.4%38.4% 106106 0.2%0.2% 1.0%1.0% 37.5%37.5% 107107 0.9%0.9%

상기 표 2에서 확인할 수 있듯이, 재생액 중화 및 농축한 경우 에틸아민의 회수율은 98%이였고, 에틸아민의 순도는 99%이상임을 알 수 있었으며, NH3/EtNH2 몰 정제비가 15-20배 이상임을 알 수 있었다.
As shown in Table 2, when the regeneration liquid was neutralized and concentrated, the recovery rate of ethylamine was 98% and the purity of ethylamine was 99% or more. The NH 3 / EtNH 2 mole purification ratio was 15-20 times Or more.

이상으로 본 발명의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서 이러한 구체적인 기술은 단지 바람직한 구현 예일 뿐이며, 이에 본 발명의 범위가 제한되는 것이 아닌 점은 명백하다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항과 그의 등가물에 의하여 정의된다고 할 것이다.While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the present invention. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (6)

다음의 단계를 포함하는 글루타민과 에틸아민을 기질로 사용하여 전환효소(glutaminase)에 의해 테아닌이 전환 생성되는 효소반응에서 생산된 테아닌 효소반응액으로부터 미반응 에틸아민을 회수 정제하는 방법:
(a) 테아닌 효소반응액을 양이온교환수지에 통액하여 효소반응액 내 테아닌, 에틸아민 및 양이온을 양이온교환수지에 흡착시킨 후 용리하여 테아닌을 회수 및 분리하는 단계;
(b) 상기 양이온 교환수지에 산성 재생제를 통액시켜 미반응 에틸아민 및 양이온을 재생액으로 회수 및 분리하는 단계;
(c) 상기 회수 및 분리된 에틸아민과 양이온을 포함하는 재생액을 염기(base)를 이용하여 pH 3-6으로 조정하고 가열농축하는 단계;
(d) 상기 재생액을 냉각하여 양이온염을 석출시키는 단계; 및
(e) 상기 재생액을 여과하여 석출된 양이온염을 제거하고 에틸아민을 회수하는 단계.
A method for recovering unreacted ethylamine from a theanine enzyme reaction solution produced in an enzyme reaction in which theanine is converted and converted by glutaminase using glutamine and ethylamine as substrates, including the following steps:
(a) passing the theanine enzyme reaction solution through a cation exchange resin, adsorbing theanine, ethylamine and cations in the enzyme reaction solution to the cation exchange resin, and eluting the theanine to recover and separate theanine;
(b) passing the acidic regenerant through the cation exchange resin to recover and separate unreacted ethylamine and cations into a regeneration liquid;
(c) regenerating the recovered solution containing the recovered and separated ethylamine and cations to a pH of 3-6 using a base, and concentrating the mixture by heating;
(d) cooling the regenerant solution to precipitate a cationic salt; And
(e) filtering the regenerated liquid to remove the precipitated cation salt and recovering ethylamine.
제 1 항에 있어서, 상기 단계 (a)의 양이온은 암모늄 이온, 나트륨 이온, 및 칼륨 이온으로 구성된 군으로부터 선택되는 양이온인 것을 특징으로 하는 방법.
The method of claim 1, wherein the cation of step (a) is a cation selected from the group consisting of ammonium ion, sodium ion, and potassium ion.
삭제delete 제 1 항에 있어서, 상기 단계 (c)의 농축은 재생액 부피를 기준으로 하여 에틸아민 20-30 (w/v)% 농도로 실시하는 것을 특징으로 하는 방법.
The method according to claim 1, wherein the concentration of the step (c) is performed at a concentration of 20-30 (w / v)% ethylamine based on the volume of the regeneration liquid.
제 1 항에 있어서, 상기 단계 (d)의 냉각은 온도 20℃ 이하로 실시하는 것을 특징으로 하는 방법.
The method according to claim 1, wherein the cooling in step (d) is performed at a temperature of 20 ° C or lower.
제 1 항에 있어서, 상기 단계 (e)의 양이온염은 염화암모늄, 염화나트륨, 및 염화칼륨인 것을 특징으로 하는 방법.The method of claim 1, wherein the cationic salt of step (e) is ammonium chloride, sodium chloride, and potassium chloride.
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