CN103058882A - Method for separating natural theanine - Google Patents
Method for separating natural theanine Download PDFInfo
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- CN103058882A CN103058882A CN2013100429760A CN201310042976A CN103058882A CN 103058882 A CN103058882 A CN 103058882A CN 2013100429760 A CN2013100429760 A CN 2013100429760A CN 201310042976 A CN201310042976 A CN 201310042976A CN 103058882 A CN103058882 A CN 103058882A
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- resin
- acid
- elutriant
- catechin
- theanine
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Abstract
The invention belongs to the technical field of deep tea processing and discloses a method for separating natural theanine. According to the method, a solution in which catechinic acid is separated or catechinic acid residue serves as a raw material, and natural theanine with the mass percent of more than or equal to 98 percent is separated by means of the technical means of continuous adsorption elution, concentration, alcohol precipitation, crystallization and the like by utilizing cationic resin and anions. An acid-base aqueous solution serves as an eluent, the separated wastewater can be mutually neutralized, the acid-base pollution problem is solved, and the method has the advantages of simple production process, convenient operation and high separation efficiency and is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of method of high efficiency separation natural theanine, belong to field of deep tea processing technology.
Background technology
Theanine (Theanine) is to separate first nineteen fifty to obtain from green tea.Theanine is the highest amino acid of content in the tealeaves, accounts for more than 50% of total free aminoacids total amount, accounts for the 1%-2% of dry weight of tea leaves.Theanine is the white needles body, and is soluble in water, and is insoluble to dehydrated alcohol.Having sweet taste and bright refreshing flavor, is the component of the flavour of tealeaves.Research finds that natural theanine has: improve learning capacity and memory; Calm; Improve the syndromes in menstrual period; The neuroprotective cell; Reduce blood pressure; Strengthen the curative effect of cancer therapy drug; The effects such as fat-reducing.In addition, find that also theanine protects liver, the effect such as anti-oxidant.The security of theanine also is proven.Now, the healthcare products of theanine and theanine interpolation food has begun to come into the market.
Theanine has D type and L-type, and the natural theanine that nature exists is L-type, and the theanine of chemosynthesis mostly is D type and L-type DL body.According to the study, what human body need to and can be absorbed and used is L-thiamine, and the physiological function of D-theanine and activity are still undistinct, and the separation of D-theanine still has very high technical difficulty with removal at present.Therefore, from tealeaves, separate L-thiamine and remain an at present good approach.
The patent of at present relevant theanine extractive technique is more, and patent CN1532186A utilizes high performance liquid chromatography to prepare the theanine of high-content, is difficult to industrialization; Patent CN1546461A can realize suitability for industrialized production, but its complex procedures needs the process multiple adsorb, and repeatedly concentrated, separation costs is high, and efficient is low; Patent CN1587258A operation is simple, but the content of the theanine that separates is not high; Patent CN1871206A process is complicated, trivial operations; Patent CN101020649A has obtained preferably separating effect, but processing step is more, and need use propyl carbinol; Patent CN101058548A adopts membrane sepn and positively charged ion or anion fiber column chromatography, the theanine content about 40% of production.Aspect the separation of theanine, mainly there is complex procedures, production cost is high, and efficient is low, the common problems such as not environmental protection.
Summary of the invention
For above the deficiencies in the prior art, the object of the present invention is to provide a kind of method of high efficiency separation natural theanine, the method behind the separating catechin solution or the catechin slag as raw material, utilize the technique means such as resin cation (R.C.) and negatively charged ion continuous adsorption wash-out, concentrated, alcohol precipitation, crystallization to separate the natural theanine of preparation quality content 〉=98%.The present invention is take the aqueous solution of acid, alkali as eluent, and the waste water after the separation can neutralize mutually, has solved the soda acid pollution problem, and simultaneously production process is simple, easy to operate, separation efficiency is high, is suitable for the large-scale industrial production.
For achieving the above object, technical scheme of the present invention is:
A kind of method of separating natural theanine, concrete steps are:
(1) preparation of stock liquid: will be from green tea extractive liquor behind the separating catechin surplus solution or catechin pulp water solution add adjusting PH with base value to 8 ~ 12, get stock liquid; Described catechin pulp water solution refers to that the catechin slag is added deionized water is mixed with the aqueous solution that mass concentration is 5%-10%; Described catechin slag is the dry thing of surplus solution behind the separating catechin from green tea extractive liquor;
(2) resin anion(R.A) absorption: stock liquid is carried out ion-exchange absorption by the chromatography column I that resin anion(R.A) is housed; Described resin anion(R.A) is strong-basicity styrene series anion exchange resin;
(3) resin anion(R.A) gradient elution: use first the deionized water wash-out resin anion(R.A) of 3 ~ 5 times of chromatography column I column volumes, gained elutriant a discards; The pH value of using again 2 ~ 3 times of chromatography column I column volumes be 5 ~ 6 contain the aqueous acid wash-out, gained elutriant b discards; Then the pH value of using 2 ~ 3 times of chromatography column I column volumes be 2 ~ 3 contain aqueous acid wash-out resin anion(R.A), get elutriant c; Described acid is selected from one or more in citric acid, hydrochloric acid, sulfuric acid and the acetic acid;
(4) resin cation (R.C.) absorption: elutriant c is directly carried out ion-exchange absorption by the chromatography column II that resin cation (R.C.) is housed; Described resin cation (R.C.) is storng-acid cation exchange resin;
(5) resin cation (R.C.) wash-out: use first the deionized water wash-out resin cation (R.C.) of 6 ~ 8 times of chromatography column II column volumes, elutriant d discards; The pH value of using again 2 ~ 3 times of resin cation (R.C.) chromatography column II column volumes is 10 ~ 12 ammoniacal liquor wash-out resin cation (R.C.), collects elutriant e;
(6) concentrated: as the elutriant e that collects to be concentrated into 24 ~ 28 degree Beaume, to get concentrated solution;
(7) alcohol precipitation: add dehydrated alcohol in concentrated solution, make the ethanol mass concentration reach 75% ~ 85%, then filtering separation gets throw out;
(8) crystallization: with the throw out heating for dissolving, after the cooling, place crystallization 20h-24h under 1 ℃ ~ 5 ℃ the condition with the deionized water that is equivalent to 3 ~ 4 times of quality of throw out, centrifugation gets crystal;
(9) drying: with crystal vacuum-drying, get theanine.
Alkali is preferably selected from one or more in sodium hydroxide, sodium bicarbonate, yellow soda ash and the ammoniacal liquor described in the described step (1).
Theanine content is preferably greater than 2% in solution described in the step (1) behind the separating catechin or the catechin slag.
Resin anion(R.A) is preferably selected from any one among AmberliteIRA-400, Diaion SA-10A or the LewatitM500 described in the step (2).
Resin cation (R.C.) is preferably selected from Amberlite IRA-200 described in the step (4), Lewatit-sp120, any one among Diaion PK or the D001.
Solution behind the described separating catechin or catechin slag refer to isolate the compositions such as catechin from green tea extractive liquor after, remaining solution or its dry thing, wherein mainly contain the compositions such as amino acid, polysaccharide, alkaloid, theanine content is generally 2 ~ 3% greater than 2%.The separation method of catechin is preferably:--column chromatography or extraction--concentrate--spraying drying or lyophilize--catechin through Aqua pure extract with green tea materials.
The below does further explanation and explanation to the present invention:
Gordian technique of the present invention is to utilize resin anion(R.A) and resin cation (R.C.), adopts and crosses first resin anion(R.A), and pickling is taken off; After resin cation (R.C.), the technical scheme of ammoniacal liquor wash-out.Theanine is amphiprotic substance, and is electronegative under alkaline condition, can be better and resin anion(R.A) generation exchange adsorption, therefore stock liquid pH value is transferred to 8 ~ 12.Adjusting by the pH value makes the theanine can be fully and resin anion(R.A) generation exchange adsorption, can obviously improve adsorption rate.
The resin anion(R.A) gradient elution: use first the deionized water wash-out resin anion(R.A) of 3 ~ 5 times of chromatography column I column volumes, elutriant a discards; Purpose is that the impurity that can not exchange is washed off.The pH value of using again 2 ~ 3 times of chromatography column I column volumes be 5 ~ 6 contain the aqueous acid wash-out, elutriant b discards; Purpose is other amino acid materials of wash-out, can wash to a great extent other amino acid materials off in this PH section.Then the pH value of using 2 ~ 3 times of chromatography column I column volumes be 2 ~ 3 contain aqueous acid wash-out resin anion(R.A), get elutriant c; When adsorbing with resin anion(R.A), the pH value should be controlled at 2 ~ 3 and be advisable, and has preferably elute effect.Described acid is selected from one or more in citric acid, hydrochloric acid, sulfuric acid and the acetic acid;
Resin cation (R.C.) absorption: elutriant c is directly carried out ion-exchange absorption by the chromatography column II that resin cation (R.C.) is housed; Described resin cation (R.C.) is storng-acid cation exchange resin;
The resin cation (R.C.) wash-out: use first the deionized water wash-out resin cation (R.C.) of 6 ~ 8 times of chromatography column II column volumes, elutriant d discards; (purpose is that the impurity that can not exchange is washed off) uses the pH value of 2 ~ 3 times of resin cation (R.C.) chromatography column II column volumes again is 10 ~ 12 ammoniacal liquor wash-out resin cation (R.C.), collects elutriant e; The pH value is controlled at 10 ~ 12, has preferably elute effect.
Adopt and cross first resin anion(R.A), pickling is taken off; After resin cation (R.C.), the ammoniacal liquor wash-out; So that final collection liquid is the ammoniacal liquor stripping liquid, rather than acidolysis imbibition, well solved concentrated problem, only need once concentration to get final product, because: when concentrated, preferably acid can not be arranged in the concentrated solution, acid meeting and theanine are mixed in together, reduce the purity of theanine, and can cause corrosion to equipment; Therefore washing lotion before concentrated is alkalescence preferably, and ammoniacal liquor has volatility, not only can not mix with theanine, also can not cause damage to equipment, is suitable elutriant, and control pH value has preferably elute effect 10 ~ 12.
Compared with prior art, advantage of the present invention is:
1, the present invention adopts the resin anion(R.A) gradient elution technique, and the content of theanine in the stripping liquid of collection is improved greatly, and its dry matter content surpasses 50%;
2, the present invention adopts and crosses first resin anion(R.A), and pickling is taken off; After resin cation (R.C.), the ammoniacal liquor wash-out; Do not cross first resin cation (R.C.) and adopt, alkali cleaning is taken off, after resin anion(R.A), and the mode that pickling is taken off, so that final collection liquid is the ammoniacal liquor stripping liquid, rather than the acidolysis imbibition, thereby concentrated problem well solved, only need to concentrate once, reduced energy consumption, improved efficient.
3, to have operation simple, easy to operate in the present invention, yield high (total recovery＞73%), and cost is low, and purity high (theanine content 〉=98%) is easy to industrialization;
4, the solvent used of the present invention only is: acid, alkali, ethanol and deionized water.Ethanol can recycling, and the waste water that the aqueous solution of acid, alkali produces can neutralize at last mutually, has solved the soda acid pollution problem.
Embodiment
The present invention is described further below in conjunction with embodiment.
Embodiment 1
Get 20kg catechin slag (theanine content 2.50%), be made into 5% the aqueous solution, add an amount of sodium hydroxide, pH is transferred to 10, solution with 1 times of column volume/hour flow velocity by the AmberliteIRA-400 resin anion(R.A), use first the deionized water wash-out resin of 4 times of column volumes (resin anion(R.A) chromatography column I), elutriant a discards; Using 2 times of column volumes (resin anion(R.A) chromatography column I) pH value is 5 the aqueous solution (preparing with acetic acid) wash-out again, and elutriant b discards; Then using 3 times of column volumes (resin anion(R.A) chromatography column I) pH value is 2.5 the aqueous solution (preparing with hydrochloric acid) wash-out, collects elutriant c, with the elutriant c that collects directly by Zeo-karb D001 chromatography column II.With the deionized water wash-out resin of 6 times of column volumes (resin cation (R.C.) chromatography column II), elutriant d discards; Using 3 times of column volumes (resin cation (R.C.) chromatography column II) pH value is 11 the aqueous solution (preparing with strong aqua) wash-out cationic resin column again, collects elutriant e.With external circulation vacuum concentrator the elutriant e that collects is concentrated into 27.5 degree Beaume, the dry detection level of taking a sample is 75.38%.Add dehydrated alcohol in the concentrated solution, make alcohol concn reach 80%, sedimentation and filtration is separated, precipitation sampling drying after testing content is 88.22%; To precipitate with 4 times of sedimentary deionized water heating for dissolving of amount, after the cooling, place crystallization 24h under 4 ℃ the condition, the centrifugation crystal.With crystal vacuum-drying, get 385g after the drying, content is 98.16% after testing, the theanine yield is 75.6%.
Embodiment 2
(solid substance is 4.8% after testing to get waste liquid behind the 400kg separating catechin, the dry sample theanine content of taking a sample is 2.86%), add an amount of yellow soda ash, pH is transferred to 10, solution with 1 times of column volume/hour flow velocity by LewatitM500 resin anion(R.A) chromatography column I, use first the deionized water wash-out resin of 5 times of column volumes (resin anion(R.A) chromatography column I), elutriant a discards; Using 3 times of column volumes (resin anion(R.A) chromatography column I) pH value is 6 the aqueous solution (preparing with citric acid) wash-out again, and elutriant is abandoned b and gone; Then using 2 times of column volumes (resin anion(R.A) chromatography column I) pH value is 2 the aqueous solution (preparing with sulfuric acid) wash-out, collects elutriant c.The elutriant c that collects is directly passed through Zeo-karb Lewatit-sp120 chromatography column II.With the deionized water wash-out resin of 8 times of column volumes (resin cation (R.C.) chromatography column II), elutriant d discards; Using 2 times of column volumes (resin cation (R.C.) chromatography column II) pH value is 12 the aqueous solution (preparing with strong aqua) wash-out cationic resin column again, collects elutriant e.With external circulation vacuum concentrator the elutriant e that collects is concentrated into 26 degree Beaume, the dry detection level of taking a sample is 74.55%.Add dehydrated alcohol in the concentrated solution, make alcohol concn reach 75%, sedimentation and filtration is separated, precipitation sampling drying after testing content is 86.38%; To precipitate with 4 times of sedimentary deionized water heating for dissolving of amount, after the cooling, place crystallization 24h under 4 ℃ the condition, the centrifugation crystal.With crystal vacuum-drying, get 412g after the drying, content is 97.46% after testing, the theanine yield is 73.1%.
Claims (5)
1. the method for a separating natural theanine is characterized in that, concrete steps are:
(1) preparation of stock liquid: will be from green tea extractive liquor behind the separating catechin surplus solution or catechin pulp water solution add adjusting PH with base value to 8 ~ 12, get stock liquid; Described catechin pulp water solution refers to that the catechin slag is added deionized water is mixed with the aqueous solution that mass concentration is 5%-10%; Described catechin slag is the dry thing of surplus solution behind the separating catechin from green tea extractive liquor;
(2) resin anion(R.A) absorption: stock liquid is carried out ion-exchange absorption by the chromatography column I that resin anion(R.A) is housed; Described resin anion(R.A) is strong-basicity styrene series anion exchange resin;
(3) resin anion(R.A) gradient elution: use first the deionized water wash-out resin anion(R.A) of 3 ~ 5 times of chromatography column I column volumes, gained elutriant a discards; The pH value of using again 2 ~ 3 times of chromatography column I column volumes be 5 ~ 6 contain the aqueous acid wash-out, gained elutriant b discards; Then the pH value of using 2 ~ 3 times of chromatography column I column volumes be 2 ~ 3 contain aqueous acid wash-out resin anion(R.A), get elutriant c; Described acid is selected from one or more in citric acid, hydrochloric acid, sulfuric acid and the acetic acid;
(4) resin cation (R.C.) absorption: elutriant c is directly carried out ion-exchange absorption by the chromatography column II that resin cation (R.C.) is housed; Described resin cation (R.C.) is storng-acid cation exchange resin;
(5) resin cation (R.C.) wash-out: use first the deionized water wash-out resin cation (R.C.) of 6 ~ 8 times of chromatography column II column volumes, elutriant d discards; The pH value of using again 2 ~ 3 times of resin cation (R.C.) chromatography column II column volumes is 10 ~ 12 ammoniacal liquor wash-out resin cation (R.C.), collects elutriant e;
(6) concentrated: as the elutriant e that collects to be concentrated into 24 ~ 28 degree Beaume, to get concentrated solution;
(7) alcohol precipitation: add dehydrated alcohol in concentrated solution, make the ethanol mass concentration reach 75% ~ 85%, then filtering separation gets throw out;
(8) crystallization: with the throw out heating for dissolving, after the cooling, place crystallization 20h-24h under 1 ℃ ~ 5 ℃ the condition with the deionized water that is equivalent to 3 ~ 4 times of quality of throw out, centrifugation gets crystal;
(9) drying: with crystal vacuum-drying, get theanine.
2. the method for a kind of separating natural theanine according to claim 1 is characterized in that, alkali is selected from one or more in sodium hydroxide, sodium bicarbonate, yellow soda ash and the ammoniacal liquor described in the described step (1).
3. the method for a kind of separating natural theanine according to claim 1 is characterized in that, theanine content is greater than 2% in the solution described in the step (1) behind the separating catechin or the catechin slag.
4. the method for a kind of separating natural theanine according to claim 1 is characterized in that, resin anion(R.A) is selected from any one among AmberliteIRA-400, Diaion SA-10A or the LewatitM500 described in the step (2).
5. the method for a kind of separating natural theanine according to claim 1 is characterized in that, resin cation (R.C.) is selected from Amberlite IRA-200 described in the step (4), Lewatit-sp120, any one among Diaion PK or the D001.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107235854A (en) * | 2017-07-28 | 2017-10-10 | 贵州芳瑞堂生物科技有限公司 | A kind of extracting method of Theanine in Tea |
| CN111620791A (en) * | 2020-06-01 | 2020-09-04 | 浙江天草生物科技股份有限公司 | Method for purifying crude product of natural theanine |
| CN112479923A (en) * | 2021-01-11 | 2021-03-12 | 华茂(湖州)保健品有限公司 | Method for extracting theanine from tea polyphenol industrial waste liquid |
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| EP0884953B1 (en) * | 1996-02-26 | 2001-12-12 | The Procter & Gamble Company | Green tea extract subjected to cation exchange treatment and nanofiltration to improve clarity and color |
| CN1546461A (en) * | 2003-12-04 | 2004-11-17 | 中国农业科学院茶叶研究所 | Theanine extraction process |
| WO2005042470A1 (en) * | 2003-10-21 | 2005-05-12 | The Procter & Gamble Company | Process for enriching extracts of natural theanine |
| CN101020649A (en) * | 2007-03-12 | 2007-08-22 | 江南大学 | Process of separating and purifying natural theanine |
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2013
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Patent Citations (4)
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| EP0884953B1 (en) * | 1996-02-26 | 2001-12-12 | The Procter & Gamble Company | Green tea extract subjected to cation exchange treatment and nanofiltration to improve clarity and color |
| WO2005042470A1 (en) * | 2003-10-21 | 2005-05-12 | The Procter & Gamble Company | Process for enriching extracts of natural theanine |
| CN1546461A (en) * | 2003-12-04 | 2004-11-17 | 中国农业科学院茶叶研究所 | Theanine extraction process |
| CN101020649A (en) * | 2007-03-12 | 2007-08-22 | 江南大学 | Process of separating and purifying natural theanine |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107235854A (en) * | 2017-07-28 | 2017-10-10 | 贵州芳瑞堂生物科技有限公司 | A kind of extracting method of Theanine in Tea |
| CN107235854B (en) * | 2017-07-28 | 2019-11-15 | 贵州芳瑞堂生物科技有限公司 | A kind of extracting method of Theanine in Tea |
| CN111620791A (en) * | 2020-06-01 | 2020-09-04 | 浙江天草生物科技股份有限公司 | Method for purifying crude product of natural theanine |
| CN111620791B (en) * | 2020-06-01 | 2023-01-31 | 浙江天草生物科技股份有限公司 | Method for purifying crude product of natural theanine |
| CN112479923A (en) * | 2021-01-11 | 2021-03-12 | 华茂(湖州)保健品有限公司 | Method for extracting theanine from tea polyphenol industrial waste liquid |
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