JP3138781B2 - Method for removing caffeine from aqueous solution containing caffeine - Google Patents
Method for removing caffeine from aqueous solution containing caffeineInfo
- Publication number
- JP3138781B2 JP3138781B2 JP04316650A JP31665092A JP3138781B2 JP 3138781 B2 JP3138781 B2 JP 3138781B2 JP 04316650 A JP04316650 A JP 04316650A JP 31665092 A JP31665092 A JP 31665092A JP 3138781 B2 JP3138781 B2 JP 3138781B2
- Authority
- JP
- Japan
- Prior art keywords
- caffeine
- aqueous solution
- clay
- solution containing
- acid
- 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
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、水溶液からカフェイン
を除去する方法に関し、さらに詳しくは活性白土または
酸性白土を吸着剤として用いる選択的吸着によってカフ
ェイン含有水溶液からカフェインを除去する方法に関す
る。The present invention relates to a method for removing caffeine from an aqueous solution, and more particularly to a method for removing caffeine from a caffeine-containing aqueous solution by selective adsorption using activated clay or acidic clay as an adsorbent. .
【０００２】[0002]
【従来の技術】アルカロイドであるカフェインは各種の
植物、特にコーヒーや茶などの嗜好飲料の原料である植
物に多く含まれる。強い中枢神経興奮作用を有するカフ
ェインを過剰に摂取すると健康人でも極度の興奮，神経
過敏，吐き気，不眠などの有害作用を引き起こす。心疾
患や胃潰瘍の患者には、特に悪影響を及ぼすと言われ、
またカフェインは胎盤を通過したり、母乳中に容易に移
行することから妊娠周辺期の女性では過剰の摂取に注意
が必要であるとの指摘もある。従って、カフェイン含有
飲料から、特にそれらの他の特性に悪影響を与えること
なく、カフェインを除去する試みが検討されてきた。こ
れまでに水溶液からカフェインを除去する方法として、
塩化メチレンあるいはクロロホルムなどの有機溶媒を用
いる方法，超臨界流体の使用によるカフェインの除去方
法などの試みがある。しかしながら、有機溶媒を用いる
方法は取扱いに危険が伴い、かつ消費者は有機溶媒と食
品との接触を望まないなどの欠点がある。超臨界二酸化
炭素等を用いた超臨界抽出によるカフェインの除去は、
高圧における操作を必要とし、高価な装置を用いるなど
コストがかかりすぎる等の問題がある。上記のカフェイ
ン除去方法に加えて、活性炭，ゼオライトなどの吸着剤
およびイオン交換樹脂の使用によりカフェインを減少さ
せる試みもある。しかしながら、これらの方法はカフェ
イン以外の望ましい風味や香気成分をも吸着し除去する
という問題があり、充分満足のいくものではない。2. Description of the Related Art Caffeine, which is an alkaloid, is abundantly contained in various plants, in particular, plants that are raw materials of favorite beverages such as coffee and tea. Excessive intake of caffeine, which has a strong central nervous excitatory effect, can cause adverse effects such as extreme excitement, irritability, nausea, and insomnia, even in healthy individuals. It is said to have a particularly bad effect on patients with heart disease and gastric ulcer,
It has also been pointed out that caffeine crosses the placenta and is easily transferred into breast milk, so it is necessary to pay attention to excessive intake in women around the pregnancy. Accordingly, attempts have been made to remove caffeine from caffeine-containing beverages, particularly without adversely affecting their other properties. As a method of removing caffeine from aqueous solutions,
There have been attempts to use an organic solvent such as methylene chloride or chloroform, and to remove caffeine by using a supercritical fluid. However, the method using an organic solvent has drawbacks such that handling is dangerous and consumers do not want to contact the organic solvent with food. Removal of caffeine by supercritical extraction using supercritical carbon dioxide, etc.
There is a problem that the operation at a high pressure is required and the cost is too high, such as using an expensive device. In addition to the caffeine removal methods described above, attempts have been made to reduce caffeine by using adsorbents such as activated carbon and zeolite and ion exchange resins. However, these methods have a problem of adsorbing and removing desirable flavors and aroma components other than caffeine, and are not sufficiently satisfactory.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、カフェイン
を含有する水溶液より選択的にカフェインを除去する方
法を提供することを目的とする。An object of the present invention is to provide a method for selectively removing caffeine from an aqueous solution containing caffeine.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、茶あるい
はコーヒーなどのカフェインを含有する水溶液を特定の
吸着剤と接触させることにより、水溶液から選択的にカ
フェインを除去する方法を検討した結果、活性白土また
は酸性白土をカフェインを含有する水溶液と接触させる
ことにより、操作が容易簡便で、かつ効率よく工業的に
カフェインを除去できることを見いだした。すなわち本
発明は、カフェインを含有する水溶液から選択的にカフ
ェインを除去する方法である。本発明におけるカフェイ
ンを含有する水溶液としてはコーヒー，カカオ，コー
ラ，紅茶，ウーロン茶，緑茶，マテ茶などのカフェイン
含有植物の抽出液が主として用いられるが、その他の植
物の抽出液、あるいは合成カフェイン含有液でも用いる
ことができる。カフェイン含有植物の抽出液を得るには
温水、好ましくは熱水を用いて抽出することができる
が、カフェイン含有植物を有機溶媒により抽出した後、
その有機溶媒を除去して得た水溶液でもよい。抽出操作
はバッチ式、またはカラムによる連続式等の従来既知の
抽出方法をそのまま採用することができる。吸着剤によ
る物質の除去手段は極めて一般的な方法であるが、通常
使用され得る吸着剤、例えば活性炭、イオン交換樹脂、
吸着用樹脂ではカフェイン含有水溶液中の他の成分も同
時に吸着してしまい、カフェインを選択的に除去するこ
とができなかった。本発明に用いる活性白土は、天然に
産出する酸性白土（モンモリロナイト系粘土）を硫酸な
どの鉱酸で処理したものであり、大きい比表面積と吸着
能を有する多孔質構造をもった化合物である。酸性白土
を更に、酸処理することにより比表面積が変化し、脱色
能の改良および物性が変化することが知られている。通
常活性白土は、油脂の脱色能，不純物吸着能を有するこ
とから主として、油脂及び石油鉱物油の精製に使用され
る。本発明において、酸性白土もその目的に適するが、
より効果的な目的達成のためには活性白土の使用が望ま
しい。活性白土，酸性白土は、共に一般的な化学成分と
して、ＳｉＯ2 ，Ａｌ2Ｏ3 ，Ｆｅ2Ｏ3 ，ＣａＯ，Ｍｇ
Ｏなどを有するが、本発明に使用する場合、ＳｉＯ2 ／
Ａｌ2Ｏ3 比は、３．０〜１２．０，望ましくは、５．
０〜９．０が適し、Ｆｅ2Ｏ3 ２〜５％，ＣａＯ ０〜
１．５％，ＭｇＯ １〜７％などを含有する組成のもの
が望ましい。また、比表面積は、酸処理の程度により異
なるが、５０〜３５０ｍ2 ／ｇ，ｐＨ（５％サスペンジ
ョン）は、２．５〜３．５の範囲のものが使用される。
カフェイン含有水溶液と活性白土または酸性白土との接
触処理はバッチ式、カラムによる連続処理等のいかなる
方法も採用することができる。一般的には粉末状活性白
土または酸性白土を添加，撹拌しカフェインを吸着後、
濾過操作によりカフェインを除去した濾液を得る方法、
あるいは顆粒状の活性白土または酸性白土を充填したカ
ラムを用いて連続処理によりカフェインを吸着する方法
が採用される。上記接触処理の条件はカフェイン含有水
溶液の種類，抽出液の濃度などに応じて適宜選択するこ
とができるが、例えばカラムによる連続処理の場合、顆
粒状の活性白土または酸性白土１容量に対して、約１〜
１００容量のカフェイン含有水溶液を通液することによ
り達成できる。かくして得られたカフェインを除去した
カラム通過液をそのまま、または減圧あるいは常圧にて
濃縮した後、噴霧乾燥，凍結乾燥，熱風乾燥等の既知の
方法により乾燥して粉末状，顆粒状その他の固体形態と
することもできる。また、活性白土または酸性白土に吸
着したカフェインを必要に応じて含水アセトンなどの有
機溶媒を用いて、溶出することも可能である。本発明の
有効性を、試験例，実施例により説明する。Means for Solving the Problems The present inventors have studied a method for selectively removing caffeine from an aqueous solution by bringing an aqueous solution containing caffeine such as tea or coffee into contact with a specific adsorbent. As a result, it has been found that, by bringing the activated clay or the acid clay into contact with an aqueous solution containing caffeine, the operation is easy and simple, and the caffeine can be industrially removed efficiently. That is, the present invention is a method for selectively removing caffeine from an aqueous solution containing caffeine. As the aqueous solution containing caffeine in the present invention, an extract of caffeine-containing plants such as coffee, cacao, cola, black tea, oolong tea, green tea, and mate tea is mainly used. An in-containing liquid can also be used. To obtain an extract of a caffeine-containing plant, it can be extracted using hot water, preferably hot water, but after extracting the caffeine-containing plant with an organic solvent,
An aqueous solution obtained by removing the organic solvent may be used. As the extraction operation, a conventionally known extraction method such as a batch type or a continuous type using a column can be employed as it is. Means for removing a substance by an adsorbent is a very common method, but an adsorbent which can be usually used, for example, activated carbon, ion exchange resin,
With the resin for adsorption, other components in the aqueous solution containing caffeine were also adsorbed at the same time, so that caffeine could not be selectively removed. The activated clay used in the present invention is obtained by treating a naturally occurring acidic clay (montmorillonite clay) with a mineral acid such as sulfuric acid, and is a compound having a large specific surface area and a porous structure having an adsorptive capacity. It is known that the acid surface treatment of acid clay further changes the specific surface area, thereby improving the decoloring ability and changing the physical properties. Usually, activated clay is mainly used for refining fats and oils and petroleum mineral oils because of its ability to decolorize fats and oils and absorb impurities. In the present invention, acid clay is also suitable for the purpose,
In order to achieve a more effective purpose, it is desirable to use activated clay. Activated clay and acid clay are both common chemical components, such as SiO 2 , Al 2 O 3 , Fe 2 O 3 , CaO, and Mg.
O or the like, but when used in the present invention, SiO 2 /
The Al 2 O 3 ratio is 3.0 to 12.0, preferably 5.
0 to 9.0 is suitable, Fe 2 O 3 2~5%, CaO 0~
A composition containing 1.5%, MgO 1 to 7% or the like is desirable. The specific surface area varies depending on the degree of the acid treatment, but a specific surface area of 50 to 350 m 2 / g and a pH (5% suspension) of 2.5 to 3.5 is used.
The contact treatment between the caffeine-containing aqueous solution and the activated clay or the acid clay can be performed by any method such as a batch method and a continuous treatment using a column. Generally, powdered activated clay or acid clay is added and stirred to adsorb caffeine.
A method of obtaining a filtrate from which caffeine has been removed by a filtration operation,
Alternatively, a method of adsorbing caffeine by continuous treatment using a column filled with granular activated clay or acid clay is employed. The conditions of the contact treatment can be appropriately selected according to the kind of the caffeine-containing aqueous solution, the concentration of the extract, and the like. For example, in the case of continuous treatment using a column, 1 volume of granular activated clay or acidic clay is used. , About 1
This can be achieved by passing 100 volumes of an aqueous solution containing caffeine. The thus-obtained liquid passing through the column from which caffeine has been removed is concentrated as it is or under reduced pressure or normal pressure, and then dried by a known method such as spray drying, freeze drying, hot air drying, etc. to obtain a powder, granule or other powder. It can also be in solid form. In addition, caffeine adsorbed on activated clay or acid clay can be eluted using an organic solvent such as aqueous acetone as necessary. The effectiveness of the present invention will be described with reference to test examples and examples.
【０００５】[0005]
試験例１ 緑茶抽出物粉末４０ｍｇを５ｍｌの脱イオン水に溶解
し、各種吸着剤を１ｇ添加し、時々撹拌しながら室温に
て３０分間保ち、上清液中のカフェインおよび緑茶ポリ
フェノールである（−）−エピカテキン（ＥＣ），
（−）−エピカテキンガレート（ＥＣｇ），（−）−エ
ピガロカテキンガレート（ＥＧＣｇ）の残存量をＨＰＬ
Ｃにより分析し、チャート上のピーク面積より残存量を
比較した。吸着剤として、カラムライト（メタケイ酸ア
ルミン酸マグネシウム，富士化学工業社製），活性炭
（粒状白鷺，武田薬品工業社製），ケラチン（ナカライ
テスク社製），セルロース粉末（片山化学工業社製），
シルトンＥＰ（水澤化学社製），トクシールＮ（徳山曹
達社製），ロカヘルプ（パーライト，三井金属鉱業社
製），ゼオライト５Ａ（水澤化学社製），ゼオライト13
Ｘ（水澤化学社製），キトパールＢＬ−０３（富士紡績
社製），ガレオンアースＮＦ−２（活性白土，水澤化学
社製），ガレオナイトＮｏ．２５１（活性白土，水澤化
学社製），活性白土（ナカライテスク社製），酸性白土
（ナカライテスク社製），の14種類を用いて試験した。
ＨＰＬＣ分析条件は、カラム：ＯＤＳ−Ｐ−５（野村化
学製），移動相：酢酸／アセトニトリル／ジメチルホル
ムアミド／水＝３／１／１５／８１，検出：ＵＶ２８０
ｎｍ，流速：０．５ｍｌ／ｍｉｎで行った。Test Example 1 40 mg of green tea extract powder was dissolved in 5 ml of deionized water, 1 g of various adsorbents were added, and the mixture was kept at room temperature for 30 minutes with occasional stirring. The supernatant was caffeine and green tea polyphenol ( −)-Epicatechin (EC),
The remaining amount of (-)-epicatechin gallate (ECg) and (-)-epigallocatechin gallate (EGCg) was determined by HPL.
Analysis was performed by C, and the remaining amount was compared based on the peak area on the chart. As an adsorbent, column light (magnesium aluminate metasilicate, manufactured by Fuji Chemical Co., Ltd.), activated carbon (granular Shirasagi, manufactured by Takeda Pharmaceutical Co., Ltd.), keratin (manufactured by Nakarai Tesque Co., Ltd.), cellulose powder (manufactured by Katayama Chemical Co., Ltd.),
Shilton EP (manufactured by Mizusawa Chemical Co., Ltd.), Toksil N (manufactured by Tokuyama Soda Co., Ltd.), LocaHelp (Perlite, manufactured by Mitsui Mining & Smelting Co., Ltd.), Zeolite 5A (manufactured by Mizusawa Chemical Co., Ltd.), zeolite 13
X (manufactured by Mizusawa Chemical), Chitopearl BL-03 (manufactured by Fuji Boseki), Galeon Earth NF-2 (activated clay, manufactured by Mizusawa Chemical), Galeonite No. 251 (active clay, manufactured by Mizusawa Chemical Co., Ltd.), activated clay (manufactured by Nacalai Tesque), and acid clay (manufactured by Nakarai Tesque) were used for the test.
HPLC analysis conditions were as follows: column: ODS-P-5 (manufactured by Nomura Chemical), mobile phase: acetic acid / acetonitrile / dimethylformamide / water = 3/1/15/81, detection: UV280
nm, flow rate: 0.5 ml / min.
【０００６】[0006]
【表１】 [Table 1]
【０００７】表１に示すように活性白土（ガレオンアー
スＮＦ−２，ガレオナイトＮｏ．２５１）または酸性白
土を用いた場合、カフェイン残存量が０．１％，５．０
％，５．４％，７．０％となり、カフェインはほぼ完全
に除去された。一方、主要な茶成分である（−）−エピ
カテキン（ＥＣ），（−）−エピカテキンガレート（Ｅ
Ｃｇ），（−）−エピガロカテキンガレート（ＥＧＣ
ｇ）は、いずれも８０％以上の残存量を示し、選択的に
カフェインが除去された。他の吸着剤では、カフェイン
がほとんど除去されないか、あるいは他の茶成分も同時
に除去されカフェインの選択的な除去効果はみられなか
った。As shown in Table 1, when activated clay (Galeon earth NF-2, Galeonite No. 251) or acid clay is used, the residual amount of caffeine is 0.1%, 5.0.
%, 5.4% and 7.0%, and caffeine was almost completely removed. On the other hand, the main tea components (-)-epicatechin (EC) and (-)-epicatechin gallate (E
Cg), (−)-epigallocatechin gallate (EGC
g) shows a residual amount of 80% or more, and caffeine was selectively removed. With other adsorbents, caffeine was hardly removed, or other tea components were also removed at the same time, and there was no effect of selectively removing caffeine.
【０００８】試験例２ 市販インスタントコーヒー（ブレンディ，味の素ゼネラ
ルフーヅ社製）２０ｍｇを５ｍｌの脱イオン水に溶解
し、試験例１と同様に各種吸着剤を添加し、時々撹拌し
ながら室温に３０分間保った。上清液を試験例１と同様
にＨＰＬＣにて分析し、カフェインおよびクロロゲン酸
の残存量を比較した。Test Example 2 20 mg of commercial instant coffee (Blendy, Ajinomoto General Foods, Inc.) was dissolved in 5 ml of deionized water, various adsorbents were added as in Test Example 1, and the mixture was kept at room temperature for 30 minutes with occasional stirring. Was. The supernatant was analyzed by HPLC in the same manner as in Test Example 1, and the remaining amounts of caffeine and chlorogenic acid were compared.
【０００９】[0009]
【表２】 [Table 2]
【００１０】表２に示すように活性白土（ガレオンアー
スＮＦ−２）０．１ｇを添加することにより、カフェイ
ンの残存率は、５．２％となりカフェインはほぼ完全に
除去された。また、酸性白土１ｇの添加でカフェインの
残存率は８．９％であった。主要成分であるクロロゲン
酸は各々８３．１％，９５．４％の残存量を示し、選択
的にカフェインが除去された。他の吸着剤では、カフェ
インがほとんど除去されないか、あるいはクロロゲン酸
も同時に除去され、カフェインの選択的な除去効果は見
られなかった。As shown in Table 2, by adding 0.1 g of activated clay (Galeon earth NF-2), the residual ratio of caffeine was 5.2%, and caffeine was almost completely removed. In addition, the residual ratio of caffeine was 8.9% by adding 1 g of acid clay. Chlorogenic acid, which is a main component, showed 83.1% and 95.4% residual amounts, respectively, and caffeine was selectively removed. With other adsorbents, caffeine was hardly removed or chlorogenic acid was also removed at the same time, and no selective effect of removing caffeine was observed.
【００１１】実施例１ 煎茶２００ｇを８５℃の熱水４リットルで３０分間撹拌
しながら抽出し、茶葉を濾過により除き、3,400 ｍｌの
抽出液を得た。この抽出液に活性白土２００ｇを添加
し、３０分間撹拌後濾過した。濾過液を減圧濃縮により
Ｂｒｉｘ３０度まで濃縮し凍結乾燥した固形物のカフェ
イン含量は、０．３２％であった。これは除去率９１．
４％に相当する。Example 1 200 g of green tea was extracted with 4 liters of hot water at 85 ° C. while stirring for 30 minutes, and the tea leaves were removed by filtration to obtain 3,400 ml of an extract. 200 g of activated clay was added to this extract, stirred for 30 minutes and filtered. The filtrate was concentrated under reduced pressure to Brix 30 ° C. and freeze-dried, and the caffeine content of the solid was 0.32%. This is a removal rate of 91.
This corresponds to 4%.
【００１２】実施例２ 粉茶２００ｇを８５℃の熱水４リットルで３０分間撹拌
しながら抽出した。得られた抽出液に２倍量の酢酸エチ
ルを加え、激しく撹拌した後、酢酸エチル層を分離し
た。減圧下、酢酸エチルを除去し、固形物１２ｇを得
た。得られた固形物１２ｇを水６００ｍｌに溶解し酸性
白土６０ｇを添加し３０分間撹拌後、濾過した。濾液を
濃縮後、常法により噴霧乾燥して得た粉末のカフェイン
含量は０．８％であった。これは除去率９２．８％に相
当する。Example 2 200 g of powdered tea was extracted with 4 liters of hot water at 85 ° C. with stirring for 30 minutes. To the obtained extract, twice the amount of ethyl acetate was added, and the mixture was vigorously stirred. Then, an ethyl acetate layer was separated. Ethyl acetate was removed under reduced pressure to obtain 12 g of a solid. 12 g of the obtained solid was dissolved in 600 ml of water, 60 g of acid clay was added, and the mixture was stirred for 30 minutes and filtered. After concentrating the filtrate, the powder obtained by spray drying by a conventional method had a caffeine content of 0.8%. This corresponds to a removal rate of 92.8%.
【００１３】実施例３ ６段階からなる多段向流抽出器中にコーヒー豆2.5 ｋｇ
を入れ、給水温度を約１８０℃として総固形分約１５
％，カフェイン含量０．６％のコーヒー抽出液を得た。
この抽出液を５倍希釈後、フィルターを通し顆粒状活性
白土1,200 ｍｌを充填したカラムに通液してカフェイン
を除去した。カラム通過液のカフェイン除去率は９５．
３％であった。Example 3 2.5 kg of coffee beans in a multistage countercurrent extractor consisting of six stages
And the feed water temperature is about 180 ° C, and the total solid content is about 15
%, And a coffee extract having a caffeine content of 0.6% was obtained.
After diluting this extract five-fold, it was passed through a filter and passed through a column filled with 1,200 ml of granular activated clay to remove caffeine. The caffeine removal rate of the liquid passing through the column was 95.
3%.
【００１４】[0014]
【発明の効果】本発明によれば、カフェイン含有水溶液
を活性白土または酸性白土と接触させることにより、カ
フェインを吸着させるという簡便な方法により工業的に
極めて有利にカフェインを選択的に除去することがで
き、産業上極めて有用である。Industrial Applicability According to the present invention, caffeine is selectively removed industrially and extremely advantageously by a simple method of adsorbing caffeine by bringing an aqueous solution containing caffeine into contact with activated clay or acid clay. It is extremely useful industrially.
フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) B01D 15/00 A23F 3/38 A23F 5/22 B01J 20/12 Continuation of the front page (58) Field surveyed (Int. Cl. 7 , DB name) B01D 15/00 A23F 3/38 A23F 5/22 B01J 20/12
Claims (1)
エピカテキンガレート（ＥＣｇ），（−）−エピガロカ
テキンガレート（ＥＧＣｇ）及びクロロゲン酸の群より
選ばれる１種以上とカフェインを含有する水溶液を、５
％サスペンジョンのｐＨが２．５〜３．５である活性白
土または酸性白土と接触させることにより、水溶液から
選択的にカフェインを除去する方法。(1) (-)-Epicatechin (EC), (-)-
An aqueous solution containing caffeine and at least one selected from the group consisting of epicatechin gallate (ECg), (−)-epigallocatechin gallate (EGCg) and chlorogenic acid is prepared by adding 5
A method for selectively removing caffeine from an aqueous solution by contacting with activated clay or acid clay having a pH of 2.5% to 3.5% suspension.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04316650A JP3138781B2 (en) | 1992-10-30 | 1992-10-30 | Method for removing caffeine from aqueous solution containing caffeine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04316650A JP3138781B2 (en) | 1992-10-30 | 1992-10-30 | Method for removing caffeine from aqueous solution containing caffeine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06142405A JPH06142405A (en) | 1994-05-24 |
| JP3138781B2 true JP3138781B2 (en) | 2001-02-26 |
Family
ID=18079388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04316650A Expired - Fee Related JP3138781B2 (en) | 1992-10-30 | 1992-10-30 | Method for removing caffeine from aqueous solution containing caffeine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3138781B2 (en) |
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