JPH0527619B2 - - Google Patents

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Publication number
JPH0527619B2
JPH0527619B2 JP59062595A JP6259584A JPH0527619B2 JP H0527619 B2 JPH0527619 B2 JP H0527619B2 JP 59062595 A JP59062595 A JP 59062595A JP 6259584 A JP6259584 A JP 6259584A JP H0527619 B2 JPH0527619 B2 JP H0527619B2
Authority
JP
Japan
Prior art keywords
lipids
carbon dioxide
algae
extracted
extraction
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 - Lifetime
Application number
JP59062595A
Other languages
Japanese (ja)
Other versions
JPS60207567A (en
Inventor
Katsumi Yamaguchi
Hiroshi Yamamoto
Norio Ando
Katsuyuki Murai
Tetsuo Kajama
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Iwatani Corp
Yaeyama Shokusan Co Ltd
Original Assignee
Iwatani Sangyo KK
Yaeyama Shokusan Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Iwatani Sangyo KK, Yaeyama Shokusan Co Ltd filed Critical Iwatani Sangyo KK
Priority to JP59062595A priority Critical patent/JPS60207567A/en
Publication of JPS60207567A publication Critical patent/JPS60207567A/en
Publication of JPH0527619B2 publication Critical patent/JPH0527619B2/ja
Granted legal-status Critical Current

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Classifications

    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/141Feedstock
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/54Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Edible Seaweed (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Description

【発明の詳細な説明】[Detailed description of the invention]

本発明は、スピルリナ、クロレラ等を代表とす
る藻類からカロチノイドを含んだ脂質を製造する
方法に関し、クロロフイルを選択的に排除した状
態で藻類内の脂質を迅速・容易に抽出する方法を
提供する。 本発明が対象とする藻類とは、水中に生育し同
化色素を有して光合成を営む下等植物の総称で、
分類学的には以下のようになる。但し、カツコ内
はその具体例を示す。 1 藍藻類(スピルリナ、スイゼンジノリ) 2 緑藻類(アオノリ、ミル、クロレラ、セネデ
スムス) 3 褐藻類(コンブ、ワカメ、ヒジキ、アラメ) 4 紅藻類(アサクサノリ、テングサ、フノリ) 5 珪藻類(クモノスケイソウ、オビケイソウ) 6 プラシノ藻類(ピラミモナス、プラチモナ
ス) 7 黄緑色藻類(フウセンモ、フシナシミドロ) 8 黄金色藻類(ヒカリモ) 9 クリプト藻類(クロオモナス) 10 緑色鞭毛藻類(シヤトネラ) 11 渦鞭毛藻類(セラチウム、ゴニオラツクス) 12 ミドリムシ藻類(ユーグレナ、コラシウム) 13 輪藻類(シヤジグモ) 上記藻類のうちでも、コンブ、ワカメ、ヒジ
キ、アサクサノリ、テングサ等は日本人の食生活
に馴染み深いものであるが、この他にも特に、ス
ピルリナ(植物分類学上の正式体系では、藍藻類
−ネンジユモ目−ユレモ亜目−ユレモ科)、クロ
レラ(同、緑藻類−クロロコツクム目−クロレラ
科)及びセネデスムス(同、緑藻類−クロロコツ
クム目−コエラストラム科)等は、その乾燥藻体
当たりのタンパク質含量が6割以上に達するの
で、当初新しいタンパク資源としての可能性を期
待された。 しかし、培養液から収穫する時に遠心分離或い
は過操作が必要であり、その処理能力にはおの
ずから限界があつて生産価格が高くつくこと(例
えば、スピルリナの生産価格は飼料用の大豆や魚
粉に対して約20倍であり、相当の開きがある)、
また、クロレラでは細胞壁が強靭で消化性に問題
があることなどのために、食糧資源としてより
も、むしろ加工健康食品或いは食品添加剤として
利用されているのが現状である。 即ち、クロレラ、スピルリナ等は健康保健薬と
して錠剤化されており、特に後者は錦鯉、金魚、
クルマエビなどの色揚げ剤として養魚飼料の一部
に利用されているほか、その藻体内に特異的に含
まれるフイコシアニンという青色色素が天然着色
料として製品化されている。 一般に、藻類に含まれる脂質は中性脂質と複合
脂質から成り、前者はトリグリセリド、カロチノ
イド、炭化水素及び遊離脂肪酸等を含み、後者は
リン脂質、糖脂質、含硫脂質等を含むが、全体と
してカロチノイドを豊富に含有している。 例えば、スピルリナ100g当たりにはカロチノ
イドが650mg含まれるが、このカロチノイドの主
要成分はβ−カロチン、ゼアキサンチン及び糖カ
ロチノイドであり、β−カロチンは腸で吸収され
てビタミンAになる(即ち、前駆体ビタミンA)
ことから栄養学的に重要であり、しかも、β−カ
ロチン、及びビタミンAはともにその癌抑制効果
が最近注目を集めている。 そして、黄色カロチノイドのゼアキサンチン
は、鯉や金魚の色揚げ剤として活用され、赤色の
糖カロチノイドは抗菌活性を有する可能性がある
ため薬剤としての用途が期待できる。 さらに、このスピルリナの複合脂質中に含まれ
るグリセロ糖脂質には抗腫瘍作用を有する可能性
があり、やはり薬剤としての使用が期待できる。 しかしながら、現状においては、藻類に対する
研究対象はタンパク質や多糖類に向けられる場合
が多く、藻類から積極的に脂質を抽出してこれを
利用しようとする試みは余り見受けられない。例
えば、前述したスピルリナからのタンパク色素フ
イコシアニンの製造においては、フイコシアニン
を水中に溶出させて回収しているが、脂質を含む
残渣は遠心分離操作で分離、除去したのち、廃棄
するか、或いはせいぜい飼料として使用する程度
である。 しかしながら、上述のように藻類に含有される
脂質には抗癌作用のあるβ−カロチンなどのカロ
チノイドを初めとして、有用な成分が豊富に含ま
れており、藻類から脂質を抽出できれば、健康食
品、色素油、薬品として付加価値の高い製品を造
ることができる。 このように、藻類からの脂質の抽出は、加工食
品や栄養強化飼料としての途を開くものである
が、一方、光合成を行なう藻類には必然的にクロ
ロフイルが多く含まれており(例えば、スピルリ
ナ100g当たりにはクロロフイル2000mgが含まれ
る)、脂質抽出に際してはこの多量のクロロフイ
ルが同時に混入して来ることを避け難い。 例えば、特公昭48−16189号公報には、藻類に
分類される藻菌類からn−ヘキサン或いは石油エ
ーテルを用いて、炭化水素型カロチノイドたるリ
コピンを抽出する方法が開示されているが、この
公報からも判るように、藻類からカロチノイドを
含む脂質を抽出する方法としては、エタノール、
アセトン、エーテル、クロロホルム、メチレンク
ロライド若しくはn−ヘキサン等の一般的な有機
溶剤を用いる多段式の溶剤抽出法が行なわれる
が、クロロフイルが上記有機溶剤に対して易溶で
あるため、脂質抽出に際してはクロロフイルも同
時に抽出されざるを得ず、クロロフイルだけを選
択的に排除できる溶剤抽出方法は存在しないのが
実情である。 ところで、この藻類中に含まれるクロロフイル
は光過敏症の原因となり、例えば飼料付与による
家畜の障害例は古くから知られており、また、ク
ロレラ錠剤の喫食過多は人体障害を引き起こすこ
とも最近広く知られるところとなつた。 これはクロロフイルが分解して生ずるフエオフ
オルバイドaに直接起因するものであつて、その
光感作反応により日光性の皮膚炎等の光過敏症を
顕現するが、このフエオフオルバイドaはシロネ
ズミを用いた光毒性試験の結果(経口投与後、翌
日照度2万ルツクス、60分間の光照射を行なう)、
LD50は45.5mg/体重100g以上、MLD50は12mg/
体重100g以上の値を有するとされる(日本農芸
化学会誌、1980年、Vol.54、No.9、721〜726頁)。 しかも、クロロフイルは酸性に傾いたり、有機
溶剤の共存によつてフエオフオルバイドaが生成
し易くなるので、全体からみれば、藻類から抽出
した脂質をそのまま健康食品や色素油として用い
ることには問題が残る。 本発明は、従来積極的には試みられなかつた藻
類からの脂質抽出に関し、上記有機溶剤抽出法で
は達成できなかつたクロロフイルを排除した状態
での脂質抽出を目的とし、この目的を達するため
に、抽出剤として炭酸ガスを使用し、炭酸ガスを
臨界点75.2Kg/cm2・31.1℃を超える超臨界ガス域
の炭酸ガスにし、この炭酸ガスを藻類に接触させ
て、クロロフイルを選択的に排除した状態で、β
−カロチン等のカロチノイドを含む脂質を藻類内
から炭酸ガス内に抽出するように構成したもので
ある。 即ち、本発明者等は、クロロフイルが第2図に
示す超臨界ガス域Aにある炭酸ガス中にはその親
和性との関係で溶出されないという事実を新しく
発見し、この発見に基いて本発明を完成したもの
である。 以下、この抽出方法を現実的に実施するための
諸工程をスピルリナに例を採り第1図を参照しな
がら、(イ)乃至(ホ)に詳述する。 (イ) 前処理工程 スピルリナは浮上性でブロツク状に固まる性
質があるので、過法により藻体を収穫し、低
温スプレードライヤー法または凍結乾燥法によ
り乾燥し青黒色の粉末とする。 この粉末は、以下の抽出工程に仕込原料とし
て供給される。 (ロ) 原料収容工程 前処理工程で得られた粉末を原料1として抽
出槽2に収容する。 (ハ) 抽出剤供給工程 抽出剤に炭酸ガスを用い、これを加圧器(コ
ンプレツサまたはポンプ等)3で加圧し熱交換
式の加熱器4で加熱して、臨界圧力75.2Kg/cm2
P1を超える超臨界圧力で、しかも臨界温度31.1
℃T1を超える超臨界温度の状態となる超臨界
ガス域Aの炭酸ガスにし(第2図参照)、抽出
槽2に供給する。 (ニ) 脂質抽出工程 抽出槽2内で超臨界状態の炭酸ガスを前記ス
ピルリナ粉末1に接触させて、粉末に含まれる
脂質を、クロロフイルを排除した状態で超臨界
状態炭酸ガス内に抽出する。 (ホ) 脂質回収工程 脂質を含む超臨界状態にある炭酸ガスを、抽
出槽2から一次圧力設定用の調圧弁6を通過さ
せて減圧し、回収槽5に連続的に注入すること
により、臨界圧力75.2Kg/cm2を下回る圧力状態
にする。 この臨界圧力以下の炭酸ガスは、脂質に対す
る親和性を失うので容易に脂質を分離し、回収
槽5にはβ−カロチンを主としたカロチノイド
を豊富に含み、且つ、クロロフイルを有しない
脂質7を迅速に回収できる。 図中、符号10はフイルタ、11は排出弁、1
2は逆止弁、9は炭酸ガス供給源、13は炭酸ガ
ス供給弁である。 尚、上記(イ)から(ホ)の各工程をより効率的に行う
ため、次の(ヘ)〜(ヌ)の少なくとも一つの工程を採用
してもよい。 (ヘ) スピルリナの細胞膜は薄く、且つ、柔らか
く、細胞成分の溶出が容易であるので、水中に
スピルリナを投与、攪拌し、その組成分のう
ち、タンパク質、炭水化物等の可溶分を水中に
溶出させたのち、水に不溶性の残渣物を遠心分
離し、低温或いは凍結等の乾燥工程を施す。 (ト) 脂質を分離した後の炭酸ガスを凝縮器8で凝
縮液化して、加圧器3・加熱器4に通じて抽出
槽2に再循環させる。 (チ) 脂質分離後の炭酸ガスを、熱交換器8を省略
して、フイルタ10から加圧器(コンプレツ
サ)3に循環させる。 (リ) 液化炭酸ガスを供給源9からポンプ3に供給
し、回収槽5から気体炭酸ガス排出弁11を通
じて外部に排出し、ポンプ3へは循環しない。 (ヌ) 脂質を含む炭酸ガスを抽出槽2から回収槽5
に断続的に移しかえる。 そこで、上記諸工程の組合せたる本発明方法を
スピルリナ及びクロレラの凍結乾燥品若しくは低
温乾燥品に適用実施した結果を、以下、順次述べ
る。 実施例 1 スピルリナの凍結乾燥品を75mlの抽出槽に収容
し、各試料量を平均流量1.0Kg/hrで、温度・圧
力を表に示す値に採つた超臨界ガス域の炭酸ガ
スを用いて3時間に亘つて脂質抽出を行ない、各
試料から得た抽出脂質量及び残留脂質量を表に
まとめた。 尚、各抽出条件において、抽出量の再現性を確
かめるため抽出実験を二回実施した。
The present invention relates to a method for producing carotenoid-containing lipids from algae such as spirulina and chlorella, and provides a method for quickly and easily extracting lipids from algae while selectively excluding chlorophyll. Algae, which is the subject of the present invention, is a general term for lower plants that grow in water, have assimilable pigments, and carry out photosynthesis.
Taxonomically, it is as follows. However, specific examples are shown in the box. 1 Blue-green algae (Spirulina, Agariculina) 2 Green algae (Aonori, Myr, Chlorella, Scenedesmus) 3 Brown algae (Kelp, Wakame, Hijiki, Arame) 4 Red algae (Amanita, Amanita, Funori) 5 Diatoms (Arachnoid, Amanita) 6 Plasinoalgae (Pyramimonas, Platymonas) 7 Yellow-green algae (Furusenmo, Fucinasimidoro) 8 Golden-colored algae (Hikarimo) 9 Cryptoalgae (Chloomonas) 10 Chloroflagellates (Shyatonella) 11 Dinoflagellates (Serratium, Goniolachus) 12 Euglena algae ( Among the algae mentioned above, kelp, wakame, hijiki, morning glory, and amanita are familiar to the Japanese diet. According to the formal academic system, blue-green algae - Chlorocycetes - Chlorochocoformes - Chlorellaceae), Chlorella (same, Green algae - Chlorochocochiformes - Chlorellaceae), and Scenedesmus (green algae - Chlorochocochiformes - Coelastolaceae), etc. Since the protein content per dry algal body reaches over 60%, it was initially expected to have potential as a new protein resource. However, centrifugation or over-operation is required when harvesting from the culture solution, which naturally limits the processing capacity and increases the production price (for example, the production price of spirulina is higher than that of soybeans and fishmeal used for feed). (approximately 20 times the difference, which is a considerable difference)
Furthermore, because chlorella has a tough cell wall and has problems with digestibility, it is currently used more as a processed health food or food additive than as a food resource. In other words, chlorella, spirulina, etc. are made into tablets as health medicines, and the latter in particular is used for Nishikigoi, goldfish,
In addition to being used in some fish feed as a coloring agent for shrimp, etc., phycocyanin, a blue pigment specifically contained within the algae, has been commercialized as a natural coloring agent. In general, the lipids contained in algae consist of neutral lipids and complex lipids, the former containing triglycerides, carotenoids, hydrocarbons, free fatty acids, etc., and the latter containing phospholipids, glycolipids, sulfur-containing lipids, etc.; Contains abundant carotenoids. For example, 100 g of spirulina contains 650 mg of carotenoids, the main components of which are β-carotene, zeaxanthin, and sugar carotenoids, and β-carotene is absorbed in the intestine to become vitamin A (i.e., the precursor vitamin A)
Therefore, β-carotene and vitamin A are nutritionally important, and both β-carotene and vitamin A have recently attracted attention for their cancer-suppressing effects. The yellow carotenoid zeaxanthin is used as a color enhancer for carp and goldfish, and the red sugar carotenoid may have antibacterial activity, so it is expected to be used as a drug. Furthermore, the glyceroglycolipids contained in the complex lipids of Spirulina may have antitumor effects, and can be expected to be used as a drug. However, at present, research on algae is often focused on proteins and polysaccharides, and there are few attempts to actively extract lipids from algae and utilize them. For example, in the production of the protein pigment phycocyanin from Spirulina mentioned above, the phycocyanin is recovered by elution into water, but the residue containing lipids is separated and removed by centrifugation and then discarded or, at most, used as feed. It is only used as a. However, as mentioned above, the lipids contained in algae are rich in useful components, including carotenoids such as β-carotene, which have anticancer effects, and if lipids can be extracted from algae, they can be used as health foods. High value-added products such as pigment oils and medicines can be made. In this way, the extraction of lipids from algae opens the door to processed foods and nutritionally enriched feed, but on the other hand, algae that carry out photosynthesis naturally contain a large amount of chlorophyll (for example, spirulina). (2000mg of chlorophyll is contained per 100g), and it is difficult to avoid this large amount of chlorophyll being mixed in at the same time when extracting lipids. For example, Japanese Patent Publication No. 48-16189 discloses a method for extracting lycopene, a hydrocarbon carotenoid, from fungi classified as algae using n-hexane or petroleum ether. As can be seen, the methods for extracting lipids containing carotenoids from algae include ethanol,
A multistage solvent extraction method using common organic solvents such as acetone, ether, chloroform, methylene chloride, or n-hexane is performed, but since chlorophyll is easily soluble in the above organic solvents, it is difficult to extract lipids. Chlorophyll must also be extracted at the same time, and the reality is that there is no solvent extraction method that can selectively remove chlorophyll alone. By the way, chlorophyll contained in this algae causes photosensitivity, and cases of damage to livestock due to feed feeding have been known for a long time, and it has recently been widely known that eating too many chlorella tablets can cause health problems in humans. It became a place where I was exposed. This is directly caused by pheophorbide a produced by the decomposition of chlorophyll, and its photosensitization reaction causes photosensitivity such as sun-induced dermatitis. The results of a phototoxicity test using white rats (after oral administration, the next day the drug was irradiated with light for 60 minutes at an illuminance of 20,000 lux),
LD 50 is 45.5 mg/100g body weight or more, MLD 50 is 12 mg/
It is said to have a weight of 100 g or more (Journal of the Japanese Society of Agricultural Chemistry, 1980, Vol. 54, No. 9, pp. 721-726). Moreover, chlorophyll tends to be acidic, and pheophorbide a tends to be produced when organic solvents coexist, so it is difficult to use lipids extracted from algae as they are as health foods or pigment oils. Problems remain. The present invention relates to lipid extraction from algae, which has not been actively attempted in the past, and aims to extract lipids while excluding chlorophyll, which could not be achieved with the organic solvent extraction method described above, and in order to achieve this purpose, Using carbon dioxide gas as an extractant, the carbon dioxide gas was converted into carbon dioxide gas in the supercritical gas range exceeding the critical point of 75.2Kg/ cm2・31.1℃, and this carbon dioxide gas was brought into contact with algae to selectively eliminate chlorophyll. In the state, β
- It is configured to extract lipids containing carotenoids such as carotene from inside algae into carbon dioxide gas. That is, the present inventors have newly discovered the fact that chlorophyll is not eluted into carbon dioxide gas in the supercritical gas region A shown in FIG. 2 due to its affinity, and based on this discovery, the present invention has been developed. This is the completed version. Hereinafter, the various steps for practically implementing this extraction method will be described in detail in (a) to (e) using spirulina as an example and with reference to FIG. 1. (a) Pre-treatment process Spirulina has the property of floating and solidifying into blocks, so the algae are harvested by a filtration method and dried by a low-temperature spray dryer method or freeze-drying method to form a blue-black powder. This powder is supplied as a raw material to the following extraction process. (b) Raw material storage step The powder obtained in the pretreatment step is stored in the extraction tank 2 as the raw material 1. (c) Extractant supply process Using carbon dioxide as the extractant, it is pressurized with a pressurizer (compressor, pump, etc.) 3 and heated with a heat exchange type heater 4 to obtain a critical pressure of 75.2 Kg/cm 2
Supercritical pressure exceeding P 1 and critical temperature 31.1
The carbon dioxide gas is converted into a supercritical gas region A, which has a supercritical temperature exceeding ℃T 1 (see Fig. 2), and is supplied to the extraction tank 2. (d) Lipid extraction step Supercritical carbon dioxide gas is brought into contact with the Spirulina powder 1 in the extraction tank 2, and the lipids contained in the powder are extracted into the supercritical carbon dioxide gas with chlorophyll removed. (E) Lipid recovery process The carbon dioxide gas containing lipids in a supercritical state is reduced in pressure by passing through the pressure regulating valve 6 for setting the primary pressure from the extraction tank 2, and then continuously injected into the recovery tank 5 to reach the critical state. Bring the pressure below 75.2Kg/ cm2 . Carbon dioxide gas below this critical pressure loses its affinity for lipids, so lipids are easily separated. Can be recovered quickly. In the figure, numeral 10 is a filter, 11 is a discharge valve, 1
2 is a check valve, 9 is a carbon dioxide gas supply source, and 13 is a carbon dioxide gas supply valve. Incidentally, in order to perform each of the above steps (A) to (E) more efficiently, at least one of the following steps (F) to (N) may be employed. (f) The cell membrane of Spirulina is thin and soft, and cell components can be easily eluted, so spirulina is administered into water and stirred to elute soluble components such as proteins and carbohydrates into the water. After that, the water-insoluble residue is centrifuged and subjected to a drying process such as low temperature or freezing. (g) After the lipids have been separated, the carbon dioxide gas is condensed and liquefied in the condenser 8, passed through the pressurizer 3 and the heater 4, and then recirculated to the extraction tank 2. (h) The carbon dioxide gas after lipid separation is circulated from the filter 10 to the compressor 3 without the heat exchanger 8. (li) Liquefied carbon dioxide is supplied from the supply source 9 to the pump 3, and is discharged from the collection tank 5 to the outside through the gaseous carbon dioxide discharge valve 11, without being circulated to the pump 3. (J) Carbon dioxide gas containing lipids is removed from extraction tank 2 and recovery tank 5.
be transferred intermittently to Therefore, the results of applying the method of the present invention, which is a combination of the above-mentioned steps, to freeze-dried products or low-temperature-dried products of Spirulina and Chlorella will be sequentially described below. Example 1 Freeze-dried spirulina was placed in a 75 ml extraction tank, and each sample was extracted using carbon dioxide in the supercritical gas range at an average flow rate of 1.0 Kg/hr and temperature and pressure as shown in the table. Lipid extraction was performed for 3 hours, and the extracted lipid amount and residual lipid amount obtained from each sample were summarized in a table. In addition, under each extraction condition, the extraction experiment was conducted twice in order to confirm the reproducibility of the extraction amount.

【表】 ここで、総脂質量は、試料100g当たりに含ま
れる粗脂肪をブライダイヤ(Bligh Dyer)法で
定量したものであり、当然に各試料を通じて同じ
数値を示す。 さらに、抽出脂質量は超臨界炭酸ガスにより回
収した抽出分中の脂質を、また、残留脂質量は抽
出後の仕込試料に残る脂質を、ブライダイヤ法に
より定量して各々100g換算したものである。 上記抽出実施例によれば、圧力を一定に保ち
(例えば、250Kg/cm2一定)、温度を上昇させると
(40→60→80℃)、抽出脂質量は増加するが、温度
を一定に保ち(例えば40℃一定)、圧力を上昇さ
せても(250→400Kg/cm2)、抽出脂質量の顕著な
増加はないことが判る。 従つて、超臨界ガス域の炭酸ガスによるスピル
リナ凍結品の脂質抽出においては、温度を高く、
且つ、圧力を低くすれば、その抽出の経済効率を
高めることができる。 実施例 2 成分が熱変性を受けないように乾燥したスピル
リナの低温乾燥品を4の抽出槽に収容し、試料
量1431.6gを、温度40℃、圧力400Kg/cm2の超臨
界ガス域の炭酸ガスを用いて、平均流量7.0Kg/
hrで1.5時間抽出したところ、次の数値を得た。 総脂質量 7.5g/試料100g 抽出脂質量 0.4g/試料100g 残留脂質量 4.7g/試料100g 実施例1及び2の結果から炭酸ガス単位重量当
たりの抽出脂質量を算出して比較すると(ともに
温度40℃、圧力400Kg/cm2抽出分を対比)、凍結乾
燥品では平均流量1.0Kg/hrで3時間流して試料
100g当たり1.29〜1.49g抽出できるので、 1.29〜1.49g/1.0Kg/hr×3hr=0.43〜0.50g/CO21Kg の数値を示すのに対し、低温乾燥品では平均流量
7.0Kg/hrで1.5時間流して試料100g当たり0.4g
抽出できるので、 0.4g/7.0Kg/hr×1.5hr=0.04g/CO21Kg の数値を示す。 実施例 3 クロレラの凍結乾燥品を75mlの抽出槽に収容
し、各試料量を平均流量1.1Kg/hrで温度・圧力
を表に示す値に採つて超臨界ガス域の炭酸ガス
を用いて3時間に亘つて脂質抽出を行ない、各試
料から得た抽出脂質量及び残留脂質量を表にま
とめた。 尚、各抽出条件において、抽出量の再現性を確
かめるため、抽出実験を二回実施した。
[Table] Here, the total lipid amount is the crude fat contained per 100 g of sample determined by the Bligh Dyer method, and naturally shows the same value for each sample. Furthermore, the extracted lipid amount is the lipid in the extract recovered by supercritical carbon dioxide gas, and the residual lipid amount is the lipid remaining in the prepared sample after extraction, which was determined by the Bligh-Diamond method and converted to 100 g. . According to the above extraction example, if the pressure is kept constant (e.g. 250Kg/ cm2 constant) and the temperature is increased (40→60→80℃), the amount of extracted lipids will increase, but if the temperature is kept constant It can be seen that even if the pressure is increased (for example, at a constant temperature of 40° C.) (from 250 to 400 Kg/cm 2 ), there is no significant increase in the amount of extracted lipids. Therefore, when extracting lipids from frozen Spirulina using carbon dioxide gas in the supercritical gas range, it is necessary to raise the temperature and
Moreover, by lowering the pressure, the economic efficiency of the extraction can be increased. Example 2 A low-temperature dried product of spirulina, which had been dried to prevent the components from undergoing thermal denaturation, was placed in an extraction tank 4, and a sample amount of 1431.6 g was extracted with carbonic acid in a supercritical gas region at a temperature of 40°C and a pressure of 400 kg/ cm2. Using gas, average flow rate 7.0Kg/
When extracted with hr for 1.5 hours, the following values were obtained. Total lipid amount 7.5g/sample 100g Extracted lipid amount 0.4g/sample 100g Residual lipid amount 4.7g/sample 100g Calculating and comparing the extracted lipid amount per unit weight of carbon dioxide from the results of Examples 1 and 2 (both at temperature 40℃, pressure 400Kg/cm 2 extraction), and for freeze-dried products, run the sample at an average flow rate of 1.0Kg/hr for 3 hours.
Since 1.29-1.49g can be extracted per 100g, the figure is 1.29-1.49g/1.0Kg/hr x 3hr = 0.43-0.50g/1Kg of CO 2 , whereas the average flow rate for low-temperature dried products is
0.4g per 100g of sample after flowing for 1.5 hours at 7.0Kg/hr
Since it can be extracted, the numerical value is 0.4g/7.0Kg/hr x 1.5hr = 0.04g/CO 2 1Kg. Example 3 Freeze-dried chlorella was placed in a 75 ml extraction tank, and each sample was extracted using carbon dioxide in the supercritical gas range at an average flow rate of 1.1 Kg/hr and temperature and pressure as shown in the table. Lipid extraction was performed over time, and the extracted lipid amount and residual lipid amount obtained from each sample were summarized in a table. In addition, in order to confirm the reproducibility of the extraction amount under each extraction condition, the extraction experiment was conducted twice.

【表】【table】

【表】 上表の総脂質量及び抽出脂質量は実施例1と同
義である。 また、上記実施例は、実施例1と同じく、圧力
を一定に保ち温度を上昇させると総抽出量は増加
するが、温度を一定に保ち圧力を上昇させても、
総抽出量の顕著な増加はない。 実施例 4 クロレラをスプレードライヤーを用いて120〜
130℃で乾燥した高温乾燥品を4の抽出槽に収
容し、試料量978.3gを温度40℃、圧力400Kg/cm2
の超臨界ガス域の炭酸ガスを用いて平均流量3.0
Kg/hrで7時間抽出したところ、次の数値を得
た。 総脂質量 2.5g/試料100g 抽出脂質量 0.95g/試料100g 残留脂質量 1.5g/試料100g 上記高温乾燥品はその総脂質量をクロレラ凍結
乾燥品の数値10.4g/試料100gと比較すると、
略4分の1の低い値に留まつているが、これは原
料クロレラに含まれる脂質中の少なくない部分が
熱変性や分解を起こしたためと推定できる。 従つて、炭酸ガス単位重量当たりの脂質抽出量
も0.05g/CO21Kg(0.95g/3.0Kg/hr×7hrより
算出)の数値を示し、クロレラ凍結乾燥品での数
値0.65〜1.33g/CO21Kgに比してかなり低い値に
留まる。 以上のように、種々の実施例によれば、スピル
リナ及びクロレラ乾燥品から超臨界ガス域にある
炭酸ガスで脂質抽出を迅速且つ容易に行なうこと
ができるが、この抽出された脂質中の組成の分析
及び当該脂質中のクロロフイルの存在の有無を確
認する必要があり、この確認のために(1)乃至(3)の
試験を行なつた。 (1) 抽出脂質における中性脂質と複合脂質の定量
試験 試験例 1 スピルリナ低温乾燥品から抽出した脂質(実施
例2の抽出分)75mgをシリカゲル(Wakogel C
−200)を充填したカラム(2×4cm)にかけ、
クロロホルム50ml及びメタノール50mlを展開液と
して脂質を順次溶出し、中性脂質画分(クロロホ
ルム画分)と複合脂質画分(メタノール画分)を
得、各画分の量比を重量法により算定して下記の
結果を得た。 スピルリナ低温乾燥品抽出脂質(総量75mg) 中性脂質 71mg(重量比94.6%) 複合脂質 3mg(重量比4.0%) 上記試験によれば、抽出脂質の大部分はグリセ
リド、カロチノイド等からなる中性脂質であり、
糖脂質等からなる複合脂質はごくわずかしか含ま
れないことが確認できる。 試験例 2 クロレラ高温乾燥品から抽出した脂質(実施例
4の抽出分)78mgを試験例1と同様の操作でカラ
ムクロマトグラフにかけ、次の結果を得た。 クロレラ高温乾燥品抽出脂質(総量78mg) 中性脂質 65.1mg(重量比83.5%) 複合脂質 4.6mg(重量比5.9%) 上記成分比によれば、スプルリナに比して、中
性脂質量が若干少なく、その分複合脂質が多くな
つている。 (2) 脂質組成の定性試験 試験例 3 実施例1に使用したスピルリナ凍結乾燥品のう
ち、400Kg/cm2・40℃の抽出条件分から得られる
総脂質、残留脂質及び炭酸ガス抽出脂質の各々に
ついて、市販のシリカゲル60F254(Merck)の薄
層板を使用し、石油エーテル/エーテル/酢酸
(90:10:1)の展開溶媒を用いて薄層クロマト
グラフにかけ第3図Aを得た。 尚、スピルリナ凍結乾燥品及び低温乾燥品は、
いずれについても同様の結果を示すので、上記抽
出分をもつて抽出試験の代表例とした。 上記A図によれば、スピルリナを構成する脂質
は、β−カロチン、クロロフイル、黄色カロチノ
イド、トリグリセリド等から成り(総脂質の展開
状態を参照)、超臨界炭酸ガスによる抽出では、
この総脂質のうちβ−カロチン、黄色カロチノイ
ド、トリグリセリド、コレステロール等が炭酸ガ
ス内に溶出されるが、クロロフイルは残留脂質と
なつて原点に止まつていることが判る。 そこで、上記薄層クロマトグラムにおいて原点
付近に止まつている脂質分の詳細な成分を確認す
るため、さらにこの炭酸ガス抽出分をクロロホル
ム/メタノール/水(65:25:4)の展開溶媒を
用いて展開させ、第3図Bを得た。 上記B図によれば、総脂質に含まれる成分とし
てはA図に示す以外に、ミキソキサントフイル、
オシラキサンチン等の赤色糖カロチノイド及びモ
ノグリコシルジグリセリド、モノグリコシルモノ
グリセリド、ジグリコシルモノグリセリド等のグ
リセロ糖脂質を挙げることができる。 また、薄層クロマトグラムの展開先端位置付近
において、総脂質分の場合にはクロロフイル及び
黄色カロチノイドの重複展開スポツトが表われて
いるが、超臨界炭酸ガスの抽出分では黄色カロチ
ノイドの展開スポツトだけが表われており、クロ
ロフイルは残留脂質分に止まつて抽出脂質分には
移行していないことが再確認できる。 従つて、超臨界炭酸ガスによる脂質抽出では、
中性指質、特にβ−カロチン、黄色カロチノイド
等のカロチノイドを高収率で回収することがで
き、しかも同時にクロロフイルを排除して残留分
に留め置くことができる。 尚、残留脂質分には、クロロフイルのほかに、
グリセロ糖脂質や赤色糖カロチノイドが濃縮され
ており、前者は抗腫瘍作用、また後者は抗菌活性
を有する可能性があり、ともに薬剤としての利用
が期待できる。 試験例 4 実施例3に使用したクロレラ凍結乾燥品(250
Kg/cm2・40℃の抽出分)から得られる残留脂質、
炭酸ガス抽出脂質の各々について、前述のシリカ
ゲル60F254(Merck)の薄層板を使用し、二種の
展開溶媒、即ち、石油エーテル/エーテル/酢酸
(90:10:1)及びクロロホルム/メタノール/
水(65:25:4)を用いて、薄層クロマトグラム
を得た。 尚、クロレラ凍結乾燥品及び高温乾燥品は、い
ずれについても同様の結果を示すので、上記抽出
分をもつて抽出試験の代表例とした。 第4図Aは石油エーテル/エーテル/酢酸系で
展開したものであり、β−カロチン、トリグリセ
リド、黄色カロチノイド、炭化水素、コレステロ
ールエステル等は炭酸ガス抽出分に移行し残留脂
質分にはほとんど残留せず、また一方、クロロフ
イルは残留脂質分中に止まり抽出脂質分中には移
行しない。 第4図Bは、上記A図で原点付近に止まる脂質
成分をより明確にするため、さらにクロロホル
ム/メタノール/水系で展開試験したものであ
り、クロロフイルは抽出脂質分中には移行しない
ことが追認できる。 また、クロレラに含まれる中性脂質は、スピル
リナのそれに比して、炭化水素、遊離脂肪酸及び
ルテイン等のカロチノイドが多く、他方、複合脂
質においては、グリセロ糖脂質、含流脂質等が多
種類含まれていることが確認できる。 (3) 抽出脂質中に含まれるカロチノイドの定性試
験 試験例2(第3図のB図)によれば、総脂質
に含まれる色素成分は、黄色カロチノイド、ク
ロロフイル、ミキソキサントフイル及びオシラ
キサンチンから成るが、超臨界ガスで抽出する
と、このうちの黄色カロチノイドを主に回収で
きる。 試験例 5 従つて、スピルリナ凍結乾燥品400Kg/cm2・40
℃から得た黄色カロチノイドを主成分とする抽出
脂質について、アセトン/石油エーテル(3:
17)の展開溶媒を用い前述のシリカゲル60F254
(Merck)で調整した薄層板上に展開させたとこ
ろ、第5図に示す薄層クロマトグラムを得た。 第5図によれば、抽出されたカロチノイドは、
β−カロチン、ゼアキサンチン、エキネノン、
3′−ヒドロキシ−エキネノン、β−クリプトキサ
ンチン等を主成分とすることが判る。 以上のように、スピルリナ及びクロレラに例を
とつて、これらから超臨界ガス域にある炭酸ガス
で脂質を抽出すれば、クロロフイルを排除してカ
ロチノイドを多く含む脂質を得ることができる
が、本発明は、スピルリナの属する藍藻類、クロ
レラの属する緑藻類を初めとして、水中で光合成
を行なう故にクロロフイルを藻体内に多く含む冒
述の藻類全体についても適用することができ、藻
類一般について実施した場合の本発明の効果を述
べると以下の通りである。 (1) 超臨界状態にある炭酸ガスは、その親和性と
の関係でクロロフイルを溶出しないという性質
を利用して、超臨界炭酸ガスを藻類に接触させ
ることによりクロロフイルを排除した状態で藻
類から脂質を抽出することができるので、従来
のように抽出脂質を摂取することにより、同時
にクロロフイルから生ずるその分解物を人体内
に取り込んで光過敏症を起こす虞れがなくな
る。 しかも、この脂質中からのクロロフイルの選
択的な除去は従来の溶剤抽出法では達成できな
かつたものなので、本発明を藻類に適用すれ
ば、藻類からβ−カロチン等を含む有用脂質の
みを容易且つ安全に抽出でき、これをそのまま
健康食品や色素油として利用することができ
る。 また、藻類に本発明の炭酸ガス抽出を施した
後の抽出残渣について従来の溶剤抽出を行なう
と、クロロフイルの濃縮物を得ることができる
ので、このクロロフイルを化粧品、歯みがき、
チユーインガム等の着色剤として利用すること
ができる。 そのうえ、クロロフイルは前述の光過敏症を
引き起こす間接的原因ともなる反面、適当量を
人体に摂取すれば体内のコレステロールを低下
せしめる薬理効果を有するので、薬剤として活
用できる。 (2) 本発明によつて藻類から抽出された脂質は、
β−カロチンを初めカロチノイドを多く含むの
で、薬効のある栄養剤や色素飼料として利用で
き、例えば、制癌作用やビタミンA活性を持つ
健康食品及び食品の着色剤、或いは、養魚用の
色揚げ剤、家鶏の肉色や卵色の改良剤等として
使用できる。 また、抽出後の残渣中には、クロロフイルを
初めとして、糖カロチノイドや糖脂質が濃縮さ
れており、種々の薬効が期待できるので、残留
分をも利用することができ、もつて、本発明の
抽出操作の付加価値をさらに高めることができ
る。 (3) 液化炭酸ガスを加圧・加熱して臨界点を超え
る超臨界状態にし、これを藻類と接触させたの
ち炭酸ガスを流去するという一段階の操作のみ
で、藻類からクロロフイルを選択排除した状態
で脂質を抽出・分離し、直接製造することがで
きる。 しかも、抽出剤は超臨界状態にある炭酸ガス
なので、所望の脂質との分離がきわめて円滑に
行なえる。 即ち、従来の溶剤抽出法では、藻類から脂質
を選択的に得ようとすれば、溶剤の種類を変え
て多段で行なわねばならないのに対し、本発明
では一段階操作のみで済ますことができる。 従つて、脂質製造に要する手間を最少に抑え
て、その製造コストを安価にできるうえ、設備
全体を大幅にコンパクトにまとめることができ
る。 (4) 超臨界状態にある炭酸ガスはガス状であるに
も拘らず、液体に近い非常に高い密度を持ち、
しかも、ガスの属性たる高い拡散係数をも併せ
持つので、抽出槽内の藻類の隅々にまで広く行
き亘り、抽出表面積及び接触の流速をともに大
きくできるうえ、液体のように高い溶出力を持
つ。 従つて、その抽出効率は高く、抽出量も
大きくできる。 (5) 抽出剤として炭酸ガスを使うので、脂質は抽
出操作の開始から終了までを通じて炭酸ガスの
不活性雰囲気中に置かれることになり、酸敗や
変質がなく、抽出脂質、特にカロチノイドの品
質を良好に維持できる。 また、不活性な炭酸ガスは、従来の溶剤抽出
法に比べて火災や爆発の危険がなく、非常に安
全に操作できる。 そのうえ、炭酸ガスを大気中に排出又は漏洩
する場合でも、大気や環境を汚染する虞れはな
い。 (6) 従来の溶剤抽出法においては、人体に有害な
有機溶剤、例えば、クロロホルム、メチレンク
ロライド等が脂質中に残留する虞れがあるが、
本発明のように炭酸ガスで抽出する方法におい
ては、炭酸ガスが気体であることから製品にこ
のガスが残留することがまず起こり得ず(たと
え微量残留したとしても、安全性が高い)、脂
質製品を保健食品や色素油として安全・無毒な
状態で活用できる。 (7) 本発明は、スピルリナ、クロレラを代表とし
て藻類一般に適用することができることから、
光合成を行なう故にクロロフイルを有する植物
についても適用の可能性が大きく、従つて本発
明を用いれば植物一般から脂質を抽出して有用
な製品をつくることが期待できる。
[Table] The total lipid amount and extracted lipid amount in the above table are the same as in Example 1. In addition, in the above example, as in Example 1, the total extraction amount increases when the pressure is held constant and the temperature is increased, but even if the temperature is held constant and the pressure is increased,
There is no significant increase in total extraction. Example 4 Chlorella was dried from 120% using a spray dryer.
The high-temperature dry product dried at 130℃ was stored in extraction tank 4, and the sample amount of 978.3g was extracted at a temperature of 40℃ and a pressure of 400Kg/ cm2.
An average flow rate of 3.0 using carbon dioxide in the supercritical gas region of
When extracted for 7 hours at Kg/hr, the following values were obtained. Total lipid amount 2.5g/sample 100g Extracted lipid amount 0.95g/sample 100g Residual lipid amount 1.5g/sample 100g Comparing the total lipid amount of the above high temperature dried product with the value of 10.4g/sample 100g of the chlorella freeze-dried product,
Although it remains at a low value of approximately one-fourth, this is presumed to be due to heat denaturation and decomposition of a considerable portion of the lipids contained in the raw material chlorella. Therefore, the amount of lipid extracted per unit weight of carbon dioxide gas is 0.05g/CO 2 1Kg (calculated from 0.95g/3.0Kg/hr x 7hr), which is 0.65 to 1.33g/CO for freeze-dried chlorella products. 2 The value remains quite low compared to 1Kg. As described above, according to the various examples, lipids can be extracted quickly and easily from dried Spirulina and Chlorella products using carbon dioxide gas in the supercritical gas range, but the composition of the extracted lipids is It was necessary to analyze and confirm the presence or absence of chlorophyll in the lipid, and for this confirmation, tests (1) to (3) were conducted. (1) Quantitative test of neutral lipids and complex lipids in extracted lipids Test example 1 75 mg of lipids extracted from low-temperature dried Spirulina (extracted amount of Example 2) was added to silica gel (Wakogel C).
-200) was applied to a column (2 x 4 cm) packed with
Lipids were sequentially eluted using 50 ml of chloroform and 50 ml of methanol as a developing solution to obtain a neutral lipid fraction (chloroform fraction) and a complex lipid fraction (methanol fraction), and the quantitative ratio of each fraction was calculated by gravimetric method. The following results were obtained. Lipids extracted from low-temperature dried Spirulina (total amount 75 mg) Neutral lipids 71 mg (94.6% by weight) Complex lipids 3 mg (4.0% by weight) According to the above test, most of the extracted lipids are neutral lipids consisting of glycerides, carotenoids, etc. and
It can be confirmed that only a small amount of complex lipids such as glycolipids are contained. Test Example 2 78 mg of lipid extracted from a high-temperature dried product of Chlorella (the extract of Example 4) was subjected to column chromatography in the same manner as in Test Example 1, and the following results were obtained. Chlorella high temperature dried product extracted lipids (total amount 78 mg) Neutral lipids 65.1 mg (weight ratio 83.5%) Complex lipids 4.6 mg (weight ratio 5.9%) According to the above component ratio, the amount of neutral lipids is slightly lower than that of Spurulina. There are fewer complex lipids, and there are more complex lipids. (2) Qualitative test of lipid composition Test example 3 Of the lyophilized Spirulina products used in Example 1, total lipids, residual lipids, and carbon dioxide extracted lipids obtained under extraction conditions of 400 Kg/cm 2 and 40°C A thin layer plate of commercially available silica gel 60F254 (Merck) was used for thin layer chromatography using a developing solvent of petroleum ether/ether/acetic acid (90:10:1) to obtain the resultant product shown in Figure 3A. In addition, spirulina freeze-dried products and low-temperature dried products are
Since similar results were obtained for both cases, the above-mentioned extract was used as a representative example of the extraction test. According to the above diagram A, the lipids that make up Spirulina consist of β-carotene, chlorophyll, yellow carotenoid, triglyceride, etc. (see the development state of total lipids), and when extracted with supercritical carbon dioxide,
It can be seen that among the total lipids, β-carotene, yellow carotenoid, triglyceride, cholesterol, etc. are eluted into carbon dioxide gas, but chlorophyll remains as a residual lipid at the origin. Therefore, in order to confirm the detailed composition of the lipids that remain near the origin in the above thin layer chromatogram, we further extracted this carbon dioxide gas using a developing solvent of chloroform/methanol/water (65:25:4). It was developed and Figure 3B was obtained. According to the above diagram B, the components included in the total lipids include myxoxanthophyll, myxoxanthophyll, and
Examples include red sugar carotenoids such as osilaxanthin, and glyceroglycolipids such as monoglycosyl diglyceride, monoglycosyl monoglyceride, and diglycosyl monoglyceride. Furthermore, near the developed tip of the thin-layer chromatogram, overlapping spots of chlorophyll and yellow carotenoid appear for the total lipid content, but only yellow carotenoid spots appear for the supercritical carbon dioxide extraction content. It can be reconfirmed that chlorophyll remains in the residual lipids and does not migrate to the extracted lipids. Therefore, in lipid extraction using supercritical carbon dioxide,
Neutral digits, especially carotenoids such as β-carotene and yellow carotenoid, can be recovered in high yield, and at the same time chlorophyll can be removed and retained as a residue. In addition to chlorophyll, residual lipids include
Glyceroglycolipids and red sugar carotenoids are concentrated, and the former may have antitumor activity, and the latter may have antibacterial activity, and both are expected to be used as drugs. Test Example 4 Chlorella freeze-dried product used in Example 3 (250
Kg/cm 2・Residual lipids obtained from 40℃ extraction),
For each carbon dioxide-extracted lipid, a thin layer of silica gel 60F254 (Merck) as described above was used and two developing solvents were used: petroleum ether/ether/acetic acid (90:10:1) and chloroform/methanol/
Thin layer chromatograms were obtained using water (65:25:4). In addition, since chlorella freeze-dried products and high-temperature dried products both showed similar results, the above-mentioned extract was used as a representative example of the extraction test. Figure 4A shows the result developed in a petroleum ether/ether/acetic acid system, and β-carotene, triglycerides, yellow carotenoids, hydrocarbons, cholesterol esters, etc. are transferred to the carbon dioxide extract, and almost no residue remains in the residual lipids. On the other hand, chlorophyll remains in the residual lipid fraction and does not migrate into the extracted lipid fraction. Figure 4B shows a further development test in a chloroform/methanol/water system in order to clarify the lipid components that stay near the origin in Figure A above, confirming that chlorophyll does not migrate into the extracted lipid components. can. In addition, the neutral lipids contained in chlorella contain more hydrocarbons, free fatty acids, and carotenoids such as lutein than those in spirulina, while the complex lipids contain many types of glyceroglycolipids, fluid-containing lipids, etc. It can be confirmed that (3) Qualitative test of carotenoids contained in extracted lipids According to Test Example 2 (Figure B in Figure 3), the pigment components contained in total lipids are composed of yellow carotenoids, chlorophyll, myxoxanthophyll, and osillaxanthin. However, when extracted with supercritical gas, mainly yellow carotenoids can be recovered. Test Example 5 Therefore, Spirulina freeze-dried product 400Kg/cm 2・40
For extracted lipids mainly composed of yellow carotenoids obtained from ℃, acetone/petroleum ether (3:
17) Silica gel 60F254 as described above using the developing solvent
When developed on a thin layer plate prepared using Merck (Merck), the thin layer chromatogram shown in FIG. 5 was obtained. According to Figure 5, the extracted carotenoids are
β-carotene, zeaxanthin, echinenone,
It is found that the main components are 3'-hydroxy-echinenone, β-cryptoxanthin, etc. As mentioned above, if lipids are extracted from spirulina and chlorella using carbon dioxide gas in the supercritical gas range, chlorophyll can be removed and lipids rich in carotenoids can be obtained. This method can be applied to all the above-mentioned algae, which contain a lot of chlorophyll in their bodies because they photosynthesize in water, including blue-green algae to which Spirulina belongs, and green algae to which Chlorella belongs; The effects of the invention are as follows. (1) Utilizing the property that carbon dioxide in a supercritical state does not elute chlorophyll due to its affinity, lipids are extracted from algae with chlorophyll removed by contacting supercritical carbon dioxide with algae. Therefore, by ingesting extracted lipids as in the past, there is no risk of the decomposition products produced from chlorophyll being taken into the human body and causing photosensitivity. Moreover, selective removal of chlorophyll from lipids could not be achieved by conventional solvent extraction methods, so if the present invention is applied to algae, only useful lipids containing β-carotene etc. can be easily and easily extracted from algae. It can be safely extracted and used as is as a health food or pigment oil. In addition, if conventional solvent extraction is performed on the extraction residue after carbon dioxide extraction of the present invention on algae, a chlorophyll concentrate can be obtained, and this chlorophyll can be used in cosmetics, toothpaste, etc.
It can be used as a coloring agent for chewing gum, etc. Furthermore, while chlorophyll is an indirect cause of the aforementioned photosensitivity, it also has the pharmacological effect of lowering cholesterol in the body when taken into the human body in appropriate amounts, so it can be used as a drug. (2) The lipids extracted from algae according to the present invention are
Contains a large amount of carotenoids, including β-carotene, so it can be used as a medicinal nutritional supplement or pigmented feed.For example, it can be used as a coloring agent for health foods and foods that have anticancer effects and vitamin A activity, or as a coloring agent for fish farming. It can be used as an improver for the color of poultry meat and eggs. In addition, the residue after extraction is enriched with chlorophyll, sugar carotenoids, and glycolipids, and various medicinal effects can be expected, so the residue can also be used. The added value of extraction operations can be further increased. (3) Chlorophyll can be selectively removed from algae with a single step of pressurizing and heating liquefied carbon dioxide gas to a supercritical state exceeding the critical point, bringing it into contact with algae, and then removing carbon dioxide gas. It is possible to extract and separate the lipids in this state and manufacture them directly. Moreover, since the extractant is carbon dioxide gas in a supercritical state, separation from the desired lipid can be carried out extremely smoothly. That is, in conventional solvent extraction methods, in order to selectively obtain lipids from algae, the extraction must be carried out in multiple stages using different types of solvents, whereas the present invention requires only one stage operation. Therefore, the labor required for lipid production can be minimized, the production cost can be reduced, and the entire equipment can be made significantly more compact. (4) Although carbon dioxide in a supercritical state is in a gaseous state, it has a very high density that is close to that of a liquid.
Furthermore, since it also has a high diffusion coefficient, which is an attribute of gas, it can spread widely to every corner of the algae in the extraction tank, increasing both the extraction surface area and the contact flow rate, and has a high elution power like a liquid. Therefore, the extraction efficiency is high and the extraction amount can be increased. (5) Since carbon dioxide gas is used as the extractant, the lipids are kept in an inert atmosphere of carbon dioxide gas from the beginning to the end of the extraction operation, which prevents rancidity and deterioration, and improves the quality of extracted lipids, especially carotenoids. Can be maintained well. Inert carbon dioxide gas also poses no risk of fire or explosion compared to traditional solvent extraction methods, making it extremely safe to operate. Furthermore, even if carbon dioxide gas is discharged or leaked into the atmosphere, there is no risk of polluting the atmosphere or the environment. (6) In conventional solvent extraction methods, there is a risk that organic solvents harmful to the human body, such as chloroform and methylene chloride, may remain in the lipids.
In the method of extraction using carbon dioxide gas as in the present invention, since carbon dioxide gas is a gas, it is unlikely that this gas will remain in the product (even if a small amount remains, it is highly safe), and the The product can be used safely and non-toxicly as a health food or pigment oil. (7) Since the present invention can be applied to algae in general, with Spirulina and Chlorella as representative examples,
Since the present invention performs photosynthesis, it has great potential to be applied to plants that have chlorophyll, and therefore, by using the present invention, it is expected that useful products can be produced by extracting lipids from plants in general.

【図面の簡単な説明】[Brief explanation of the drawing]

図面は本発明に係るもので、第1図は本発明の
フローチヤート、第2図は抽出剤として用いる炭
酸ガスの圧力・温度状態図、第3図A,B、第4
図A,B及び第5図はともに種々の展開溶媒を用
いて試みた脂質の薄層クロマトグラムである。 1……藻類、2……抽出槽、3……加圧器、4
……加熱器、5……回収層、6……調圧弁、P1
……臨界圧力、T1……臨界温度、A……超臨界
ガス域。
The drawings are related to the present invention; Fig. 1 is a flow chart of the present invention, Fig. 2 is a pressure/temperature state diagram of carbon dioxide gas used as an extractant, Fig. 3 is A, B, and Fig. 4 is a flowchart of the present invention.
Figures A, B and Figure 5 are thin layer chromatograms of lipids tested using various developing solvents. 1... Algae, 2... Extraction tank, 3... Pressurizer, 4
... Heater, 5 ... Recovery layer, 6 ... Pressure regulating valve, P 1
...Critical pressure, T 1 ...Critical temperature, A...Supercritical gas region.

Claims (1)

【特許請求の範囲】[Claims] 1 抽出剤として炭酸ガスを使用し、炭酸ガスを
加圧・加熱して臨界圧力75.2Kg/cm2、臨界温度
31.1℃を超える超臨界ガス域の炭酸ガスにし、こ
の炭酸ガスを藻類に接触させて、クロロフイルを
選択的に排除した状態で、カロチノイドを含む脂
質を藻類内から炭酸ガス内に抽出する事を特徴と
する藻類からのカロチノイドを含む脂質の製造方
法。
1 Using carbon dioxide gas as an extractant, pressurize and heat the carbon dioxide gas to a critical pressure of 75.2Kg/cm 2 and a critical temperature.
It is characterized by converting carbon dioxide gas in the supercritical gas range over 31.1℃, bringing this carbon dioxide gas into contact with algae, selectively removing chlorophyll, and extracting lipids including carotenoids from within the algae into carbon dioxide gas. A method for producing lipids containing carotenoids from algae.
JP59062595A 1984-03-29 1984-03-29 Production of lipid containing carotinoids from algae Granted JPS60207567A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP59062595A JPS60207567A (en) 1984-03-29 1984-03-29 Production of lipid containing carotinoids from algae

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP59062595A JPS60207567A (en) 1984-03-29 1984-03-29 Production of lipid containing carotinoids from algae

Publications (2)

Publication Number Publication Date
JPS60207567A JPS60207567A (en) 1985-10-19
JPH0527619B2 true JPH0527619B2 (en) 1993-04-21

Family

ID=13204830

Family Applications (1)

Application Number Title Priority Date Filing Date
JP59062595A Granted JPS60207567A (en) 1984-03-29 1984-03-29 Production of lipid containing carotinoids from algae

Country Status (1)

Country Link
JP (1) JPS60207567A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY146635A (en) * 2004-09-01 2012-09-14 Malaysian Palm Oil Board Specialty palm oil products and other specialty vegetable oil products
JP2008201694A (en) * 2007-02-19 2008-09-04 Noevir Co Ltd Skin preparation
JP5770461B2 (en) * 2010-12-13 2015-08-26 Dicライフテック株式会社 Cyanobacteria powder for coloring and method for producing the same
TWI414362B (en) 2011-05-18 2013-11-11 Ind Tech Res Inst Extraction apparatus
CN107778337B (en) * 2016-08-26 2020-12-08 国投生物科技投资有限公司 Method for extracting glycolipids in spirulina by supercritical carbon dioxide
JP2021013313A (en) * 2019-07-10 2021-02-12 オーピーバイオファクトリー株式会社 Novel microalgae

Also Published As

Publication number Publication date
JPS60207567A (en) 1985-10-19

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