JP3344887B2 - Method for concentrating fats and oils containing highly unsaturated fatty acids - Google Patents
Method for concentrating fats and oils containing highly unsaturated fatty acidsInfo
- Publication number
- JP3344887B2 JP3344887B2 JP33457695A JP33457695A JP3344887B2 JP 3344887 B2 JP3344887 B2 JP 3344887B2 JP 33457695 A JP33457695 A JP 33457695A JP 33457695 A JP33457695 A JP 33457695A JP 3344887 B2 JP3344887 B2 JP 3344887B2
- Authority
- JP
- Japan
- Prior art keywords
- fatty acids
- supercritical fluid
- extraction
- fats
- 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
Links
Landscapes
- Fats And Perfumes (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は高度不飽和脂肪酸含
有油脂の濃縮方法及び装置に関し、特にアラキドン酸
（以下ＡＡと略す）、エイコサペンタエン酸（以下ＥＰ
Ａと略す）、ドコサヘキサエン酸（以下ＤＨＡと略す）
等の高度不飽和脂肪酸を、トリグリセリドの形で簡便か
つ効率よく濃縮できる高度不飽和脂肪酸含有油脂の濃縮
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for concentrating fats and oils containing highly unsaturated fatty acids, and more particularly to arachidonic acid (hereinafter abbreviated as AA), eicosapentaenoic acid (hereinafter referred to as EP).
A), docosahexaenoic acid (hereinafter abbreviated as DHA)
Polyunsaturated fatty acids, enriched in highly unsaturated fatty acid-containing oil can be simply and efficiently concentrated in the form of triglycerides and the like
About the method .
【０００２】[0002]
【従来の技術】魚油などの油脂に含まれるＡＡ、ＥＰ
Ａ、ＤＨＡは、ｎ−６系及びｎ−３系高度不飽和脂肪酸
として、それぞれ生体内で重要な役割をはたしている。
そのため、これら高度不飽和脂肪酸含有油脂類は、健康
食品を始めとする食品全般、さらには医薬品分野など多
岐にわたって使用されている。2. Description of the Related Art AA and EP contained in fats and oils such as fish oils
A and DHA play important roles in vivo as n-6 and n-3 highly unsaturated fatty acids, respectively.
Therefore, these highly unsaturated fatty acid-containing fats and oils are used in a wide variety of foods, including health foods, and in the pharmaceutical field.
【０００３】一般に、上記高度不飽和脂肪酸は天然物に
おいてはグリゼリドの形で存在しており、その含有量は
さまざまである。このため、グリセリドの中に含まれる
ＡＡ、ＥＰＡ、ＤＨＡなどの分離・精製にあたっては、
これら高度不飽和脂肪酸の低級アルコールエステルを調
製した後、真空蒸留法、分子蒸留法、超臨界抽出法、酵
素法、ウインタリング法（低温分別法または低温溶媒分
別法）、尿素付加法、銀錯体形成法、クロマト法などの
方法によって分離・精製しているのが一般的である。[0003] In general, the above-mentioned polyunsaturated fatty acids are present in the form of glycerides in natural products, and their contents vary. Therefore, when separating and purifying AA, EPA, DHA, etc. contained in glyceride,
After preparing lower alcohol esters of these highly unsaturated fatty acids, vacuum distillation, molecular distillation, supercritical extraction, and yeast
In general , separation and purification are carried out by a method such as elementary method, wintering method (low-temperature fractionation method or low-temperature solvent fractionation method), urea addition method, silver complex formation method, and chromatographic method.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記の
ごとき従来方法にあっては、高度不飽和脂肪酸の低級ア
ルコールエステルを調製した後、真空蒸留法等で分離・
精製するので、工程が複雑で効率が悪く、コスト高にな
るという不具合があった。However, in the conventional method as described above, after preparing a lower alcohol ester of a polyunsaturated fatty acid, it is separated by a vacuum distillation method or the like.
Since the purification is performed, the steps are complicated, the efficiency is low, and the cost is high.
【０００５】そこで、この不具合を回避するために、直
接トリグリセリドの形で特定の高度不飽和脂肪酸を多く
含む画分を濃縮する方法が種々提案されている。In order to avoid this problem, various methods have been proposed for directly enriching a fraction containing a large amount of a specific polyunsaturated fatty acid in the form of triglyceride.
【０００６】例えば、（１）冷却によって析出する固体
部を除去することにより、相対的に不飽和脂肪酸含有量
の高い魚油を得るウインタリング法（低温分別法または
低温溶媒分別法）、（２）ある種のリパーゼを用いて、
トリグリセリド中の高度不飽和脂肪酸以外の構成脂肪酸
のエステル結合を選択的に加水分解し、除去することに
より、高度不飽和脂肪酸含有グリセリドを濃縮する酵素
法、（３）銀イオンが二重結合を多く持つ化合物と錯体
を形成することを利用して、高度不飽和脂肪酸含有トリ
グリセリドを選択的に濃縮する銀錯体形成法、等であ
る。For example, (1) a wintering method (low-temperature fractionation or low-temperature solvent fractionation) for obtaining a fish oil having a relatively high unsaturated fatty acid content by removing a solid portion precipitated by cooling, (2) Using certain lipases,
Enzymatic method of enriching glycerides containing polyunsaturated fatty acids by selectively hydrolyzing and removing ester bonds of constituent fatty acids other than polyunsaturated fatty acids in triglyceride, (3) silver ions contain many double bonds A silver complex forming method for selectively enriching triglycerides containing highly unsaturated fatty acids by utilizing the formation of a complex with a compound having the same.
【０００７】しかし、これらの方法でも技術上あるいは
コスト面において問題が多く、高度不飽和脂肪酸をトリ
グリセリドの形のままで濃縮するための実用的有効手段
は知られていないのが現状である。However, these methods have many technical and cost problems, and practically effective means for concentrating polyunsaturated fatty acids in the form of triglycerides is not known at present.
【０００８】本発明は、上記のごとき従来の課題に鑑み
てなされたもので、その目的とするところは、高度不飽
和脂肪酸をトリグリセリドの形のままで、簡便かつ効率
よく濃縮できる高度不飽和脂肪酸含有油脂の濃縮方法を
提供することにある。The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to provide a polyunsaturated fatty acid which can easily and efficiently concentrate polyunsaturated fatty acids in the form of triglycerides. It is an object of the present invention to provide a method for concentrating fats and oils.
【０００９】[0009]
【課題を解決するための手段】上記目的を達成するため
に、請求項１の発明は、エイコサペンタエン酸及びドコ
サヘキサエン酸をはじめとする高度不飽和脂肪酸を含有
するトリグリセリドを主成分とした原料油脂を用い、エ
イコサペンタエン酸及びドコサヘキサエン酸を含む高度
不飽和脂肪酸含有量の多い画分を超臨界流体抽出法で抽
出する高度不飽和脂肪酸含有油脂の濃縮方法であって、
超臨界ガスとして二酸化炭素を用い、この二酸化炭素を
加圧・加温して超臨界状態とし、超臨界流体を発生させ
るステップと、上記発生された超臨界流体が超臨界流体
抽出塔塔底部より導入されるとともに、上記原料油脂が
塔中位部より導入され、原料油脂を超臨界流体抽出法に
よって高度不飽和脂肪酸含有量の多い画分とそうでない
画分に分離するステップと、上記超臨界流体抽出塔塔頂
部より流出した画分を減圧するステップと、上記減圧さ
れた画分を第１の抽出物と超臨界ガスとに分離するステ
ップと、上記超臨界流体抽出塔塔底部より抽出残分を第
２の抽出物として採取するステップと、を有し、上記超
臨界流体抽出塔内温度を臨界温度以上の４０〜１１０℃
に設定するとともに塔底部から塔頂部にいくに従って所
定の温度勾配を有して上昇させるようにして、塔内圧力
を臨界圧力以上の２００〜３５０ｋｇ／ｃｍ2 にし、高
度不飽和脂肪酸含有量の少ない画分を第１の抽出物とし
て採取するとともに、高度不飽和脂肪酸含有量の多い画
分を上記抽出残分として第２の抽出物として採取し、 上
記第２の抽出物として採取された高度不飽和脂肪酸含有
量の多い画分中のエイコサペンタエン酸に対するドコサ
ヘキサエン酸の割合は原料油脂のときより増加している
ことを特徴とする。In order to achieve the above-mentioned object, the invention of claim 1 comprises an eicosapentaenoic acid and
Contains highly unsaturated fatty acids such as sahexaenoic acid
Using raw oils and fats containing triglyceride as the main component
A method for concentrating highly unsaturated fatty acid-containing fats and oils by extracting a fraction having a high content of highly unsaturated fatty acids containing icosapentaenoic acid and docosahexaenoic acid by a supercritical fluid extraction method,
Using carbon dioxide as a supercritical gas, pressurizing and heating this carbon dioxide to a supercritical state, generating a supercritical fluid, and the generated supercritical fluid is supplied from the bottom of the supercritical fluid extraction column. The raw oil and fat is introduced from the middle part of the column, and the raw oil and fat is separated into a fraction having a high content of unsaturated fatty acids and a fraction having no high unsaturated fatty acid content by a supercritical fluid extraction method; and Depressurizing the fraction flowing out from the top of the fluid extraction column, separating the decompressed fraction into a first extract and a supercritical gas, extracting the fraction remaining from the bottom of the supercritical fluid extraction column. And collecting the fraction as a second extract, wherein the temperature in the supercritical fluid extraction column is 40 to 110 ° C. which is equal to or higher than the critical temperature.
From the bottom and sets so as to increase with a predetermined temperature gradient toward the top of the column in to the tower pressure to critical pressure or more 200~350kg / cm 2, high
A fraction having a low content of unsaturated fatty acids as the first extract
And extract with high polyunsaturated fatty acid content.
Minute was taken as the second extract as the extraction residue, the upper
The polyunsaturated fatty acid content collected as the second extract
Docosa against eicosapentaenoic acid in high fractions
It is characterized in that the ratio of hexaenoic acid is higher than that of the raw material fat .
【００１０】超臨界流体抽出は、よく知られているよう
に高沸点あるいは不揮発性の物質を超臨界状態のガスを
用いて抽出するもので、本発明では抽剤として二酸化炭
素を使用しているため、溶媒除去などの後処理がいらな
いこと、また他の方法と比べて品質的、コスト的に有利
であることなどの利点を有している。As is well known, supercritical fluid extraction is for extracting a high boiling point or non-volatile substance using a gas in a supercritical state. In the present invention, carbon dioxide is used as an extractant. Therefore, there are advantages that no post-treatment such as solvent removal is required, and that it is advantageous in terms of quality and cost as compared with other methods.
【００１１】以下、その詳細を述べる。The details will be described below.
【００１２】本発明で原料として用いる高度不飽和脂肪
酸含有油脂としては、構成脂肪酸中に高度不飽和脂肪酸
を含んでいる限り特に制約はないが、一般には、魚油、
藻類脂質などの水産油脂類、その他の動植物油脂類、微
生物油脂類などの、ＡＡ、ＥＰＡ、ＤＨＡなどをトリグ
リセリドの形で含有する、全ての一般的な油脂を使用す
ることが可能である。The polyunsaturated fatty acid-containing fat or oil used as a raw material in the present invention is not particularly limited as long as the polyunsaturated fatty acid is contained in the constituent fatty acids.
All common fats and oils containing AA, EPA, DHA and the like in the form of triglycerides, such as marine fats and oils such as algal lipids, other animal and vegetable fats and oils, and microbial fats and oils can be used.
【００１３】上記原料油脂を使用するに際しては、脱ガ
ム、脱酸処理などし、不純物を低減した精製油脂とする
ことが望ましいが、必ずしも本発明の必要条件ではな
い。When the above-mentioned raw material fats and oils are used, it is desirable to use degumming and deacidification treatments to obtain purified fats and oils with reduced impurities, but this is not a necessary condition of the present invention.
【００１４】本発明における超臨界流体抽出は、通常の
抽出槽、または分離能を高めるために、ラシヒリング、
ディクソン、ヘリパック等の充填剤を内部に充填し、下
部から上部に温度を段階的に上昇させることで温度勾配
を設けた精留機能を有する抽出塔などに、連続的に原料
を供給する。そして、抽出槽または抽出塔の上部から取
り出した超臨界流体を減圧して、抽出された高度不飽和
脂肪酸が少ない画分を分離し、下部から抽出残分を採取
することによって、容易に特定の高度不飽和脂肪酸をト
リグリセリドの形で濃縮分離するものである。The supercritical fluid extraction in the present invention is carried out by a conventional extraction tank or Raschig ring,
Fillers such as Dickson and Helipack are filled inside, and the temperature is gradually increased from the lower part to the upper part, so that the raw material is continuously supplied to an extraction tower having a rectification function having a temperature gradient. Then, the pressure of the supercritical fluid taken out from the upper part of the extraction tank or the extraction column is reduced, the fraction containing less extracted polyunsaturated fatty acids is separated, and the extraction residue is easily taken out from the lower part to obtain a specific product. It concentrates and separates highly unsaturated fatty acids in the form of triglycerides.
【００１５】必要ならば、得られた抽出残分を再び超臨
界流体抽出することで更に精製し、特定の脂肪酸の濃縮
を行っても良い。また、分離能を高めるため、エントレ
ーナなどを使用することも可能である。If necessary, the obtained extraction residue may be further purified by extracting it with a supercritical fluid again to concentrate a specific fatty acid. Further, an entrainer or the like can be used to enhance the separation ability.
【００１６】抽出槽または抽出塔の温度は臨界温度以上
の温度に設定することが必要であり、超臨界流体として
二酸化炭素を使用する場合には３１．１℃以上であり、
また、高度不飽和脂肪酸の変質を防止するために１５０
℃以下とすることが好ましい。It is necessary to set the temperature of the extraction tank or the extraction column to a temperature higher than the critical temperature. When carbon dioxide is used as a supercritical fluid, the temperature is 31.1 ° C. or higher;
In addition, in order to prevent the deterioration of polyunsaturated fatty acids, 150
It is preferable that the temperature is set to not more than ° C.
【００１７】圧力は臨界圧以上であり、超臨界流体とし
て二酸化炭素を使用する場合には７８ｋｇ／ｃｍ2 以上
とすることが必要である。The pressure is equal to or higher than the critical pressure, and when carbon dioxide is used as the supercritical fluid, the pressure must be equal to or higher than 78 kg / cm 2 .
【００１８】操作上安定な超臨界状態とするために、温
度は４０℃以上、圧力は８０ｋｇ／ｃｍ2 以上とするこ
とが望ましいが、特に望ましくは、温度は４０〜１１０
℃、圧力は２００〜３５０ｋｇ／ｃｍ2 である。In order to obtain an operationally stable supercritical state, the temperature is preferably at least 40 ° C. and the pressure is preferably at least 80 kg / cm 2 , and particularly preferably, the temperature is from 40 to 110.
C., pressure is 200 to 350 kg / cm 2 .
【００１９】抽出槽または抽出塔より流出した超臨界炭
酸ガスは、臨界圧力以下に減圧することにより、抽出物
と二酸化炭素に分離ができ、必要ならばその二酸化炭素
を精製後、再び超臨界炭酸ガスとして利用することもで
きる。The supercritical carbon dioxide gas flowing out of the extraction tank or the extraction column can be separated into an extract and carbon dioxide by reducing the pressure to below the critical pressure. It can also be used as a gas.
【００２０】得られた製品は、濃縮前の油脂と比較し
て、高度不飽和脂肪酸の含有量が高くなっているととも
に、ＤＨＡ／ＥＰＡ比などそれぞれの高度不飽和脂肪酸
間の比率なども変化している点が特徴として挙げられ
る。The obtained product has a higher content of polyunsaturated fatty acids than the fats and oils before concentration, and the ratio between polyunsaturated fatty acids such as DHA / EPA ratio also changes. Is a feature.
【００２１】[0021]
【発明の実施の形態】以下、本発明の実施の形態を実施
例に基づいて説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below based on examples.
【００２２】[0022]
【実施例１】方法 未精製イワシ油を定法（安田耕作他：油脂製品の知識、
Ｐ６３〜８５、幸書房、１９７７）に準拠して、脱ガ
ム、脱酸処理し、本実施例で用いる試料、すなわち精製
イワシ油を調製した。分析値は表１に示す通りである。
この精製イワシ油１００ｇを原料とし、抽出槽に温度勾
配を設けた超臨界抽出装置を用いて、抽出分と抽出残分
に分離し、それぞれの脂肪酸組成を分析した。Example 1 Method Unrefined sardine oil was prepared by a conventional method (Kousaku Yasuda et al .: Knowledge of oil and fat products,
P63-85, Koshobo, 1977), degummed and deacidified to prepare a sample used in the present example, that is, a purified sardine oil. The analysis values are as shown in Table 1.
Using 100 g of this refined sardine oil as a raw material, an extraction component and an extraction residue were separated using a supercritical extraction apparatus having a temperature gradient in an extraction tank, and the fatty acid composition of each was analyzed.
【００２３】装置 装置は、図１に示す超臨界抽出装置を使用した。以下に
その具体的構成を示す。The device apparatus using supercritical extraction apparatus shown in FIG. The specific configuration is shown below.
【００２４】まず、ボンベなどの二酸化炭素貯槽１に貯
留してある二酸化炭素を加圧装置２に供給して加圧・加
温し、二酸化炭素を超臨界状態とし、この超臨界状態と
された二酸化炭素を抽出塔３の下部より供給する。First, carbon dioxide stored in a carbon dioxide storage tank 1 such as a cylinder is supplied to a pressurizing device 2 to be pressurized and heated to bring the carbon dioxide into a supercritical state. Carbon dioxide is supplied from the lower part of the extraction tower 3.
【００２５】抽出塔３は、内径４０ｍｍ、高さ３ｍで、
内部には充填物６として直径３ｍｍのディクソンが充填
してあり、周囲には任意の温度に調整可能な加熱ヒータ
ー７が４個配設されている。ここで、４個の加熱ヒータ
ー７は下方のヒーターから上方のヒーターにいくにした
がって設定温度が高くなるよう調節され、４個の加熱ヒ
ーター７の設定温度を調節することにより所望の温度勾
配を抽出塔３内に設定できる。これによって、抽出塔３
内に二酸化炭素濃度の異なる領域が形成され、精留機能
を有することができる。The extraction tower 3 has an inner diameter of 40 mm and a height of 3 m.
The inside is filled with Dickson having a diameter of 3 mm as a filler 6, and four heaters 7 that can be adjusted to an arbitrary temperature are provided around the periphery. Here, the four heaters 7 are adjusted so that the set temperature increases from the lower heater to the upper heater, and a desired temperature gradient is extracted by adjusting the set temperature of the four heaters 7. Can be set in tower 3. Thereby, the extraction tower 3
Regions having different carbon dioxide concentrations are formed therein, and can have a rectification function.
【００２６】次に、濃縮分離する原料４は、加圧装置５
に供給されて抽出塔３内の圧力と同等にまで加圧され、
抽出塔３の下から１ｍのところから供給する。Next, the raw material 4 to be concentrated and separated is supplied to a pressure device 5
And pressurized to the same pressure as in the extraction column 3,
It is supplied from a place 1 m below the extraction tower 3.
【００２７】抽出塔３の塔頂部からは抽出分を含む超臨
界流体が取り出され、減圧弁８によって３０ｋｇ／ｃｍ
2 に減圧されて分離槽９に移され、そこで抽出物１０と
二酸化炭素に分離される。分離された二酸化炭素は減圧
弁１１によってさらに減圧され、気体処理装置１２によ
って再生されて、再度濃縮分離工程において用いられ
る。From the top of the extraction column 3, a supercritical fluid containing the extract is taken out.
The pressure is reduced to 2 and transferred to a separation tank 9, where it is separated into extract 10 and carbon dioxide. The separated carbon dioxide is further reduced in pressure by the pressure reducing valve 11, regenerated by the gas treatment device 12, and used again in the concentration separation step.
【００２８】一方、塔底部よりは、連続的に目的の抽出
残分１３が得られる。On the other hand, the desired extraction residue 13 is continuously obtained from the bottom of the column.
【００２９】なお、さらに精製する場合は、抽出残分１
３を三方弁１４を切り替えることにより、異なる条件に
て再度超臨界流体抽出し、目的の物質を得ることができ
る。In the case of further purification, extraction residue 1
By switching the three-way valve 14 to the three-way valve 14, the supercritical fluid can be extracted again under different conditions to obtain the target substance.
【００３０】 分離条件 抽出塔温度 加熱ヒーター７の温度を上部から順に５８，５４， ５０，４６℃に設定 抽出塔圧力 ２５０ｋｇ／ｃｍ2 原料供給速度 ６０ｇ／ｈ 二酸化炭素供給速度 １６ｋｇ／ｈ Separation conditions Extraction tower temperature The temperature of the heater 7 was set to 58, 54, 50 and 46 ° C. in order from the top. Extraction tower pressure 250 kg / cm 2 Raw material feed rate 60 g / h Carbon dioxide feed rate 16 kg / h
【００３１】分析方法 脂肪酸組成はガスクロマトグラフィーにより、キャピラ
リーカラムを用いて面積％として求めた。（参考文献：
ＡＣＫＭＡＮ Ｒ．Ｇ．；Ａｃｔａ Ｍｅｄ．Ｓｃａ
ｎ，２２２，９９−１０３，１９８７） 酸価（ＡＶ）は１９９４年版基準油脂分析試験法２．
４．１−８３（日本油化学協会編）に準拠して分析し
た。 Analysis Method The fatty acid composition was determined by gas chromatography as an area% using a capillary column. (References:
ACKMAN R. G. FIG. Acta Med. Sca
n, 222, 99-103, 1987) The acid value (AV) is the standard fat and oil analysis test method of 1994 edition.
The analysis was performed in accordance with 4.1-83 (edited by the Japan Oil Chemists' Society).
【００３２】結果及び考察 表１に示すように、抽出物と抽出残分に分かれ、大略下
記事項が確認された。 １．分子量の小さい脂肪酸（炭素数１８以下）から構成
された油脂（トリグリセリド）は抽出物の側に多く、分
子量の大きい脂肪酸（炭素数２０以上）の油脂は抽出残
分に分画された。即ち、高度不飽和脂肪酸から構成され
た油脂は抽出物に少なく、抽出残分に多く分画された。 ２．得られた抽出残分のＡＶは減少した。 Results and Discussion As shown in Table 1, the extract and the extract residue were separated, and the following items were confirmed. 1. Fats and oils (triglycerides) composed of fatty acids having a low molecular weight (having 18 or less carbon atoms) were more present on the extract side, and fats and oils having a fatty acid having a high molecular weight (having a carbon number of 20 or more) were fractionated into extraction residues. That is, fats and oils composed of polyunsaturated fatty acids were less in the extract and more in the extraction residue. 2. The resulting extraction residue AV was reduced.
【００３３】以上の結果から、精製イワシ油（原料）を
超臨界流体抽出することにより、抽出残分として、ＥＰ
Ａ，ＤＨＡなどの高度不飽和脂肪酸が濃縮された製品を
得ることを目的とした本発明の意図が実証された。From the above results, the purified sardine oil (raw material) was subjected to supercritical fluid extraction to obtain EP as an extraction residue.
The intention of the present invention for obtaining a product enriched in polyunsaturated fatty acids such as A and DHA was demonstrated.
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【実施例２】未精製カツオ油を実施例１に準拠して精製
し、精製カツオ油（原料）を調整した。分析値は表２に
示すとおりである。Example 2 Unrefined skipjack oil was refined according to Example 1 to prepare a refined skipjack oil (raw material). The analytical values are as shown in Table 2.
【００３６】精製カツオ油（原料）１００ｇを用いて、
実施例１と同様な装置を用いて、抽出物と抽出残分に分
画し、それぞれの脂肪酸組成等を分析した。Using 100 g of refined skipjack oil (raw material),
Using the same apparatus as in Example 1, fractionation into an extract and an extraction residue was performed, and the fatty acid composition of each fraction was analyzed.
【００３７】分離条件は以下に示すとおりである。 抽出塔温度 加熱ヒーター７の温度を上部から順に５８，５４， ５０，４６℃に設定 抽出塔圧力 ２５０ｋｇ／ｃｍ2 原料供給速度 ５０ｇ／ｈ 二酸化炭素供給速度 １８ｋｇ／ｈThe separation conditions are as follows. Extraction tower temperature The temperature of the heater 7 was set to 58, 54, 50 and 46 ° C. in order from the top. Extraction tower pressure 250 kg / cm 2 Raw material supply rate 50 g / h Carbon dioxide supply rate 18 kg / h
【００３８】その結果、表２に示すとおり、大略実施例
１と同様の結果が得られた。As a result, as shown in Table 2, almost the same results as in Example 1 were obtained.
【００３９】以上の結果から、精製カツオ油（原料）を
超臨界流体抽出することにより、抽出残分として、ＤＨ
Ａなどの高度不飽和脂肪酸が濃縮された製品を得ること
を目的とした本発明の意図が実証された。From the above results, the purified bonito oil (raw material) was extracted by supercritical fluid, and DH was extracted as an extraction residue.
The intent of the present invention aimed at obtaining a product enriched in polyunsaturated fatty acids such as A has been demonstrated.
【００４０】[0040]
【表２】 [Table 2]
【００４１】[0041]
【実施例３】オゴノリ（Ｇｒａｃｉｌａｒｉａ ｖｅｒ
ｒｕｃｏｓａ）原油は、オゴノリの凍結乾燥品をｎ−ヘ
キサンによって抽出し、溶媒除去後、実施例１に準拠し
て精製し、精製オゴノリ油（原料）を調製した。分析値
は表３に示すとおりである。Example 3 Ogonori (Graciliaria ver.)
rucosa) crude oil was obtained by extracting a freeze-dried product of Ogonori with n-hexane, removing the solvent, and purifying according to Example 1 to prepare a purified Ogonori oil (raw material). The analysis values are as shown in Table 3.
【００４２】精製オゴノリ油（原料）１００ｇを用い
て、実施例１と同様な装置を用いて、抽出物と抽出残分
に分画し、それぞれの脂肪酸組成等を分析した。Using 100 g of purified oil (raw material), an extract and an extraction residue were fractionated using the same apparatus as in Example 1, and the fatty acid composition of each was analyzed.
【００４３】分離条件は以下に示すとおりである。 抽出塔温度 加熱ヒーター７の温度を上部から順に６２，５８， ５４，５０℃に設定 抽出塔圧力 ２４０ｋｇ／ｃｍ2 原料供給速度 ６０ｇ／ｈ 二酸化炭素供給速度 １６ｋｇ／ｈThe separation conditions are as follows. Extraction tower temperature The temperature of the heater 7 is set to 62, 58, 54, 50 ° C. in order from the top. Extraction tower pressure 240 kg / cm 2 Raw material supply rate 60 g / h Carbon dioxide supply rate 16 kg / h
【００４４】その結果、表３に示すとおり、大略実施例
１と同様の効果が得られた。As a result, as shown in Table 3, substantially the same effects as in Example 1 were obtained.
【００４５】以上の結果から、精製オゴノリ油（原料）
を超臨界流体抽出することにより、抽出残分として、Ａ
Ａなどの高度不飽和脂肪酸が濃縮された製品を得ること
を目的とした本発明の意図が実証された。From the above results, refined Ogonori oil (raw material)
Is extracted by a supercritical fluid to obtain A as an extraction residue.
The intent of the present invention aimed at obtaining a product enriched in polyunsaturated fatty acids such as A has been demonstrated.
【００４６】[0046]
【表３】 [Table 3]
【００４７】[0047]
【実施例４】実施例１で得られた抽出残分６０ｇを用
い、実施例１と同様な装置を用いて、抽出物と抽出残分
に区画し、それぞれの脂肪酸組成等を分析した。Example 4 Using 60 g of the extraction residue obtained in Example 1 and using the same apparatus as in Example 1, the extract and the extraction residue were partitioned, and their fatty acid compositions and the like were analyzed.
【００４８】分離条件は以下に示すとおりである。 抽出塔温度 加熱ヒーター７の温度を上部から順に５４，５０， ４６，４２℃に設定 抽出塔圧力 ２６０ｋｇ／ｃｍ2 原料供給速度 ２０ｇ／ｈ 二酸化炭素供給速度 １８ｋｇ／ｈThe separation conditions are as follows. Extraction tower temperature The temperature of the heater 7 is set to 54, 50, 46, and 42 ° C. in order from the top. Extraction tower pressure 260 kg / cm 2 Raw material supply rate 20 g / h Carbon dioxide supply rate 18 kg / h
【００４９】その結果、表４に示すとおり、ＤＨＡなど
の分子量の特に大きい脂肪酸以外がほぼ抽出されたこと
が分かった。As a result, as shown in Table 4, it was found that almost all but fatty acids having particularly high molecular weight such as DHA were extracted.
【００５０】以上の結果から、抽出残分を超臨界流体抽
出することにより、抽出物として、ＥＰＡが更に濃縮さ
れた製品を得ることができ、本発明の意図が実証され
た。From the above results, it was possible to obtain a product in which EPA was further concentrated as an extract by extracting the extraction residue with a supercritical fluid, and the intention of the present invention was proved.
【００５１】[0051]
【表４】 [Table 4]
【００５２】[0052]
【発明の効果】以上説明したように、本発明では、高度
不飽和脂肪酸含有油脂から高度不飽和脂肪酸含有量の多
い画分を取得するに当たり、原料油脂を超臨界流体抽出
することにより高度不飽和脂肪酸の少ない画分等を不純
物として除去し、高度不飽和脂肪酸含量の多い製品を得
るようにしたので、高度不飽和脂肪酸をトリグリセリド
の形のままで、簡便かつ効率よく濃縮できる。As described above, according to the present invention, in obtaining a fraction having a high content of polyunsaturated fatty acids from fats and oils containing polyunsaturated fatty acids, the raw material fats and oils are extracted by supercritical fluid to obtain highly unsaturated fatty acids. Since the fraction containing less fatty acid or the like is removed as impurities to obtain a product having a higher content of polyunsaturated fatty acid, polyunsaturated fatty acid can be easily and efficiently concentrated in the form of triglyceride.
【００５３】また、本発明では、通常の超臨界抽出装置
を用いることができるので、工業的規模で高度不飽和脂
肪酸含量の多い製品を得ることができ、低コストにこの
種製品を得ることができる。Further, in the present invention, since a normal supercritical extraction device can be used, a product having a high content of highly unsaturated fatty acids on an industrial scale can be obtained, and this type of product can be obtained at low cost. it can.
【図１】本発明の抽出分離に使用する超臨界抽出装置の
概略構成図。FIG. 1 is a schematic configuration diagram of a supercritical extraction device used for extraction and separation of the present invention.
１ 二酸化炭素貯槽 ２ 加圧装置 ３ 抽出塔 ４ 原料 ５ 加圧装置 ６ 充填物 ７ 加熱装置 ８ 減圧弁 ９ 分離槽 １０ 抽出物 １１ 減圧弁 １２ 気体処理装置 １３ 製品（抽出残分） １４ 三方弁 DESCRIPTION OF SYMBOLS 1 Carbon dioxide storage tank 2 Pressurizing device 3 Extraction tower 4 Raw material 5 Pressurizing device 6 Packing 7 Heating device 8 Pressure reducing valve 9 Separation tank 10 Extract 11 Pressure reducing valve 12 Gas processing device 13 Product (extraction residue) 14 Three-way valve
───────────────────────────────────────────────────── フロントページの続き (72)発明者 万倉 三正 広島県福山市箕沖町95番地７ 池田食研 株式会社研究室内 (56)参考文献 特開 平１−249102（ＪＰ，Ａ) 特開 昭60−115698（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C11B 1/10,7/00 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Mitsumasa Mankura 95-7, Minokiki-cho, Fukuyama-shi, Hiroshima Ikeda Food Research Laboratories Co., Ltd. (56) References JP-A-1-249102 (JP, A) JP-A 60-115698 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C11B 1/10, 7/00
Claims (1)
エン酸をはじめとする高度不飽和脂肪酸を含有するトリ
グリセリドを主成分とした原料油脂を用い、エイコサペ
ンタエン酸及びドコサヘキサエン酸を含む高度不飽和脂
肪酸含有量の多い画分を超臨界流体抽出法で抽出する高
度不飽和脂肪酸含有油脂の濃縮方法であって、 超臨界ガスとして二酸化炭素を用い、この二酸化炭素を
加圧・加温して超臨界状態とし、超臨界流体を発生させ
るステップと、 上記発生された超臨界流体が超臨界流体抽出塔塔底部よ
り導入されるとともに、上記原料油脂が塔中位部より導
入され、原料油脂を超臨界流体抽出法によって高度不飽
和脂肪酸含有量の多い画分とそうでない画分に分離する
ステップと、 上記超臨界流体抽出塔塔頂部より流出した画分を減圧す
るステップと、 上記減圧された画分を第１の抽出物と超臨界ガスとに分
離するステップと、 上記超臨界流体抽出塔塔底部より抽出残分を第２の抽出
物として採取するステップと、 を有し、 上記超臨界流体抽出塔内温度を臨界温度以上の４０〜１
１０℃に設定するとともに塔底部から塔頂部にいくに従
って所定の温度勾配を有して上昇させるようにして、塔
内圧力を臨界圧力以上の２００〜３５０ｋｇ／ｃｍ2 に
し、高度不飽和脂肪酸含有量の少ない画分を第１の抽出物と
して採取するとともに、高度不飽和脂肪酸含有量の多い
画分を上記抽出残分として第２の抽出物として採取し、 上記第２の抽出物として採取された高度不飽和脂肪酸含
有量の多い画分中のエイコサペンタエン酸に対するドコ
サヘキサエン酸の割合は原料油脂のときより増加してい
る ことを特徴とする高度不飽和脂肪酸含有油脂の濃縮方
法。(1)Eicosapentaenoic acid and docosahexa
Birds containing polyunsaturated fatty acids such as enic acid
Eicosape using glyceride-based raw material fats and oils
Contains pentanoic acid and docosahexaenoic acidHighly unsaturated fat
Extraction of fractions with high fatty acid content by supercritical fluid extraction
A method for concentrating fats and oils containing unsaturated fatty acids, using carbon dioxide as a supercritical gas,
Pressurized and heated to supercritical state to generate supercritical fluid
The supercritical fluid generated above from the bottom of the supercritical fluid extraction column.
And the above-mentioned raw material is introduced from the middle of the tower.
And the raw oil and fat is highly unsaturated by supercritical fluid extraction.
Separation into fractions with high content of fatty acids and fractions without
Step, and depressurizing the fraction flowing out from the top of the supercritical fluid extraction tower.
Separating the decompressed fraction into a first extract and a supercritical gas.
Separating the extraction residue from the bottom of the supercritical fluid extraction column.
Collecting the material as a substance; and setting the temperature in the supercritical fluid extraction column to 40 to 1 above the critical temperature.
Set the temperature to 10 ° C and proceed from the bottom to the top.
The tower is raised with a predetermined temperature gradient
The internal pressure is 200 to 350 kg / cm which is higher than the critical pressureTwoTo
AndThe fraction having a low content of polyunsaturated fatty acids is referred to as the first extract.
With high unsaturated fatty acid content
Collecting the fractions as a second extract as the extraction residue, Containing the polyunsaturated fatty acids collected as the second extract
DOCOMO for eicosapentaenoic acid in the abundant fraction
The ratio of sahexaenoic acid is higher than that of raw fats and oils.
To Method of concentrating fats and oils containing polyunsaturated fatty acids characterized by the following
Law.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33457695A JP3344887B2 (en) | 1995-12-22 | 1995-12-22 | Method for concentrating fats and oils containing highly unsaturated fatty acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33457695A JP3344887B2 (en) | 1995-12-22 | 1995-12-22 | Method for concentrating fats and oils containing highly unsaturated fatty acids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09176678A JPH09176678A (en) | 1997-07-08 |
| JP3344887B2 true JP3344887B2 (en) | 2002-11-18 |
Family
ID=18278950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33457695A Expired - Fee Related JP3344887B2 (en) | 1995-12-22 | 1995-12-22 | Method for concentrating fats and oils containing highly unsaturated fatty acids |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3344887B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8372812B2 (en) | 2009-02-26 | 2013-02-12 | Aker Biomarine Asa | Phospholipid and protein tablets |
| US8697138B2 (en) | 2007-03-28 | 2014-04-15 | Aker Biomarine As | Methods of using krill oil to treat risk factors for cardiovascular, metabolic, and inflammatory disorders |
| US9028877B2 (en) | 2007-03-28 | 2015-05-12 | Aker Biomarine Antarctic As | Bioeffective krill oil compositions |
| US9867856B2 (en) | 2014-01-10 | 2018-01-16 | Aker Biomarine Antarctic As | Phospholipid compositions and their preparation |
| US10456412B2 (en) | 2015-02-11 | 2019-10-29 | Aker Biomarine Antarctic As | Lipid extraction processes |
| US10704011B2 (en) | 2013-06-14 | 2020-07-07 | Aker Biomarine Antarctic As | Lipid extraction processes |
| US10864223B2 (en) | 2015-02-11 | 2020-12-15 | Aker Biomarine Antarctic As | Lipid compositions |
-
1995
- 1995-12-22 JP JP33457695A patent/JP3344887B2/en not_active Expired - Fee Related
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9730966B2 (en) | 2007-03-28 | 2017-08-15 | Aker Biomarine Antartic As | Method of reducing appetite in a human subject comprising administering krill oil composition |
| US10010567B2 (en) | 2007-03-28 | 2018-07-03 | Aker Biomarine Antarctic As | Bioeffective krill oil compositions |
| US9028877B2 (en) | 2007-03-28 | 2015-05-12 | Aker Biomarine Antarctic As | Bioeffective krill oil compositions |
| US9034388B2 (en) | 2007-03-28 | 2015-05-19 | Aker Biomarine Antartic As | Bioeffective krill oil compositions |
| US9072752B1 (en) | 2007-03-28 | 2015-07-07 | Aker Biomarine Antarctic As | Bioeffective krill oil compositions |
| US9078905B2 (en) | 2007-03-28 | 2015-07-14 | Aker Biomarine Antarctic As | Bioeffective krill oil compositions |
| US9119864B2 (en) | 2007-03-28 | 2015-09-01 | Aker Biomarine Antarctic As | Bioeffective krill oil compositions |
| US9220735B2 (en) | 2007-03-28 | 2015-12-29 | Aker Biomarine Antarctic As | Methods of using krill oil to treat risk factors for cardiovascular, metabolic, and inflammatory disorders |
| US9320765B2 (en) | 2007-03-28 | 2016-04-26 | Aker Biomarine Antarctic As | Bioeffective krill oil compositions |
| US9375453B2 (en) | 2007-03-28 | 2016-06-28 | Aker Biomarine Antarctic As | Methods for producing bioeffective krill oil compositions |
| US11865143B2 (en) | 2007-03-28 | 2024-01-09 | Aker Biomarine Antarctic As | Bioeffective krill oil compositions |
| US9644170B2 (en) | 2007-03-28 | 2017-05-09 | Aker Biomarine Antarctic As | Bioeffective krill oil compositions |
| US9644169B2 (en) | 2007-03-28 | 2017-05-09 | Aker Biomarine Antarctic As | Bioeffective krill oil compositions |
| US9816046B2 (en) | 2007-03-28 | 2017-11-14 | Aker Biomarine Antarctic As | Bioeffective krill oil compositions |
| US10543237B2 (en) | 2007-03-28 | 2020-01-28 | Aker Biomarine Antarctic As | Bioeffective krill oil compositions |
| US9889163B2 (en) | 2007-03-28 | 2018-02-13 | Aker Biomarine Antarctic As | Bioeffective krill oil compositions |
| US8697138B2 (en) | 2007-03-28 | 2014-04-15 | Aker Biomarine As | Methods of using krill oil to treat risk factors for cardiovascular, metabolic, and inflammatory disorders |
| US8372812B2 (en) | 2009-02-26 | 2013-02-12 | Aker Biomarine Asa | Phospholipid and protein tablets |
| US10704011B2 (en) | 2013-06-14 | 2020-07-07 | Aker Biomarine Antarctic As | Lipid extraction processes |
| US11578289B2 (en) | 2013-06-14 | 2023-02-14 | Aker Biomarine Antarctic As | Lipid extraction processes |
| US9867856B2 (en) | 2014-01-10 | 2018-01-16 | Aker Biomarine Antarctic As | Phospholipid compositions and their preparation |
| US10456412B2 (en) | 2015-02-11 | 2019-10-29 | Aker Biomarine Antarctic As | Lipid extraction processes |
| US10864223B2 (en) | 2015-02-11 | 2020-12-15 | Aker Biomarine Antarctic As | Lipid compositions |
| US11819509B2 (en) | 2015-02-11 | 2023-11-21 | Aker Biomarine Antarctic As | Lipid compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09176678A (en) | 1997-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2469647C (en) | Extraction and winterization of lipids from oilseed and microbial sources | |
| EP1436370B1 (en) | Method for producing mixtures of triglycerides of natural polyunsaturated fatty acids with high polyunsaturated fatty acid content | |
| CA2492720C (en) | A process for decreasing the amount of cholesterol in a marine oil using a volatile working fluid | |
| CN103221524B (en) | Method for concentrating omega-3 fatty acids | |
| Mishra et al. | Extraction and purification of ω-3 fatty acids with an emphasis on supercritical fluid extraction—A review | |
| JP2014511406A (en) | Eicosapentaenoic acid concentrate | |
| Guil-Guerrero et al. | γ-Linolenic acid purification from seed oil sources by argentated silica gel chromatography column | |
| JP6423436B2 (en) | Chromatographic method for producing polyunsaturated fatty acids | |
| WO2015029364A1 (en) | Method for producing high purity omega-3 fatty acid ethyl ester | |
| JPH09157684A (en) | Purification of highly unsaturated fatty acid ester | |
| KR20150021920A (en) | Method for continuously enriching an oil produced by microalgae with ethyl esters of dha | |
| JP6581090B2 (en) | Method for chromatographic purification of fatty acids | |
| US20110124728A1 (en) | Dha enrichment process | |
| JP3344887B2 (en) | Method for concentrating fats and oils containing highly unsaturated fatty acids | |
| JPH0789944B2 (en) | Method for producing oil and fat composition for confectionery | |
| JP3611222B2 (en) | Method for reducing peroxides of highly unsaturated fatty acids | |
| JP6467426B2 (en) | Purification of fatty acids by chromatographic methods. | |
| JP3678317B2 (en) | Method for concentrating eicosapentaenoic acid-containing material | |
| JP3340182B2 (en) | Method for producing triglyceride containing docosahexaenoic acid | |
| Guil-Guerrero et al. | Isolation of some PUFA from edible oils by argentated silica gel chromatography | |
| Juaneda et al. | Conjugated linoleic acid (CLA) isomers in heat-treated vegetable oils | |
| KR102520377B1 (en) | Method for preparing triglyceride with high purity by using short path distillation or wet fractionation | |
| JP2005255971A (en) | Method for concentrating highly unsaturated fatty acid | |
| KR20220107225A (en) | Microbial oil composition fortified with polyunsaturated fatty acids | |
| JP2001354991A (en) | Purification process for highly unsaturated fatty acid- containing oil and fat |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20000602 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080830 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090830 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100830 Year of fee payment: 8 |
|
| LAPS | Cancellation because of no payment of annual fees |