JPH07242895A - Eicosapentaenoic acid of high purity and isolation and purification of lower alcohol ester thereof - Google Patents

Eicosapentaenoic acid of high purity and isolation and purification of lower alcohol ester thereof

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JPH07242895A
JPH07242895A JP5528193A JP5528193A JPH07242895A JP H07242895 A JPH07242895 A JP H07242895A JP 5528193 A JP5528193 A JP 5528193A JP 5528193 A JP5528193 A JP 5528193A JP H07242895 A JPH07242895 A JP H07242895A
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epa
fatty acids
acid
silver nitrate
high purity
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Mitsumasa Mansou
Katsuyuki Nishioka
Yasuyuki Takagaki
三正 万倉
功志 西岡
康幸 高垣
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Ikeda Shiyotsuken Kk
池田食研株式会社
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Abstract

PURPOSE:To provide a method for obtaining eicosapentaenoic acid or its lower alkyl ester of high purity from natural fat and oil containing 2 or more kinds of high saturated fatty acids such as eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA) and the like. CONSTITUTION:In the isolation and purification of EPA or its lower alkyl ester from natural, fat and oil containing more than 2 kinds of high saturated fatty acids such as EPA, DHA and the like, EPA or its lower alkyl ester is partially purified by the vacuum rectification refinement, then treated in aqueous silver nitrate to recover EPA or its ester of high purity as a water-soluble component.

Description

【発明の詳細な説明】 DETAILED DESCRIPTION OF THE INVENTION

【0001】 [0001]

【産業上の利用分野】本発明は高純度エイコサペンタエン酸又はその低級アルコールエステルの分離精製法に関し、更に詳細には、高度不飽和脂肪酸類又はそれらの誘導体を含む天然油脂から工業的規模で高純度エイコサペンタエン酸又はその低級アルコールエステルを製造する方法に関する。 The present invention relates to an method for the separation and purification of high purity eicosapentaenoic acid or a lower alcohol esters, more particularly, high on an industrial scale from natural fats and oils containing polyunsaturated fatty acids or their derivatives It relates to a process for producing pure eicosapentaenoic acid or a lower alcohol ester.

【0002】 [0002]

【従来の技術】高度不飽和脂肪酸はその広範な生理活性から、食品、医薬品、飼料等への実施が考えられており、すでに、実施されている分野もある(「機能性脂質の開発と応用」,佐藤清隆他監修,シーエムシー (199 BACKGROUND ART Polyunsaturated fatty acids from the broad physiological activities, food, medicine, the implementation of the feed and the like are considered, already some areas has been carried out (development of "functional lipid Applications "Kiyotaka Sato other supervised, CMC (199
2))。 2)). ここで、高度不飽和脂肪酸とは炭素数 16 個以上でかつ不飽和結合数が3個以上の脂肪酸群を指し、例えば、オクタデカテトラエン酸、ジホモ- γ- リノレン酸、アラキドン酸、エイコサペンタエン酸(以下、EP Here, the highly unsaturated fatty acids refers to three or more fatty acid groups and unsaturated bond number is the number 16 or more carbon atoms, such as octadecatetraenoic acid, dihomo - .gamma.-linolenic acid, arachidonic acid, eicosapentaenoic acid (hereinafter, EP
Aという)、ドコサペンタエン酸、ドコサヘキサエン酸(以下、DHAという)などが挙げられる。 Of A), docosapentaenoic acid, docosahexaenoic acid (hereinafter, referred to as DHA), and the like. また、これら脂肪酸の誘導体としては、脂肪酸のメチルエステル又はエチルエステルがある。 Derivatives of these fatty acids, methyl esters or ethyl esters of fatty acids.

【0003】高度不飽和脂肪酸の中でも、特に、EPA [0003] Among the polyunsaturated fatty acids, in particular, EPA
は血小板凝集能の低下、血液粘度の低下、血中脂質(中性脂質、コレステロール)濃度の適正化、血圧低下などの機能が期待できる(鹿山光:臨床栄養、68、345-350 Reduction of platelet aggregation, the lowering of blood viscosity, blood lipids (neutral lipids, cholesterol) optimization of the concentration, functions such as hypotensive can be expected (Hikari Kayama: Clinical Nutrition, 68,345-350
(1986) )ことから、特定保健用食品素材としても関心が持たれており、また、飼料素材としても注目されており(HW HULAN et al , Can. J. Anim. Sci. 68 ,533 (1986)), it has been also have interest as specified health food material, also, has been attracting attention as a feed material (HW HULAN et al, Can. J. Anim. Sci. 68, 533
-547(1988) ;特開平1-215245, 特開平3-228652他)、さらに、EPAエチルエステルの高純度品は医薬品としても利用されている。 -547 (1988); JP-A 1-215245, JP-A-3-228652, etc.), furthermore, high purity of EPA-ethyl ester is utilized as a pharmaceutical.

【0004】EPAは一般に魚油中に広く分布している(日本水産油脂協会編:魚介類の脂肪酸組成表(1989), [0004] EPA is generally widely distributed in fish oil (Nippon Suisan fat Kyokai: fish and shellfish of the fatty acid composition table (1989),
光琳( 東京))ほか、微生物(鈴木修,油化学,41, 77 Korin (Tokyo)) In addition, microorganisms (Osamu Suzuki, oil chemistry, 41, 77
9-786(1992) ; 清水昌・山田秀明, 醸協, 87, 36-43(19 9-786 (1992); Akira Shimizu Yamada, Hideaki, 醸協, 87, 36-43 (19
92) ; 矢沢一良, 微生物, 5,66-75(1989))、藻類(鈴木修,油化学,41, 779-786(1992) )、高等植物(TR 92); Kazuyoshi Yazawa, microorganisms, 5,66-75 (1989)), algae (Osamu Suzuki, oil chemistry, 41, 779-786 (1992)), higher plants (TR
Omara-Alwala et al, JAOCS, 68 , 198-199(1991) ) Omara-Alwala et al, JAOCS, 68, 198-199 (1991))
等々に存在が知られているが、いずれの場合もEPAは糖脂質、燐脂質、トリグリセリド等のグリセリドの形で存在している場合が多く、そのままの形で高純度化することは困難である。 Although present in so is known, either the EPA glycolipids case of, phospholipids, often are present in the form of glycerides such as triglycerides, it is difficult to highly purified intact . 従って、上記天然油脂原料中の脂肪酸又はそれらの誘導体を調製し、EPA又はその誘導体のみを分離精製する手法が採用され、下記の如き方法がある。 Thus, the fatty acids or their derivatives of the natural fat in the raw material is prepared, EPA or a derivative thereof alone is employed method of separation and purification is, there is such method follows.

【0005】すなわち、従来のEPA又はその誘導体の濃縮方法としては、尿素付加法(特開昭57-164196, 特開昭59-118740, 特開平2-19338, 特開平2-25447 Namely, as a method for concentrating a conventional EPA or a derivative thereof, urea addition method (JP 57-164196, JP 59-118740, JP-A 2-19338, JP-A-2-25447
他)、分子蒸留法(特開昭57-96095, 特開昭59-113099 Other), molecular distillation method (JP-A-57-96095, JP-A-59-113099
, 特開昭59-172596, 特開昭60-234930, 特開昭64- , JP-A-59-172596, JP-A-60-234930, JP-A-64
70439他)、真空精密蒸留法(特開昭57-144900, 特開昭57-187397, 特開昭58-8037 , 特開昭64-48898 ,特開平4-41457 , 特開平4-128250, 特開平4-268133他)、クロマトグラフィー(特開昭56-115736, 特開昭58-10944 70439, etc.), vacuum precision distillation method (JP 57-144900, JP 57-187397, JP 58-8037, Sho 64-48898, Hei 4-41457, Hei 4-128250, JP No. 4-268133, etc.), chromatography (JP 56-115736, JP 58-10944
4, 特開昭63-45235 ,特開昭64-70439 , 特開平2-2587 4, JP 63-45235, JP 64-70439, JP-A-2-2587
42, 特開平3-167294他)、超臨界流体利用法(特開昭60 42, JP-A 3-167294 etc.), supercritical fluid usage (JP 60
-214757,特開昭61-225139,特開昭62-29550,特開昭62-72 -214757, JP-A-61-225139, JP-A-62-29550, JP-A-62-72
793, 特開平1-249742他)、硝酸銀担持カラムと超臨界流体利用法の組み合わせ(特開昭63-208549, 特開平2- 793, JP-A-1-249742, etc.), the combination of silver nitrate bearing columns and supercritical fluid usage (JP 63-208549, JP-2-
8298, 特開平2-194802他)、硝酸銀錯体法(特開平4-10 8298, JP-A-2-194802, etc.), silver nitrate complex method (JP-A-4-10
3558 , 特開平4-154896 ,特開平4-159398 , 特開平4- 3558, JP-A 4-154896, JP-A-4-159398, JP-A-4-
218596, 特開平4-243849)等々が公知である。 218596, JP-A-4-243849), etc. are known.

【0006】 [0006]

【発明が解決しようとする課題】しかしながら、上記の如き従来手法のうち、まず、尿素付加法は経済的かつ簡便な方法であるが、EPA以外の高度不飽和脂肪酸類も同時に濃縮されるため、一般に、複数の高度不飽和脂肪酸類を含む天然油脂由来の脂肪酸又はそれらの誘導体を出発原料とした時、EPA又はその誘導体のみを選択的に濃縮することは困難であることから、尿素付加法単独でEPAを濃縮することは実際的方法とは見做されない。 [SUMMARY OF THE INVENTION However, among the above-mentioned conventional method, firstly, because the urea addition method is a economical and simple way, the highly unsaturated fatty acids other than EPA is also concentrated at the same time, in general, when the fatty acid or derivative thereof derived from natural fats and oils containing a plurality of highly unsaturated fatty acids was used as a starting material, since it is difficult to selectively enrich only EPA or a derivative thereof, urea addition method alone in concentrating the EPA it is not considered the practical method.

【0007】分子蒸留法は経済的かつ簡便な方法であり、しかも、一般に、真空精密蒸留法よりも低温で処理出来るため熱変性の危険性も少ないが、高度不飽和脂肪酸類又はそれらの誘導体の相互分離が困難であり、複数の高度不飽和脂肪酸類を含む天然油脂由来の脂肪酸類又はそれらの誘導体を出発原料とした時、高純度EPAまたはそのエステルを分子蒸留法単独で得ることは実際的方法とは言えない。 [0007] Molecular distillation is economical and simple method, moreover, in general, is also less risk of thermal denaturation for possible processing at lower temperatures than the vacuum precision distillation method, polyunsaturated fatty acids or their derivatives separated from each other it is difficult, impractical when the fatty acids or their derivatives from natural fats and oils were used as a starting material, to obtain highly pure EPA or esters thereof with molecular distillation alone containing multiple highly unsaturated fatty acids it can not be said of the method.

【0008】真空精密蒸留法は経済的かつ簡便な方法であり、しかも、一般に、分子蒸留法よりも分離能が高く、パルミチン酸、ステアリン酸、オレイン酸などの飽和脂肪酸類、モノエン脂肪酸類の相互分離には適しているが、高温で長時間処理するため高度不飽和脂肪酸類は熱変性する危険性が高く、複数の高度不飽和脂肪酸類を含む天然油脂由来の脂肪酸類又はそれらの誘導体を出発原料とした時、高純度EPAまたはそのエステルを真空蒸留法単独で得ることは実際的方法とは言えない。 [0008] Vacuum precision distillation method is economical and simple method, moreover, in general, higher resolution than the molecular distillation process, palmitic acid, stearic acid, saturated fatty acids such as oleic acid, mutual monoenoic fatty acids is suitable for the separation starting polyunsaturated fatty acids for treatment at a high temperature for a long time has a high risk of thermal denaturation, the fatty acids or their derivatives from natural fats and oils containing a plurality of polyunsaturated fatty acids when the raw material, is not a practical method to obtain highly pure EPA or esters thereof in a vacuum distillation alone.

【0009】液体クロマトグラフィーに代表されるクロマトグラフィーによる方法は、一般に、穏和な条件下で、確実に複数の高度不飽和脂肪酸類を含む天然油脂由来の脂肪酸類又はそれらの誘導体から高純度EPAまたはそのエステルを分離精製出来るが、カラム充填剤や移動相に要するコストが高価になり、しかも、原理的に大量処理が困難であり、工業的に実際的な方法とは言えない。 [0009] Method chromatographic typified by liquid chromatography, generally under mild conditions, ensuring high purity EPA or from fatty acids or their derivatives from natural fats and oils containing a plurality of polyunsaturated fatty acids its ester can give the more expensive the cost of the column packing material or the mobile phase, moreover, it is difficult to theoretically mass treatment can not be said industrially practical method.

【0010】超臨界流体利用法及び硝酸銀担持カラムと超臨界流体利用法の組み合わせ法は複数の高度不飽和脂肪酸類を含む天然油脂由来の脂肪酸類又はそれらの誘導体から高純度EPAまたはそのエステルを分離精製出来るが、設備費用が高価となり、コスト上不利である。 [0010] Supercritical fluid usage and silver nitrate bearing columns and the combination method of the supercritical fluid usage separation of high purity EPA or its ester from the fatty acids or their derivatives from natural fats and oils containing a plurality of polyunsaturated fatty acids Although purification can, equipment cost becomes expensive, the cost on a disadvantage.

【0011】硝酸銀錯体法は複数の高度不飽和脂肪酸類を含む天然油脂由来の脂肪酸類又はそれらの誘導体から高度不飽和脂肪酸類又はそれらのエステル類を分別する事が出来るが、複数の高度不飽和脂肪酸類又はそれらのエステル類が同時に同一画分に濃縮されるため、高純度EPAまたはそのエステルのみを選択的に分離する事は硝酸銀錯体法単独では困難である。 [0011] Silver nitrate complex method may be used to separate the natural fats fatty acids derived from or highly unsaturated fatty acids or their esters derivatives thereof including a plurality of highly unsaturated fatty acids, but more highly unsaturated since the fatty acids or their esters are enriched in the same fraction simultaneously, it is difficult with silver nitrate complex method alone to selectively separate only pure EPA or esters thereof.

【0012】以上に述べてきた如く、高度不飽和脂肪酸類は酸化し易く、高温下では熱異性体を生じるなどの変性を起こし易いので、従来法によっては複数の高度不飽和脂肪酸類を含む天然油脂由来の脂肪酸類又はそれらの誘導体から選択的に高純度EPAまたはそのエステルのみを低コストに、かつ工業的規模で分離精製する事は困難であった。 [0012] As has been described above, highly unsaturated fatty acids easily oxidized, so prone to denaturation, such as produce thermal isomer at a high temperature, the natural by conventional methods including a plurality of polyunsaturated fatty acids selectively pure EPA or low cost esters thereof only from fatty acids or their derivatives from oil, and that the separation and purification on an industrial scale is difficult.

【0013】この発明は、上記の如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、高度不飽和脂肪酸類を2種類以上含有する天然油脂由来の脂肪酸類又はそれらの誘導体から選択的に高純度EPAまたはその低級アルコールエステルのみを低コストに、かつ工業的規模で分離精製する方法を提供することにある。 [0013] The present invention has been made in view of conventional problems such as above, it is an object of the fatty acids or their derivatives from natural fats and oils containing polyunsaturated fatty acids of two or more selectively in high purity EPA or only low cost that a lower alcohol esters, and to provide a method for separating and purifying an industrial scale.

【0014】 [0014]

【課題を解決するための手段】上記目的を達成するために、本発明は、エイコサペンタエン酸、ドコサヘキサエン酸等の高度不飽和脂肪酸を2種類以上含有する天然油脂類から得られる脂肪酸混合物又はそれらの誘導体を真空精密蒸留に付し、EPA又はその低級アルコールエステルの含有量が50重量%以上で、かつ、EPA以外の高度不飽和脂肪酸又はそれらの低級アルコールエステルの含有量が合計10重量%以下の留分を採取し、しかる後に、それら留分と30〜70%硝酸銀水溶液(W/V) とを容量比で 1:100 〜50:100 の割合で混合せしめ、高度不飽和脂肪酸類又はそれらのエステル類を分離することを特徴とする。 To achieve the above object of the Invention The present invention provides eicosapentaenoic acid, polyunsaturated fatty acids of 2 fatty acid mixtures obtained from natural fats and oils containing more than or thereof such as docosahexaenoic acid subjected derivative vacuum precision distillation, the content of EPA or its lower alcohol ester is at least 50% by weight, and, other than the EPA highly unsaturated fatty acid or the content of total 10 wt% or less of their lower alcohol esters the fractions were collected, and thereafter, at their fraction and 30% to 70% silver nitrate aqueous solution (W / V) and a volume ratio of 1: 100 to 50: allowed mixing 100 ratio of polyunsaturated fatty acids or their and separating the esters.

【0015】以下にその詳細を述べる。 [0015] described the following in the details. EPAを含む高度不飽和脂肪酸を含有する天然油脂原料としては、例えば、水産油脂類(魚油、藻類脂質他)、微生物油脂類、 The natural fat feedstock containing polyunsaturated fatty acids including EPA, for example, marine oils (fish oil, algae lipids, etc.), microorganism oils,
高等植物油脂などを用いることができる。 Or the like can be used higher vegetable oils and fats. これらの天然油脂原料からの脂肪酸の調製、その誘導体の合成等は定法(稲葉恵一・平野二郎編、「新版脂肪酸化学」、幸書房(1981) 、東京)により達成することが出来る。 Preparation of fatty acids from these natural oils and fats raw materials, synthesis and the like of its derivatives are a standard method (Inaba, Keiichi Jiro Hirano, ed., "New Edition fatty acid chemistry", Saiwai Shobo (1981), Tokyo, Japan) can be achieved by.

【0016】EPAの他、複数の高度不飽和脂肪酸類を含む上記天然油脂由来の脂肪酸類又はそれらの誘導体からEPAを濃縮精製するに際し、原料中のEPA含量が30%以下の場合、又は、炭素数18個以下の全脂肪酸含有量が 50 重量%以上の場合、真空精密蒸留に先立ち予備精製し、不純物を少なくしておいてもよい。 [0016] Other EPA, upon concentrating purified EPA from fatty acids or their derivatives from the natural fats and oils containing a plurality of highly unsaturated fatty acids, when EPA content in the feedstock is less than 30%, or, carbon If the number 18 or less of the total fatty acids content is more than 50 wt%, prepurified before the vacuum precision distillation, it may have been less impurities. 予備精製の方法としては、低温溶媒分別結晶法(佃信夫:食品工業,9 下,30-35(1985) )、尿素付加法(佃信夫:食品工業,9下,30-35(1985) ; WMN RARNAYAKE e As a method of pre-purification, low temperature solvent fractional crystallization (TsukudaShinobu: food industry, under 9, 30-35 (1985)), urea addition method (TsukudaShinobu: food industry, under 9, 30-35 (1985); WMN RARNAYAKE e
t al: FaT Sci. Technol, 90 , 381-386(1988))などを品質上、コスト上の理由から実際的に用いることが出来る。 t al:. FaT Sci Technol, 90, 381-386 (1988)), such as the quality, practically used, it is possible for reasons of cost. 但し、本発明においてはEPA又はそのエステルの濃縮精製のため、常に上記予備精製工程をそのプロセスに組み込む必要があるわけではなく、本発明の必要要件ではない。 However, since the concentration and purification of EPA or its ester in the present invention, not always it is necessary to incorporate the pre-purification step in the process, not a necessary requirement of the present invention.

【0017】EPAの他、複数の高度不飽和脂肪酸類を含む上記天然油脂由来の脂肪酸類又はそれらの誘導体、 [0017] Other EPA, fatty acids or their derivatives from the natural fats and oils containing a plurality of highly unsaturated fatty acids,
或いは、これらの上記方法による予備精製品から高純度EPA又はその誘導体を濃縮精製するに際し、先ず、真空精密蒸留法によりEPA又はそのエステルの含有量が Alternatively, when the high-purity EPA or a derivative thereof from the prepurification products by these aforementioned methods concentrating purified, first, the content of EPA or its ester by vacuum rectification method
50 重量%以上で、かつ、EPA以外の高度不飽和脂肪酸又はそのエステルの含有量が合計10重量%以下の留分を得る事が必要である。 50 wt% or more and the content of highly unsaturated fatty acids or esters thereof other than EPA is necessary to obtain a fraction of the total 10% by weight or less. これは次の硝酸銀水溶液による処理で、高純度EPA又はその誘導体を得るための要件を満たす為である。 This is a treatment with the following aqueous silver nitrate solution, it is to meet the requirements for obtaining a high purity EPA or a derivative thereof.

【0018】一般に、真空精密蒸留法は減圧下において複数成分をそれぞれの沸点の差により分別するため、その操作上、系内圧力と温度、蒸留方式(バッチ式、半連続式、連続式等の別)等の因子と試料の状態が重要である。 [0018] Generally, because a vacuum precision distillation method of fractionated by differences in their respective boiling multiple components under reduced pressure, its operation, system pressure and temperature, the distillation method (batch, semi-continuous, continuous system, etc. another) factors and samples the state of the like are important. 本発明の目的成分であるEPAは熱変性を起こし易いことから、出来るだけ低温で操作することが望ましい。 EPA is a target component of the present invention since it prone to thermal denaturation, it is desirable to operate at low temperature as possible.

【0019】これらの点を考慮し、種々検討を重ねたところ、系内圧力は5 mmHg以下、望ましくは1 mmHg以下、 [0019] Considering these points, was extensive studies, system pressure is 5 mmHg or less, preferably 1 mmHg or less,
フラスコ温度(釜温度) 215℃以下、望ましくは 210℃ Flask temperature (pot temperature) 215 ° C. or less, preferably 210 ° C.
以下とすることが必要であることを見出した。 We have found that it is necessary to the following. 系内圧力が 5mmHgを越えるとフラスコ温度を 215℃以上とする必要が生じるため、製品の熱変性を招きやすい。 Since the system pressure exceeds 5mmHg need to flask temperature and 215 ° C. or higher occurs, it tends to cause thermal denaturation of the product.

【0020】充填方式の場合、充填剤の種類により分離能は大きく左右される。 In the case of the filling method, resolution depending on the type of filler greatly influenced. しかしながら、真空精密蒸留においては装置のスケール、形状、目的とする対象物の物性等により充填剤の種類を含む諸条件が変わり得ることが経験的に知られており、実際、EPA又はそのエステルの場合も同様である。 However, the device is a vacuum precision distillation scale, shape, are known from experience that the conditions are obtained instead of including the type of filler by the physical properties of the object such that the object, in fact, the EPA or esters thereof If the same is true. 従って、本発明においては充填剤の種類そのものは制限されないことは当然である。 Therefore, it is naturally possible to type itself of filler is not limited in the present invention. このことは上記充填式の場合のみならず棚段式、スプリング式等の他の方式の場合も同様であり、方式そのものは限定されない。 This is the filling formula in the case not only tray type, The same applies to the case of other types of spring or the like, method itself is not limited.

【0021】真空精密蒸留法によりEPA又はそのエステルの含有量が 50 重量%以上で、かつ、EPA以外の高度不飽和脂肪酸又はそのエステルの含有量が合計10重量%以下の留分から、EPA又はそのエステルの含有量が、例えば、 90 重量%以上の製品を得るためには、さらに続けて、本留分を硝酸銀水溶液中で処理し、硝酸銀水溶液に対し可溶な成分としてのエイコサペンタエン酸又はその誘導体を回収する事(本発明においては硝酸銀錯体法と称する)が必要である。 [0021] In the content of EPA or its ester by vacuum rectification method 50 wt% or more and the content of highly unsaturated fatty acids or esters thereof other than EPA from a total of 10 wt% or less of the fraction, EPA or the content of esters, for example, in order to obtain a product of more than 90% by weight, more continue to process the distillate in an aqueous solution of silver nitrate, or eicosapentaenoic acid as soluble components to an aqueous silver nitrate solution possible to recover the derivative (in the present invention is referred to as the silver nitrate complex method) is required.

【0022】即ち、上記留分と30〜70%硝酸銀水溶液(W/V )とを 1:100 〜50:100 (容量比)の割合で混合せしめ、該硝酸銀水溶液に可溶な高度不飽和脂肪酸類又はそれらのエステル類を分離することにより、例えば、 90 重量%以上のEPA又はそのエステルを製品として得ることが出来る。 [0022] That is, the fraction and 30% to 70% silver nitrate aqueous solution (W / V) and 1: 100 to 50: 100 allowed mixed at a ratio (by volume), soluble polyunsaturated fatty acids to the aqueous silver nitrate solution by separating the class or their esters, for example, it can be obtained 90% or more by weight of EPA or its ester as a product. このことは、硝酸銀水溶液中における硝酸銀と、例えば、上記留分を仮に高度不飽和脂肪酸のエチルエステルとし、平均分子量を 315と仮定した時の両者のモル比で示すと、およそ、82:1 〜1.7 : This silver nitrate in the silver nitrate solution, for example, the ethyl ester of if polyunsaturated fatty acids of the above fraction, indicating a molar ratio of both when assuming average molecular weight 315 and, approximately, 82: 1 to 1.7:
1 の範囲として示すことが出来る。 It can be shown as one of the range.

【0023】上記範囲内でのある一定濃度においては、 [0023] In certain concentrations is within the above range,
硝酸銀水溶液中における各高度不飽和脂肪酸類又はそれらのエステル類の錯体の形成のされ方は一律ではなく、 And how the formation of complexes of the highly unsaturated fatty acids or their esters in the aqueous silver nitrate solution is not uniform,
錯体を形成し易い高度不飽和脂肪酸類又はそれらのエステル類とそうでないものがある。 There is not, the complex is formed easily highly unsaturated fatty acids or their esters. 従って、本発明の目的物であるEPA又はそれらのエステル類を硝酸銀錯体法で精製する場合、硝酸銀水溶液中の硝酸銀濃度、硝酸銀と原料(留分)の比、原料(留分)中の高度不飽和脂肪酸組成等が重要な因子となるのは当然である。 Therefore, when purifying the target product is EPA or esters thereof of the present invention with silver nitrate complex method, silver nitrate concentration in the aqueous silver nitrate solution, the ratio of silver nitrate and raw material (fraction), a high degree of the raw material (fraction) non the like saturated fatty acid composition is an important factor is of course.

【0024】硝酸銀水溶液と上記留分の混合は 45 分間以上、5 ℃以上 90 ℃以下で行う事が出来るが、操作性、製品の品質保全の見地から、1時間程度(常温)で充分に目的を達する事が出来る。 The aqueous silver nitrate solution and the fraction of the mixture is more than 45 minutes, but can be carried out at 5 ° C. or higher 90 ° C. or less, operability, from the viewpoint of quality maintenance of the product, sufficiently purpose in about 1 hour (room temperature) a reach that can be. 攪拌速度は処理量、設備のスケール等により変わるため、本発明では特には限定されないが、一般的に、1000〜5000rpm が適当と見做される。 Stirring speed throughput, since the change by the scale, etc. of equipment, but is not limited particularly in the present invention, generally, 1000 to 5000 rpm is suitable regarded.

【0025】硝酸銀水溶液中で銀イオンと錯体を形成し可溶化された高度不飽和脂肪酸又はそれらのエステルは、常温で 15 分間以上静置後、錯体を形成しないまま上層に分離浮上している不純物成分と分離した後、例えば、有機溶媒と混合する事により製品を硝酸銀水溶液相から有機溶媒相へ移行させ、該有機溶媒を除くことにより目的とする高純度EPA又はそのエステルを得る事が出来る。 The impurity highly unsaturated fatty acids or their esters which are formed by solubilization of silver ions and complex with silver nitrate aqueous solution is separating floating after standing for more than 15 minutes at room temperature, the upper layer without forming the complex after separating the components, for example, to shift the product from an aqueous silver nitrate solution phase to organic solvent phase by mixing with an organic solvent, it is possible to obtain high-purity EPA or esters thereof and an object by removing the organic solvent.

【0026】更に具体的に説明すると、硝酸銀水溶液と上記留分との混合終了後、混合物を例えば分液ロート中に移し、5 ℃以上 50 ℃以下、望ましくは常温で、 15 [0026] More specifically, after the end of mixing the silver nitrate aqueous solution and the distillate, the mixture e.g. transferred into a separatory funnel, 5 ° C. or higher 50 ° C. or less, preferably at room temperature, 15
分間以上、望ましくは 1〜2 時間程度静置後、下層のみ分取し、硝酸銀水溶液相(100 )に対し、 10 〜1000、 Min or more, preferably 1 to 2 hours approximately After standing, was collected only lower layer, to an aqueous silver nitrate solution phase (100), 10-1000,
望ましくは 100の割合(容量比)でクロロホルム、ジエチルエーテル、ヘキサン、石油エーテル、ベンゼン、トルエン、四塩化炭素等の硝酸銀水溶液相と混ざり合わない有機溶媒を加え、銀イオンと錯体を形成している高度不飽和脂肪酸又はそれらのエステルを有機溶媒相へ移行させ、エバポレーター等により溶媒を除き、その残渣として製品である高純度EPA又はそのエステルを得るものである。 Desirably chloroform 100 ratio (by volume), diethyl ether, hexane, petroleum ether, benzene, toluene, the organic solvent immiscible with the aqueous silver nitrate solution phase such as carbon tetrachloride was added to form a silver ion and complex highly unsaturated fatty acids or their esters is shifted into the organic solvent phase, the solvent removed by an evaporator or the like, is intended to obtain a high-purity EPA or its ester is a product as the residue. 製品中に混入してくる極微量の銀イオン、硝酸イオン等をはじめとする不純物は必要に応じて、例えば、酸性白土、活性白土、活性炭、ケイ酸等で定法(宮川高明:「食用油製造の実際」,幸書房,(1988))に従い処理する事により除去することが出来る。 Trace amounts of silver ions coming mixed in the product, depending on the impurity need, including nitrate ions, etc., e.g., acid clay, activated clay, activated carbon, silicic acid titration (Takaaki Miyagawa: "edible oil production in fact ", Saiwai Shobo, can be removed by processing in accordance with (1988)) of. 必要に応じて、本操作を複数回繰り返し、所定の品質を求める事が出来ることは言うまでもない。 If necessary, this operation is repeated a plurality of times, it is of course capable of obtaining a predetermined quality.

【0027】この様にして得られた、例えば純度 90 % [0027] was obtained in this way, for example, 90% purity
以上の高純度EPA又はそのエステルは必要に応じて過酸化物除去、抗酸化物質添加等の処理後、ゼラチンソフトカプセルなどへ封入して健康食品、医薬品等の用途に用いることができる。 More highly pure EPA or its ester peroxides optionally removed, after processing such as addition of antioxidants, enclosed into such as gelatin soft capsules can be used for health foods, such as pharmaceutical applications. また、水産、畜産用の飼料原料としての用途もある。 Further, there is marine, also use as feed ingredients in livestock. 更に、これを粉末化して使い易くする場合の原料としても利用出来る。 Furthermore, this can also be utilized as raw material in the case of ease of use was triturated.

【0028】 [0028]

【作用】この発明では、エイコサペンタエン酸(EP [Action] in the present invention, eicosapentaenoic acid (EP
A)、ドコサヘキサエン酸(DHA)等の高度不飽和脂肪酸を2種類以上含有する天然油脂類から得られる脂肪酸混合物又はそれらの誘導体から高純度のEPA又はその低級アルコールエステルを分離精製するに当たり、真空精密蒸溜法によりEPA又はその低級アルコールエステルを部分精製し、しかる後に、硝酸銀水溶液中で処理し、硝酸銀水溶液に対し可溶な成分としてのEPA又はそのエステルを回収する事により、高純度のEPA又はその低級アルコールエステルを得ることができる。 A), Upon the polyunsaturated fatty acids of 2 fatty acid mixtures obtained from natural fats and oils containing more than or high purity EPA or its lower alcohol ester derivatives thereof, such as docosahexaenoic acid (DHA) separated and purified, vacuum precision EPA or its lower alcohol ester was partially purified by distillation method, and thereafter, treated in an aqueous solution of silver nitrate, by recovering the EPA or its ester as the soluble components to an aqueous silver nitrate solution, high purity EPA or it is possible to obtain a lower alcohol ester.

【0029】 [0029]

【実施例】次に、実施例により本発明を具体的に説明する。 EXAMPLES Next, the present invention will be explained concretely by examples. 本実施例においては魚油(イワシ油)から純度 90 Purity fish oil in this embodiment (sardine oil) 90
%以上の高純度EPAエチルエステルを得る場合について説明する。 It will be described for obtaining% or more of high purity EPA ethyl ester.

【0030】[実施例1]イワシ油からの高純度EPA [0030] The high purity EPA from [Example 1] sardine oil
エチルエステルの調整 フィッシュミール工場から入手したイワシ油 1000 g Sardine oil was obtained from the adjustment fish meal factory of ethyl ester 1000 g
(以後、イワシ油 (TG) と略記)に対し、水酸化ナトリウム 50 gを溶解させた無水エタノール溶液 1000 ml (Hereinafter, sardine oil (TG) for short) to anhydrous ethanol solution 1000 ml prepared by dissolving sodium hydroxide 50 g
を加え、70〜80℃にて1 時間混合攪拌後、更に、水 500 Was added, after 1 hour mixing and stirring at 70 to 80 ° C., further, water 500
mlを加えて良く混合し、分液ロートに移し、1 時間静置し、分離した油層を残し、油層を数回水洗し、洗液が中性になったことを確認後、イワシ油エチルエステル試料(以後、イワシ油 (EE) と略記)820 gを得た。 Added ml well mixed, transferred to a separatory funnel, allowed to stand for 1 hour, leaving the separated oil layer, after confirming that oil layer is washed with water several times, washings became neutral, sardine oil ethyl ester samples (hereinafter, abbreviated as sardine oil (EE)) was obtained 820 g. このイワシ油(EE)は表1に示す通り、EPA (20:5)18.5 The sardine oil (EE) is as shown in Table 1, EPA (20: 5) 18.5
%の他、オクタデカテトラエン酸(18:4)、アラキドン酸 % Other, octadecatetraenoic acid (18: 4), arachidonic acid
(20:4)、ドコサペンタエン酸(22:5)、DHA(22:6)等の高度不飽和脂肪酸を計 15.3%含有していた。 (20: 4), docosapentaenoic acid (22: 5), DHA (22: 6) was found to contain highly unsaturated fatty acids in total 15.3% of the like.

【0031】続いて、真空精密蒸留により精製するため、イワシ油(EE)120 gを200 ml容の蒸留器に入れ、ヘリパック(1.5 ×3.0 ×3.0 mm)を充填した精留塔(直径:4.0 cm ,高さ :40.0cm)を用いて、0.05mmHg [0031] Then, for purification by vacuum rectification, placed sardine oil (EE) 120 g in distiller 200 ml of volume, seminal filled with Helipack (1.5 × 3.0 × 3.0 mm) column (diameter: 4.0 cm, height: 40.0cm) by using the, 0.05mmHg
で分留し、蒸留器温度 205〜208 ℃の時、目的とする主留画分 12.7 g を得た。 In fractionated, when the distiller temperature 205 to 208 ° C., to obtain a ShuTome fractions 12.7 g of interest. この留分はEPA含有量 8 This fraction EPA content 8
1.3%、その他の高度不飽和脂肪酸(オクタデカテトラエン酸、アラキドン酸、ドコサペンタエン酸、DHA 1.3%, other polyunsaturated fatty acids (octadecatetraenoic acid, arachidonic acid, docosapentaenoic acid, DHA
他)の総和は 4.5%であり、本発明の必要条件を満たすものであった。 The sum of the other) is 4.5%, and with the requirements of the present invention. この留分を以後 イワシ油(主留)と称する。 This fraction is referred to hereinafter as sardine oil (main fraction).

【0032】続いて、イワシ油(主留)10.0g と50% [0032] Subsequently, sardine oil (main fraction) 10.0g and 50%
硝酸銀水溶液(W/V )100 mlを常温で1 時間、マグネットスターラー(1500rpm) にて攪拌混合後、200 ml容分液ロートに移し、2 時間、常温で静置した。 1 hour 100 ml of silver nitrate solution (W / V) at room temperature, after stirring and mixing at a magnetic stirrer (1500 rpm), transferred to a 200 ml capacity separating funnel, 2 hours, and allowed to stand at room temperature. 下層を別の30 Another the lower 30
0 ml容分液ロートに移し、100 ml のクロロホルムで3 Transferred to a 0 ml capacity separating funnel, 3 with 100 ml of chloroform
回繰り返し抽出し、クロロホルム層を合わせ、無水硫酸ナトリウムで脱水後、ロータリーエバポレーターで溶媒を除いたところ、EPA含有量 93.4%、その他の高度不飽和脂肪酸の総和が 3.6%の製品が 2.9g 得られた。 Times repeatedly extracted, combined chloroform layer was dehydrated over anhydrous sodium sulphate and the solvent was removed on the rotary evaporator, EPA content 93.4%, total of other highly unsaturated fatty acids is 3.6% Product obtained 2.9g It was.
本品を以後イワシ油(製品)と称する。 This product hereinafter referred to as sardine oil (products).

【0033】下表(表1)にイワシ油 (TG) 、イワシ油 (EE) 、イワシ油(主留)及びイワシ油(製品)の主な脂肪酸組成を示す。 [0033] A principal fatty acid composition in the following table (Table 1) in sardine oil (TG), sardine oil (EE), sardine oil (main fraction) and sardine oil (product).

【0034】 [0034]

【表1】 [Table 1] 脂肪酸分析は下記条件にて、ガスクロマトグラフィー法により行った。 Fatty acid analysis under the following conditions was carried out by gas chromatography. 機種 GC− 14 A((株)島津製作所) カラム DB− 23 (J&W社),φ Model GC- 14 A ((Ltd.) Shimadzu Corporation) column DB- 23 (J & W Inc.), φ
0.25mm×30m 検出器 FID 注入口(検出器)温度 250 ℃(250 ℃) キャリアーガス(He) 50ml/min 水素(空気) 0.6 (0.5 )kg/cm 2カラム温度( 昇温条件) 初期温度 160 ℃(保持時間 0.25 mm × 30 m Detector FID Inlet (detector) Temperature 250 ° C. (250 ° C.) carrier gas (the He) 50 ml / min hydrogen (air) 0.6 (0.5) kg / cm 2 Column temperature (heating conditions) Initial Temperature 160 ℃ (retention time
0 min ) 最終温度 230 ℃(保持時間 5 min ) 昇温速度 4 ℃/min インテグレーター C−R5 A((株)島津製作所) なお、脂肪酸組成はガスクロマトグラフィー法によって得られた各成分の面積%から換算した重量%として示してある。 0 min) Final temperature 230 ° C. (holding time 5 min) heating rate 4 ° C. / min Integrator C-R5 A ((Ltd.) Shimadzu) The area of ​​each component fatty acid composition obtained by gas chromatography% It is shown as wt% in terms of.

【0035】[実施例2]イワシ油 (EE) の尿素付加精製品からの高純度EPAエチルエステルの調整 尿素 4500 gを15l のエタノールと混合し、75℃で攪拌しながら溶解させ、続いて、実施例1と同様にして作成したイワシ油 (EE) 1500g を加え、更に、60分間攪拌を続けた後、常温まで冷却し、沈殿物( 尿素付加品)と上清(尿素付加精製品)を濾別し、上清よりエタノールを除き、その残渣に水 2l を加えて溶解させ、6 N 塩酸によりpHを3 〜4 とし、上層に分離浮上した油分を分離し、この油分を洗液が中性となり、かつ、洗液中への尿素の混入が定性的に(ニンヒドリン反応的に)認められなくなるまで数回水洗を繰り返し、尿素付加精製品 55 [0035] [Example 2] The adjustment urea 4500 g of high purity EPA-ethyl ester from the urea addition the purified product of sardine oil (EE) was mixed with ethanol 15l, and dissolved with stirring at 75 ° C., followed by sardine oil was produced in the same manner as in example 1 (EE) 1500 g was added, further, stirring was continued for 60 minutes, cooled to room temperature, the precipitate (the urea addition product) supernatant (urea additional purified product) was filtered off, remove ethanol from the supernatant, dissolved in water 2l added to the residue, pH and 3-4 of the 6 N hydrochloric acid, separate the oil component separated floating on the upper layer, middle this oil washings becomes sex, and incorporation of urea into the wash solution is qualitatively repeatedly (ninhydrin reactively) number until observed longer times washing, urea additional purified product 55
4.8g を得た。 It was obtained 4.8g. このもののEPA含有量は 42.5 %、その他の高度不飽和脂肪酸の総和は 38.7 %であった。 EPA content of this product 42.5%, the sum of the other highly unsaturated fatty acids was 38.7%.

【0036】上記尿素付加精製品 120.0g を実施例1と同様にして真空精密蒸留に付し、主留画分43.9g を得た。 [0036] The above urea additional purified product 120.0g in the same manner as in Example 1 and subjected to vacuum precision distillation to give the main Tomega minutes 43.9 g. この留分はEPA含有量 85.4%、その他の高度不飽和脂肪酸の総和は8.1 %であった。 This fraction EPA content 85.4%, total of other highly unsaturated fatty acids was 8.1%.

【0037】続いて、上記留分 10.0g を実施例1と同様にして硝酸銀水溶液にて処理し、最終的にEPA含有量 95.9%、その他の高度不飽和脂肪酸の総和が 3.3% [0037] Then, the fraction 10.0g in the same manner as in Example 1 was treated with aqueous silver nitrate solution, finally EPA content 95.9%, total of other highly unsaturated fatty acids 3.3%
の精製品が 5.2g 得られた。 Of purified product was obtained 5.2g.

【0038】更に、上記精製品から残留している銀イオン、硝酸イオン等の不純物を除くため、本品100 g を集め、これを5回水洗後、油脂に対して5重量%の活性炭を加え、1時間攪拌後、活性炭を濾別し、製品 83.7g [0038] Furthermore, to remove silver ions, impurities such as nitrate ions remaining from the purified product, collect the product 100 g, after which 5 times washing, 5% by weight of activated carbon with respect to fat added after stirring for 1 hour and then filtered to remove the activated carbon, the product 83.7g
を得た。 It was obtained. このものはEPA含有量 95.6%であった。 This product was EPA content 95.6%.

【0039】表2に各工程で得られた脂肪酸エチルエステルの組成を示す。 [0039] The composition of the fatty acid ethyl ester obtained in each step in Table 2. 分析法等は実施例1と同様である。 Analysis method is the same as in Example 1.
また、表中、イワシ油 (TG) 及びイワシ油 (EE) の組成は表1と同一であるので、表2から除いてある。 Further, in the table, since the composition of the sardine oil (TG) and sardine oil (EE) is the same as Table 1, it is omitted from Table 2.

【0040】 [0040]

【表2】 [Table 2] <比較例> [比較例1]イワシ油 (EE) の硝酸銀錯体処理 実施例1で用いたものと同一のイワシ油 (EE) 10 g <Comparative Example> [Comparative Example 1] sardine oil (EE) identical sardine oil as used in silver nitrate complex process Example 1 (EE) 10 g
と 50%硝酸銀水溶液を用いて、実施例1と同様に硝酸銀錯体処理を行い、製品 3.6 gを得た。 When using a 50% aqueous silver nitrate solution, similarly performs nitrate complex treatment as in Example 1 to obtain the product 3.6 g. このものの脂肪酸組成をみたところ、EPA含量( 29.7 %)、その他の高度不飽和脂肪酸含量( 26.4 %)であり、90%以上の高純度EPAを得ることは出来なかった。 When viewed fatty acid composition of this product, EPA content (29.7 percent), a more highly unsaturated fatty acid content (26.4%), was not able to obtain highly pure EPA 90% or more.

【0041】[比較例2]イワシ油 (尿素付加精製品) [0041] [Comparative Example 2] sardine oil (urea additional purified product)
の硝酸銀錯体処理 実施例2で用いたものと同一のイワシ油 (尿素付加精製品) 10 gと 50%硝酸銀水溶液を用いて、実施例2と同様に硝酸銀錯体処理を行い、製品 4.5g を得た。 Those used in silver nitrate complex process Example 2 the same sardine oil (urea additional purified product) using 10 g and 50% aqueous silver nitrate solution, similarly performs nitrate complex treatment as in Example 2, to give the product 4.5g It was. このものの脂肪酸組成をみたところ、EPA含量( 51.7 Apparently the fatty acid composition of this thing, EPA content (51.7
%)、その他の高度不飽和脂肪酸含量( 47.7 %)であり、90%以上の高純度EPAを得ることは出来なかった。 %), And other is a polyunsaturated fatty acid content (47.7%), it was not able to obtain highly pure EPA 90% or more.

【0042】 [0042]

【発明の効果】以上説明したように、本発明では、EP As described in the foregoing, in the present invention, EP
A、DHA等の高度不飽和脂肪酸を2種類以上含有する魚油、微生物油脂、藻類・高等植物等の油脂などの天然油脂類から得られる脂肪酸又はそれらの誘導体から、経済的かつ簡便な手段で純度 90%以上の高純度EPA又はその低級アルコールエステルを得ることが出来る。 A, the polyunsaturated fatty acids of fish oil containing two or more types, microorganism oils, fatty acids or derivatives thereof obtained from natural fats and oils, such as oils and fats, such as algae, higher plants such as DHA, purity economical and convenient means it can be obtained more than 90% of the high purity EPA or its lower alcohol ester. 現実のEPA原料は殆ど全てが複数の高度不飽和脂肪酸から構成されているので、本発明はこれら原料から高純度EPA又はその低級アルコールエステルを精製するための実際的な手段を提供している。 Since actual EPA raw material almost all is composed of a plurality of polyunsaturated fatty acids, the present invention provides a practical means for purifying the high purity EPA or its lower alcohol ester from these raw materials.

【0043】更に、本発明の方法は上記天然油脂類中のEPA以外の高度不飽和脂肪酸類又はそれらの誘導体を精製する場合にも応用出来る。 [0043] Furthermore, the method of the present invention can be applied even when purifying highly unsaturated fatty acids or their derivatives other than EPA in the natural fats and oils.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl. 6識別記号 庁内整理番号 FI 技術表示箇所 C11B 1/08 2115−4H 1/10 2115−4H 3/02 2115−4H ────────────────────────────────────────────────── ─── of the front page continued (51) Int.Cl. 6 in the identification symbol Agency Docket No. FI technology display part C11B 1/08 2115-4H 1/10 2115-4H 3/02 2115-4H

Claims (1)

    【特許請求の範囲】 [The claims]
  1. 【請求項1】 エイコサペンタエン酸、ドコサヘキサエン酸等の高度不飽和脂肪酸を2種類以上含有する天然油脂類から得られる脂肪酸混合物又はそれらの誘導体を真空精密蒸留に付し、EPA又はその低級アルコールエステルの含有量が50重量%以上で、かつ、EPA以外の高度不飽和脂肪酸又はそれらの低級アルコールエステルの含有量が合計10重量%以下の留分を採取し、しかる後に、それら留分と30〜70%硝酸銀水溶液とを容量比で 1. A eicosapentaenoic acid, denoted by the polyunsaturated fatty acids of two or more fatty acid mixtures obtained from natural fats and oils containing or their derivatives, such as docosahexaenoic acid to a vacuum precision distillation, the EPA or its lower alcohol ester in content is 50 wt% or more and the content of highly unsaturated fatty acids or their lower alcohol esters other than EPA is collected fractions total of 10 wt% or less, and thereafter, and their fractions 30-70 % and a silver nitrate solution in a volume ratio
    1:100 〜50:100 の割合で混合せしめ、高度不飽和脂肪酸類又はそれらのエステル類を分離することを特徴とする高純度エイコサペンタエン酸又はその低級アルコールエステルの分離精製法。 1: 100-50: allowed mixing 100 ratio of polyunsaturated fatty acid or high purity eicosapentaenoic acid or the method for the separation and purification their lower alcohol esters and separating the esters thereof.
JP5528193A 1993-03-16 1993-03-16 Eicosapentaenoic acid of high purity and isolation and purification of lower alcohol ester thereof Pending JPH07242895A (en)

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WO1997046649A1 (en) * 1996-06-03 1997-12-11 Croda International Plc Treatment of oils
EP1065196A1 (en) * 1999-06-28 2001-01-03 Nisshin Flour Milling Co., Ltd. Process of selectively separating and purifying eicosapentaenoic and docosahexaenoic acids or their esters
JP2011505138A (en) * 2007-11-29 2011-02-24 モンサント テクノロジー エルエルシー Meat products, including the beneficial fatty acids increased levels
WO2012038833A1 (en) * 2010-09-24 2012-03-29 Pronova Biopharma Norge As Process for concentrating omega-3 fatty acids
WO2015029364A1 (en) 2013-08-30 2015-03-05 備前化成株式会社 Method for producing high purity omega-3 fatty acid ethyl ester
WO2015046436A1 (en) * 2013-09-26 2015-04-02 キユーピー株式会社 Method for producing lower alcohol fatty acid esterified product-containing composition, and lower alcohol fatty acid esterified product-containing composition
JP2015108000A (en) * 2009-12-30 2015-06-11 ビーエイエスエフ ファーマ(コーラニッシュ)リミテッド Simulated moving bed chromatographic separation process
US9365800B2 (en) 2012-10-01 2016-06-14 Nisshin Pharma Inc. Method for producing composition containing highly unsaturated fatty acid alkyl ester
WO2016158605A1 (en) * 2015-04-01 2016-10-06 キユーピー株式会社 Method for manufacturing lower alcohol fatty acid esterification product-containing composition and lower alcohol fatty acid esterification product-containing composition
WO2017038861A1 (en) * 2015-08-31 2017-03-09 日本水産株式会社 Free-polyunsaturated-fatty-acid-containing composition and method for manufacturing same
US9694302B2 (en) 2013-01-09 2017-07-04 Basf Pharma (Callanish) Limited Multi-step separation process
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WO1997046649A1 (en) * 1996-06-03 1997-12-11 Croda International Plc Treatment of oils
EP1065196A1 (en) * 1999-06-28 2001-01-03 Nisshin Flour Milling Co., Ltd. Process of selectively separating and purifying eicosapentaenoic and docosahexaenoic acids or their esters
JP2011505138A (en) * 2007-11-29 2011-02-24 モンサント テクノロジー エルエルシー Meat products, including the beneficial fatty acids increased levels
KR101454060B1 (en) * 2007-11-29 2014-10-28 몬산토 테크놀로지 엘엘씨 Meat products with increased levels of beneficial fatty acids
JP2015108000A (en) * 2009-12-30 2015-06-11 ビーエイエスエフ ファーマ(コーラニッシュ)リミテッド Simulated moving bed chromatographic separation process
US20160016877A1 (en) * 2009-12-30 2016-01-21 Basf Pharma (Callanish) Limited Simulated Moving Bed Chromatographic Separation Process
US9790162B2 (en) 2009-12-30 2017-10-17 Basf Pharma (Callanish) Limited Simulated moving bed chromatographic separation process
US20130317241A1 (en) * 2010-09-24 2013-11-28 Harald Breivik Process for concentrating omega-3 fatty acids
US9145533B2 (en) * 2010-09-24 2015-09-29 Pronova Blopharm Norge AS Process for concentrating omega-3 fatty acids
WO2012038833A1 (en) * 2010-09-24 2012-03-29 Pronova Biopharma Norge As Process for concentrating omega-3 fatty acids
US9771542B2 (en) 2011-07-06 2017-09-26 Basf Pharma Callanish Ltd. Heated chromatographic separation process
US9365800B2 (en) 2012-10-01 2016-06-14 Nisshin Pharma Inc. Method for producing composition containing highly unsaturated fatty acid alkyl ester
US9694302B2 (en) 2013-01-09 2017-07-04 Basf Pharma (Callanish) Limited Multi-step separation process
WO2015029364A1 (en) 2013-08-30 2015-03-05 備前化成株式会社 Method for producing high purity omega-3 fatty acid ethyl ester
WO2015046436A1 (en) * 2013-09-26 2015-04-02 キユーピー株式会社 Method for producing lower alcohol fatty acid esterified product-containing composition, and lower alcohol fatty acid esterified product-containing composition
JP5753963B1 (en) * 2013-09-26 2015-07-22 キユーピー株式会社 Preparation and lower alcohol fatty acid ester-containing composition of the lower alcohol fatty acid ester-containing composition
WO2016158605A1 (en) * 2015-04-01 2016-10-06 キユーピー株式会社 Method for manufacturing lower alcohol fatty acid esterification product-containing composition and lower alcohol fatty acid esterification product-containing composition
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