WO2016194360A1 - 高度不飽和脂肪酸エチルエステルの新規製造方法 - Google Patents
高度不飽和脂肪酸エチルエステルの新規製造方法 Download PDFInfo
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- WO2016194360A1 WO2016194360A1 PCT/JP2016/002613 JP2016002613W WO2016194360A1 WO 2016194360 A1 WO2016194360 A1 WO 2016194360A1 JP 2016002613 W JP2016002613 W JP 2016002613W WO 2016194360 A1 WO2016194360 A1 WO 2016194360A1
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- mixture
- fatty acid
- unsaturated fatty
- highly unsaturated
- silver salt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/60—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/58—Esters of straight chain acids with eighteen carbon atoms in the acid moiety
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
Definitions
- the present invention relates to a novel method for producing highly unsaturated fatty acid ethyl ester.
- the present invention also relates to a method for purifying highly unsaturated fatty acid ethyl esters.
- Highly unsaturated fatty acid is a general term for fatty acids containing many double bonds.
- Patent Documents 1 to 4 describe that silver salts used for purification of polyunsaturated fatty acids and their derivatives can be reused, but silver salts are very susceptible to deterioration. .
- highly unsaturated fatty acid and its derivatives are purified using a deteriorated silver salt, impurities are mixed in and the flavor is deteriorated, and a good refined product cannot be obtained. Therefore, it is very difficult in practice to reuse the silver salt.
- industrially purifying highly unsaturated fatty acids and derivatives thereof it is necessary to prepare a new aqueous silver salt solution every time, and the purification cost is reduced. There was a problem that would be very expensive.
- the free fatty acid content in the reused silver salt aqueous solution is a technique that enables the silver salt aqueous solution to be reused repeatedly over a long period of time.
- the method of making it below a fixed value was developed (patent document 5). This method is characterized in that the free fatty acid content in the silver salt aqueous solution is controlled to 0.2 meq or less per 1 g of silver by bringing the silver salt aqueous solution into contact with a free fatty acid reducing agent.
- the inventors have clarified that, as described below, when attention is paid only to the acid value of the raw material and attention is not paid to the peroxide value, the peroxide of the raw material causes deterioration of silver nitrate in the silver nitrate aqueous solution, and the production yield is reduced. It can cause a decrease in rate. As shown below, the inventors have clarified that the peroxide of the raw material causes silver nitrate deterioration in the aqueous silver nitrate solution, causing a decrease in production yield, etc., and the peroxide value in the raw material is 10 or less. Thus, the present invention is characterized by reducing silver nitrate deterioration.
- patent document 5 describes the acid value regarding the quality of a raw material, it does not describe the peroxide value.
- the acid value which is an index of raw material quality, does not correlate with the peroxide value. Therefore, in the invention described in Patent Document 5, there may arise a problem that the peroxide as a raw material causes deterioration of silver nitrate in the aqueous silver nitrate solution, resulting in a decrease in production yield and the like.
- the yield in purification and production of the highly unsaturated fatty acid derivative is reduced by reducing the peroxide value of the mixture. It is an object of the present invention to improve.
- the present inventors have found that the lipid peroxide of highly unsaturated fatty acid ethyl ester as a raw material has a significant influence on the deterioration of the aqueous silver salt solution, and have completed the present invention. While not wishing to be bound by theory, the present inventors believe that lipid peroxides and / or lipid peroxide oxidation products and / or lipid peroxide degradation products bind to aqueous silver salt solutions. Therefore, it was estimated that the processing ability of the silver salt aqueous solution was lowered. Therefore, the present inventors consider that it is important to remove lipid peroxide and / or lipid peroxide oxidation products and / or lipid peroxide degradation products in the raw material, and are raw materials.
- a raw material highly unsaturated fatty acid ethyl ester having a low peroxide value is provided by reducing the peroxide value of the highly unsaturated fatty acid ethyl ester as a raw material.
- the present invention provides the following.
- (Item 1) A method for purifying a highly unsaturated fatty acid derivative from a mixture comprising the highly unsaturated fatty acid derivative, the method comprising: (B) A method comprising the step of bringing the mixture into contact with an aqueous solution of silver salt, wherein the peroxide value of the mixture is 10 or less.
- (Item 2) A method for purifying a highly unsaturated fatty acid derivative from a mixture comprising the highly unsaturated fatty acid derivative, the method comprising: (B) A method comprising the step of mixing the mixture and an aqueous solution of silver salt, wherein the peroxide value of the mixture is 10 or less.
- (Item 3) A method for purifying a highly unsaturated fatty acid derivative from a mixture comprising the highly unsaturated fatty acid derivative, the method comprising: (A) reducing the peroxide value of the mixture to 10 or less; and (B) A method comprising the step of bringing the mixture into contact with an aqueous silver salt solution.
- (Item 4) A method for purifying a highly unsaturated fatty acid derivative from a mixture comprising the highly unsaturated fatty acid derivative, the method comprising: (A) reducing the peroxide value of the mixture to 10 or less; and (B) A method comprising a step of mixing the mixture with an aqueous silver salt solution. (Item 5) Item 5.
- step (a) comprises contacting the mixture with a POV reducing agent selected from the group consisting of acidic clay, activated clay, activated carbon, and silicic acid.
- a POV reducing agent selected from the group consisting of acidic clay, activated clay, activated carbon, and silicic acid.
- step (c) is performed before the step (b).
- step (Item 11) Item 5.
- the method according to any one of Items 1 to 4, wherein the step (b) is performed under conditions selected from the group consisting of a nitrogen gas environment and a light shielding environment.
- a method for purifying a highly unsaturated fatty acid derivative from a mixture comprising the highly unsaturated fatty acid derivative comprising: (B) including contacting the mixture with an aqueous solution of silver salt, wherein the method manages the peroxide number of the mixture to 10 or less by contacting the mixture with a POV reducing agent.
- a method characterized by. (Item 13) A method for purifying a highly unsaturated fatty acid derivative from a mixture comprising the highly unsaturated fatty acid derivative, the method comprising: (B) including the step of mixing the mixture with an aqueous solution of silver salt, wherein the method manages the peroxide number of the mixture to 10 or less by mixing the mixture with a POV reducing agent.
- a method characterized by. (Item 14) 14. The method according to item 12 or 13, wherein the highly unsaturated fatty acid derivative is a highly unsaturated fatty acid ethyl ester.
- (Item 15) Item 15. The item 14, wherein the highly unsaturated fatty acid ethyl ester is selected from the group consisting of 18: 3 ⁇ 3, 18: 3 ⁇ 6, 18: 4 ⁇ 3, 20: 4 ⁇ 6, 20: 5 ⁇ 3, 22: 5 ⁇ 3, and 22: 6 ⁇ 3.
- Method. (Item 16) 14. The method according to item 12 or 13, wherein the aqueous silver salt solution is an aqueous silver nitrate solution. (Item 17) 14.
- (Item 18) further, (C) The method of item 12 or 13 including the process of adding an antioxidant to the said mixture.
- (Item 20) 14 The method according to item 12 or 13, wherein the step (b) is performed under conditions selected from the group consisting of a nitrogen gas environment and a light shielding environment.
- a method for producing and purifying a highly unsaturated fatty acid and / or derivative thereof while suppressing deterioration of the aqueous silver salt solution Is provided.
- raw oil and fat refers to an oil and fat used as a raw material for the purification of the present invention.
- the raw oil and fat may or may not be deoxidized.
- the raw material fat according to the present invention is a deoxidized raw material fat.
- purification refers to any operation that increases the concentration of a substance to be purified.
- peroxide number is used interchangeably with “POV” and represents the amount of peroxide, which is a primary product generated in the early stage of fat auto-oxidation.
- deterioration of silver salt occurs due to lipid peroxide contained in the mixture (raw oil and fat). That is, it is considered that silver salts such as silver nitrate are altered by the reaction of silver peroxide such as silver nitrate with lipid peroxide.
- a peroxide exists in a mixture (raw material fat), since a peroxide is unstable, it decomposes
- the POV of the mixture (for example, raw oil) used in the purification method of the present invention is 14 or less, 13 or less, 12 or less, 11 or less, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0.5 or less.
- the “peroxide value (POV)” can be measured by reacting potassium iodide with a sample and titrating iodine liberated from potassium iodide by hydroperoxide in the oil or fat. More specifically, it is as described in the 2003 edition standard oil fat analysis test method (edited by Japan Oil Chemists' Society).
- the term “acid value” used in the present specification is an index of carboxylic acid contained in fatty acid, and mg of potassium hydroxide required to neutralize free fatty acid contained in 1 g of a sample. Numbers.
- the method for measuring the acid value is as described in the 2003 standard oil analysis method (edited by Japan Oil Chemists' Society).
- Peroxide value is not directly related to “acid value”. The peroxide value increases as oxidation proceeds and peroxide is generated. However, peroxide is unstable and will decompose over time. Even when the acid value of the mixture is low, the peroxide value (POV) may be high. For example, when a sample is brought into contact with a POV lowering agent, the POV is not necessarily 10 or less. Therefore, in order to confirm that the POV is 10 or less, it is necessary to measure the POV. Even if the acid value is 5 or less, the POV does not necessarily become 10 or less, but the POV often exceeds 10.
- Patent Document 5 it is essential that the free fatty acid content is 0.2 meq or less per 1 g of silver, because it is not possible to obtain a sufficient result in preventing deterioration of the silver salt aqueous solution only by setting the acid value to 5 or less. there were.
- the lipid peroxide and / or lipid peroxide oxidation products and / or lipid peroxide degradation products in the feed are removed. By doing so, a decrease in the processing ability of the aqueous silver salt solution is suppressed.
- the peroxide value by the “POV lowering agent” treatment is used.
- the present invention is not limited to this.
- the term “POV lowering agent” refers to a drug having an action of lowering a “peroxide value (POV)”.
- POV peroxide value
- examples of the POV lowering agent include, but are not limited to, acid clay, activated clay, activated carbon, and silicic acid.
- silicic acid also referred to as silica
- silica gel that is gelled silicic acid can be used.
- the mixture and the “POV lowering agent” are contacted or the mixture and the “POV lowering agent” are mixed.
- polyunsaturated fatty acid means an unsaturated fatty acid having 16 or more carbon atoms and having two or more double bonds in the molecule.
- docosahexaenoic acid C22: 6, DHA
- eicosapentaenoic acid C20: 5, EPA
- arachidonic acid C20: 4, AA
- docosapentaenoic acid C22: 5, DPA
- stearidonic acid C18: 4
- linolenic acid C18) : 3
- linoleic acid (C18: 2) and the like but are not limited thereto.
- Derivatives of highly unsaturated fatty acids obtained by the acquisition method of the present invention refer to fatty acids that are not free and those that are free, for example, highly unsaturated fatty acids, methyl esters of highly unsaturated fatty acids, ethyl Examples include, but are not limited to, ester type derivatives such as esters, amide type derivatives such as amides and methylamides, fatty alcohol type derivatives, triglycerides, diglycerides, and monoglycerides.
- silver salt refers to a silver salt that can form a complex with an unsaturated bond in an unsaturated fatty acid. Examples thereof include, but are not limited to, silver nitrate, silver perchlorate, silver acetate, silver trichloroacetate, and silver trifluoroacetate. These silver salts are dissolved in water to a concentration of preferably 15% or more, more preferably 20% or more, and even more preferably 40% or more to form a silver salt aqueous solution, which is used for the purification of highly unsaturated fatty acid derivatives. To do.
- the silver salt concentration in the silver salt aqueous solution is not particularly limited, but preferably the saturation concentration is the upper limit.
- antioxidant refers to a substance that attenuates or eliminates harmful reactions involving oxygen in living bodies, foods, daily necessities, and industrial raw materials.
- antioxidants include but are not limited to butylhydroxytoluene, tocopherol, and tocopherol derivatives.
- tocopherol derivatives include d- ⁇ -tocopherol, d- ⁇ -tocopherol, d- ⁇ -tocopherol, d- ⁇ -tocopherol, l- ⁇ -tocopherol, l- ⁇ -tocopherol, l- ⁇ -tocopherol, l- ⁇ -tocopherol, mixtures thereof dl- ⁇ -tocopherol, dl- ⁇ -tocopherol, dl- ⁇ -tocopherol, dl- ⁇ -tocopherol, their derivatives tocopherol acetate, tocopherol succinate, tocopherol phosphate, Examples include, but are not limited to, tocophenol aspartate, tocophenol glutamate, tocopherol palmitate, tocopherol nicotinate, tocopherol linoleate, polyethoxylated tocophenol and the like.
- a method of selectively separating a highly unsaturated fatty acid derivative from a mixture of fatty acid derivatives typically involves mixing a mixture of fatty acid derivatives containing the highly unsaturated fatty acid derivative with a mixture of fatty acid derivatives.
- An aqueous solution of a silver salt capable of forming a complex with a saturated bond is added and preferably stirred for 5 minutes to 4 hours, more preferably 10 minutes to 2 hours to form a water-soluble silver salt-highly unsaturated fatty acid derivative complex.
- it is carried out by selectively dissolving only a highly unsaturated fatty acid derivative in an aqueous silver salt solution, but is not limited thereto.
- the reaction temperature between the above highly unsaturated fatty acid derivative and the aqueous silver salt solution may be a lower limit as long as the aqueous silver salt solution is liquid and the upper limit is up to 100 ° C. From the viewpoint of stability, solubility of silver salt in water, complex formation rate, etc., 10 to 30 ° C. is preferable.
- the light is shielded from light under an inert gas such as a nitrogen atmosphere.
- an inert gas such as a nitrogen atmosphere.
- the method for dissociating the highly unsaturated fatty acid derivative from the complex of the highly unsaturated fatty acid derivative and the silver salt is not particularly limited.
- extraction with an organic solvent or addition of water makes the highly unsaturated fatty acid derivative insoluble.
- the free fatty acid content in the silver salt aqueous solution is 0.5 meq or less, 0.4 meq or less, 0.3 meq or less, 0.25 meq or less, 0.2 meq or less, 0.15 meq or less. , 0.1 meq or less, or 0.07 meq or less.
- the acid value in the mixture (raw material) is 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, Can be managed.
- Example 2 (using various POV and acid value raw materials) High fatty acid ethyl ester was obtained from the fatty acid ethyl ester mixture by the following method.
- a mixture of fatty acid ethyl esters (acid value 0.2 to 1.5, POV 1.0 to 9.5, EPA ethyl ester purity 40 to 48% (fatty acid composition area%), DHA ethyl ester purity 5 to 10%) was mixed and stirred at 20 ° C. for 30 minutes. Then, it left still for 30 minutes and was made to isolate
- Example 3 (Using POV 15 raw material reduced to POV 1 with activated clay) High fatty acid ethyl ester was obtained from the fatty acid ethyl ester mixture by the following method.
- activated clay 10 g was added to 1 kg of a mixture of fatty acid ethyl esters (acid value 0.5, POV 15, EPA ethyl ester purity 45.3% (fatty acid composition area%), DHA ethyl ester purity 6.8%), and nitrogen was added. It stirred for 30 minutes at 50 degreeC under atmosphere. Thereafter, the activated clay was removed by filtration, and POV was measured and found to be 1.0.
- the upper layer was separated to obtain a highly unsaturated fatty acid ethyl ester concentrate. Separately, a lower layer containing silver nitrate was taken and the free fatty acid content was measured. This lower layer containing silver nitrate was used again for the purification of highly unsaturated fatty acid ethyl ester. The above reaction was carried out under a nitrogen atmosphere. This operation was repeated.
- a method for producing and purifying a highly unsaturated fatty acid and / or derivative thereof while suppressing deterioration of the aqueous silver salt solution Is provided.
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Abstract
Description
(項目1)
高度不飽和脂肪酸誘導体を含む混合物から高度不飽和脂肪酸誘導体を精製する方法であって、該方法は、
(b)該混合物と銀塩の水溶液とを接触させる工程
を包含し、ここで、該混合物の過酸化物価が10以下である、方法。
(項目2)
高度不飽和脂肪酸誘導体を含む混合物から高度不飽和脂肪酸誘導体を精製する方法であって、該方法は、
(b)該混合物と銀塩の水溶液とを混合する工程
を包含し、ここで、該混合物の過酸化物価が10以下である、方法。
(項目3)
高度不飽和脂肪酸誘導体を含む混合物から高度不飽和脂肪酸誘導体を精製する方法であって、該方法は、
(a)該混合物の過酸化物価を10以下に低減する工程;および、
(b)該混合物と銀塩の水溶液とを接触させる工程
を包含する方法。
(項目4)
高度不飽和脂肪酸誘導体を含む混合物から高度不飽和脂肪酸誘導体を精製する方法であって、該方法は、
(a)該混合物の過酸化物価を10以下に低減する工程;および、
(b)該混合物と銀塩の水溶液とを混合する工程
を包含する方法。
(項目5)
前記高度不飽和脂肪酸誘導体が高度不飽和脂肪酸エチルエステルである、項目1~4のいずれか一項に記載の方法。
(項目6)
前記高度不飽和脂肪酸エチルエステルが18:3ω3、18:3ω6、18:4ω3、20:4ω6、20:5ω3、22:5ω3、および、22:6ω3からなる群から選択される、項目5に記載の方法。
(項目7)
前記銀塩の水溶液が硝酸銀水溶液である、項目1~4のいずれか一項に記載の方法。
(項目8)
前記工程(a)が、前記混合物を、酸性白土、活性白土、活性炭、および、ケイ酸からなる群から選択されるPOV低下剤と接触させることを包含する、項目3または4に記載の方法。
(項目9)
さらに、
(c)前記混合物に抗酸化剤を添加する工程
を包含する、項目1~4のいずれか一項に記載の方法。
(項目10)
前記工程(c)が前記工程(b)の前に行われる、項目9に記載の方法。
(項目11)
前記工程(b)が、窒素ガス環境下および光遮断環境下からなる群から選択される条件下で行われる、項目1~4のいずれか一項に記載の方法。
(項目12)
高度不飽和脂肪酸誘導体を含む混合物から高度不飽和脂肪酸誘導体を精製する方法であって、該方法は、
(b)該混合物と銀塩の水溶液とを接触させる工程
を包含し、ここで、該方法は、該混合物をPOV低下剤と接触させることによって該混合物の過酸化物価を10以下に管理することを特徴とする、方法。
(項目13)
高度不飽和脂肪酸誘導体を含む混合物から高度不飽和脂肪酸誘導体を精製する方法であって、該方法は、
(b)該混合物と銀塩の水溶液とを混合する工程
を包含し、ここで、該方法は、該混合物をPOV低下剤と混合することによって該混合物の過酸化物価を10以下に管理することを特徴とする、方法。
(項目14)
前記高度不飽和脂肪酸誘導体が高度不飽和脂肪酸エチルエステルである、項目12または13に記載の方法。
(項目15)
前記高度不飽和脂肪酸エチルエステルが18:3ω3、18:3ω6、18:4ω3、20:4ω6、20:5ω3、22:5ω3、および、22:6ω3からなる群から選択される、項目14に記載の方法。
(項目16)
前記銀塩の水溶液が硝酸銀水溶液である、項目12または13に記載の方法。
(項目17)
前記POV低下剤が、酸性白土、活性白土、活性炭、および、ケイ酸からなる群から選択される、項目12または13に記載の方法。
(項目18)
さらに、
(c)前記混合物に抗酸化剤を添加する工程
を包含する、項目12または13に記載の方法。
(項目19)
前記工程(c)が前記工程(b)の前に行われる、項目18に記載の方法。
(項目20)
前記工程(b)が、窒素ガス環境下および光遮断環境下からなる群から選択される条件下で行われる、項目12または13に記載の方法。
以下に本明細書において特に使用される用語の定義を列挙する。
本明細書において使用される用語「POV低下剤」とは、「過酸化物価(POV)」を低下させる作用を有する薬剤をいう。POV低下剤としては、例えば、酸性白土、活性白土、活性炭、および、ケイ酸が挙げられるがこれらに限定されない。ケイ酸(シリカともいう)としては、例えば、ゲル化したケイ酸であるシリカゲルを利用することが可能である。本発明において、高度不飽和脂肪酸誘導体を含む混合物の過酸化物価を10以下とする方法としては、例えば、混合物と「POV低下剤」とを接触させるか、混合物と「POV低下剤」とを混合するか、混合物中に「POV低下剤」を投入して撹拌するか、あるいは、「POV低下剤」を充填したカラムに混合物を通液する方法等が挙げられるがこれらに限定されない。
以下の方法により、脂肪酸エチルエステル混合物から高度脂肪酸エチルエステルを精製した。
以下の方法により、脂肪酸エチルエステル混合物から高度脂肪酸エチルエステルを取得した。
以下の方法により、脂肪酸エチルエステル混合物から高度脂肪酸エチルエステルを取得した。
以下の方法により、脂肪酸エチルエステル混合物から高度脂肪酸エチルエステルを取得した。
以下の方法により、脂肪酸エチルエステル混合物から高度脂肪酸エチルエステルを取得した。
Claims (16)
- 高度不飽和脂肪酸誘導体を含む混合物から高度不飽和脂肪酸誘導体を精製する方法であって、以下の(1)~(4):
(1)(a)過酸化物価が10以下である該混合物を提供する工程、および、
(b)該混合物と銀塩の水溶液とを接触させる工程;
(2)(a)過酸化物価が10以下である該混合物を提供する工程、および、
(b)該混合物と銀塩の水溶液とを混合する工程;
(3)(a)該混合物の過酸化物価を10以下に低減する工程、および、
(b)該混合物と銀塩の水溶液とを接触させる工程;ならびに、
(4)(a)該混合物の過酸化物価を10以下に低減する工程、および、
(b)該混合物と銀塩の水溶液とを混合する工程、
からなる群から選択される工程を包含する方法。 - 前記高度不飽和脂肪酸誘導体が高度不飽和脂肪酸エチルエステルである、請求項1に記載の方法。
- 前記高度不飽和脂肪酸エチルエステルが18:3ω3、18:3ω6、18:4ω3、20:4ω6、20:5ω3、22:5ω3、および、22:6ω3からなる群から選択される、請求項2に記載の方法。
- 前記銀塩の水溶液が硝酸銀水溶液である、請求項1に記載の方法。
- 請求項1の(3)または(4)において、前記工程(a)が、前記混合物を、酸性白土、活性白土、活性炭、および、ケイ酸からなる群から選択されるPOV低下剤と接触させることを包含する、請求項1に記載の方法。
- さらに、
(c)前記混合物に抗酸化剤を添加する工程
を包含する、請求項1に記載の方法。 - 前記工程(c)が前記工程(b)の前に行われる、請求項6に記載の方法。
- 前記工程(b)が、窒素ガス環境下および光遮断環境下からなる群から選択される条件下で行われる、請求項1に記載の方法。
- 高度不飽和脂肪酸誘導体を含む混合物から高度不飽和脂肪酸誘導体を精製する方法であって、以下:
(1)該混合物と銀塩の水溶液とを接触させる工程;および
(2)該混合物と銀塩の水溶液とを混合する工程
からなる群から選択される工程を包含し、ここで、該方法は、該混合物をPOV低下剤と接触させることによって該混合物の過酸化物価を10以下に管理することを特徴とする、方法。 - 前記高度不飽和脂肪酸誘導体が高度不飽和脂肪酸エチルエステルである、請求項9に記載の方法。
- 前記高度不飽和脂肪酸エチルエステルが18:3ω3、18:3ω6、18:4ω3、20:4ω6、20:5ω3、22:5ω3、および、22:6ω3からなる群から選択される、請求項10に記載の方法。
- 前記銀塩の水溶液が硝酸銀水溶液である、請求項9に記載の方法。
- 前記POV低下剤が、酸性白土、活性白土、活性炭、および、ケイ酸からなる群から選択される、請求項9に記載の方法。
- さらに、
(3)前記混合物に抗酸化剤を添加する工程
を包含する、請求項9に記載の方法。 - 前記工程(3)が前記工程(1)または(2)の前に行われる、請求項14に記載の方法。
- 前記工程(1)または(2)が、窒素ガス環境下および光遮断環境下からなる群から選択される条件下で行われる、請求項9に記載の方法。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107162910A (zh) * | 2017-05-19 | 2017-09-15 | 陕西源邦生物技术有限公司 | 从鱼油中制备高纯度epa‑ee的方法 |
WO2018230622A1 (ja) | 2017-06-14 | 2018-12-20 | 日清ファルマ株式会社 | 高度不飽和脂肪酸含有組成物の製造方法 |
US10597607B2 (en) | 2016-05-02 | 2020-03-24 | Nisshin Pharma Inc. | Method for producing polyunsaturated fatty acid-containing composition |
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CN114762775B (zh) * | 2021-01-11 | 2023-08-08 | 尚鼎环境科技(江苏)有限公司 | 一种乳酸溶液的脱色处理系统及饱和活性炭的脱酸处理方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58109444A (ja) * | 1981-11-19 | 1983-06-29 | Kureha Chem Ind Co Ltd | エイコサペンタエン酸又はそのエステル、ドコサヘキサエン酸又はそのエステルの分離精製法 |
JPH0390046A (ja) * | 1989-08-31 | 1991-04-16 | Mochida Pharmaceut Co Ltd | エイコサペンタエン酸またはそのエステルを含有する安定化組成物 |
JPH0838050A (ja) * | 1994-01-14 | 1996-02-13 | Cpc Internatl Inc | 改良された安定性を有する、エステル化されたアルコキシル化ポリオール |
JPH08100191A (ja) * | 1994-09-30 | 1996-04-16 | Nisshin Flour Milling Co Ltd | 高度不飽和脂肪酸またはそのエステルの精製方法 |
JP2010064974A (ja) * | 2008-09-10 | 2010-03-25 | Q P Corp | 高度不飽和脂肪酸誘導体の取得方法 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR840000593A (ko) * | 1982-07-30 | 1984-02-25 | 이용철 | Tpa와 eg 혼합물의 유동성을 개선하는 방법 |
US5006281A (en) * | 1985-03-26 | 1991-04-09 | Century Laboratories, Inc. | Process for the production of a marine animal oil |
JP2895258B2 (ja) | 1990-04-24 | 1999-05-24 | ハリマ化成株式会社 | 高度不飽和脂肪酸類の選択的取得方法 |
JP3001954B2 (ja) | 1990-10-24 | 2000-01-24 | 財団法人相模中央化学研究所 | 高度不飽和脂肪酸の取得方法 |
JP2935555B2 (ja) | 1990-10-19 | 1999-08-16 | ハリマ化成株式会社 | 高度不飽和脂肪酸の分離精製法 |
CA2040925C (en) | 1990-04-24 | 2000-01-25 | Yoshihisa Misawa | Method of purifying polyunsaturated aliphatic compounds |
JP2786748B2 (ja) | 1991-01-28 | 1998-08-13 | ハリマ化成株式会社 | 高度不飽和脂肪酸類の精製方法 |
CN101538508B (zh) * | 2009-04-14 | 2010-08-25 | 江南大学 | 一种降低植物油反式脂肪酸含量的脱色方法 |
CN102994236B (zh) * | 2012-12-11 | 2015-03-25 | 成都圆大生物科技有限公司 | 一种制备Omega-3大于90%的脂肪酸乙酯的方法 |
WO2015015716A1 (ja) * | 2013-07-31 | 2015-02-05 | 備前化成株式会社 | 疑似移動床クロマトグラフィーによる脂溶性物質の分離法およびそのための装置 |
JP6302310B2 (ja) * | 2013-08-30 | 2018-03-28 | 備前化成株式会社 | 高純度オメガ3系脂肪酸エチルエステルの生産方法 |
EP2883860B1 (fr) * | 2013-12-11 | 2016-08-24 | Novasep Process | Procédé chromatographique de production d'acides gras polyinsaturés |
JP6464144B2 (ja) * | 2014-02-28 | 2019-02-06 | 備前化成株式会社 | ステアリドン酸の精製方法 |
-
2016
- 2016-05-30 JP JP2017521690A patent/JP6751086B2/ja active Active
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- 2016-05-30 KR KR1020177037095A patent/KR102569302B1/ko active IP Right Grant
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58109444A (ja) * | 1981-11-19 | 1983-06-29 | Kureha Chem Ind Co Ltd | エイコサペンタエン酸又はそのエステル、ドコサヘキサエン酸又はそのエステルの分離精製法 |
JPH0390046A (ja) * | 1989-08-31 | 1991-04-16 | Mochida Pharmaceut Co Ltd | エイコサペンタエン酸またはそのエステルを含有する安定化組成物 |
JPH0838050A (ja) * | 1994-01-14 | 1996-02-13 | Cpc Internatl Inc | 改良された安定性を有する、エステル化されたアルコキシル化ポリオール |
JPH08100191A (ja) * | 1994-09-30 | 1996-04-16 | Nisshin Flour Milling Co Ltd | 高度不飽和脂肪酸またはそのエステルの精製方法 |
JP2010064974A (ja) * | 2008-09-10 | 2010-03-25 | Q P Corp | 高度不飽和脂肪酸誘導体の取得方法 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10597607B2 (en) | 2016-05-02 | 2020-03-24 | Nisshin Pharma Inc. | Method for producing polyunsaturated fatty acid-containing composition |
CN107162910A (zh) * | 2017-05-19 | 2017-09-15 | 陕西源邦生物技术有限公司 | 从鱼油中制备高纯度epa‑ee的方法 |
CN107162910B (zh) * | 2017-05-19 | 2019-12-31 | 陕西源邦生物技术有限公司 | 从鱼油中制备高纯度epa-ee的方法 |
WO2018230622A1 (ja) | 2017-06-14 | 2018-12-20 | 日清ファルマ株式会社 | 高度不飽和脂肪酸含有組成物の製造方法 |
US10899994B2 (en) | 2017-06-14 | 2021-01-26 | Nisshin Pharma Inc. | Method for producing polyunsaturated fatty acid-containing composition |
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