CN1036008A - The method for separating and preparing of timnodonic acid and docosahexenoic acid and ester class thereof - Google Patents
The method for separating and preparing of timnodonic acid and docosahexenoic acid and ester class thereof Download PDFInfo
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- CN1036008A CN1036008A CN 88101811 CN88101811A CN1036008A CN 1036008 A CN1036008 A CN 1036008A CN 88101811 CN88101811 CN 88101811 CN 88101811 A CN88101811 A CN 88101811A CN 1036008 A CN1036008 A CN 1036008A
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- unsaturated fatty
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Abstract
The present invention separates the method for preparing timnodonic acid, docosahexenoic acid and ester class thereof from the marine organisms grease.
Be characterized in that an an alkali metal salt crystallization process and urea inclusion method combine, constitute a novel process.By the EPA and the DHA mixture purity height of this explained hereafter, and prevented isomerization.Reduced the consumption and the temperature of reaction of alkali and alcohol in addition, shortened the reaction times, reduced cost effectively, processing unit is simple, and is easy to operate.
Description
The invention belongs to the technical field of separating preparation lipid acid or its lipid from grease.
ω-3 type long-chain highly unsaturated fatty acid, as timnodonic acid (EPA) docosahexenoic acid (DHA) is to keep the necessary active ingredient of human body normal physiological function, can effectively prevent and treat diseases such as coronary heart disease, cerebral thrombosis, hyperlipidemia, but enhanced stability after EPA, the DHA esterification, weaken GI pungency, still can keep above-mentioned activity simultaneously.
It should be noted that, the non-conjugated type feature of the double bond structure tool of EPA and DHA, in preparation process, be subjected to effects such as high temperature, highly basic, be easy to form the conjugated type isomer, and reduce its curative effect, therefore prevent that in preparation process isomerization from being most important.
The main method of separation and purification EPA and DHA has at present
1, layer folding partition method
2, subzero fractionation method
3, molecular distillation method
4, vacuum precision fractionating process
5, urea inclusion method (JP57-164196)
6, an alkali metal salt crystallization process (JP59-21641)
The shortcoming of above-mentioned 1,2,3,4 all methods is to need special technique conditions such as high vacuum, cryogenic freezing, chromatography, fractionation, and operation is also rather numerous and diverse.5, the technology of 6 two methods, equipment is simple.Wherein 5 methods can be removed saturated fatty acid and the low unsaturated fatty acids in the degrease, but direct handling oil fat raw material, also be not easy to remove oil-soluble impuritieses such as de-cholesterol, 5 methods need be equivalent to lipid acid or fatty acid ester weight 1-2 times urea and about 10 times solvent approximately in addition, therefore need bigger equipment, operation more numerous, the also corresponding increase of urea-containing waste water amount causes cost up.6 methods can be removed oil-soluble impuritieses such as saturated fatty acid and cholesterol, also direct handling oil fat raw material, but can not remove low unsaturated fatty acids, and saponification alkali charge and temperature of reaction are obviously higher, saponification time is long, the EPA and the DHA of method preparation produce isomerization significantly and form a part of conjugated isomers thus, thereby its curative effect is weakened.
In a word, the common drawback of 5,6 two methods is to prepare high-load EPA and DHA mixture.
The object of the present invention is to provide a kind of easy, economic industrial process, in order to the non-isomerized EPA of separate and prepare high-content from the marine organisms grease and DHA or its ester derivative.
In technology of the present invention, basic metal crystallization process and urea inclusion method are improved, and it is combined, remove oil-soluble impuritieses such as saturated fatty acid in the degrease and cholesterol with preceding method, remove low unsaturated fatty acids with the back method, make the non-isomerized EPA of high-content, DHA or its ester derivative thus.Its concrete technology is as follows:
1, the tankage with food-processings such as the marine organisms of being rich in EPA, DHA or its, tail, internal organ are raw material, press the poach formulation and extract grease.
2, the alcoholic solution that adds alkali metal hydroxide in above-mentioned grease carries out saponification.The mole number of per 1 kilogram of used alkali metal hydroxide of grease is 100-125 times of mole number that its saponification value is amounted to, and the consumption of alcohol (80-95%) is the 5-9 liter.Saponification temperature is 60-70 ℃, and saponification time is 10-50 minute.
3, reaction solution is cooled to below 25 ℃, make it separate out saturated fatty hydrochlorate crystal, after the filtering crystallization, concentrate pure filtrate, thin up, make wherein pure content be lower than 50%, use organic solvent, for example hexane extraction removes oil-soluble impuritieses such as de-cholesterol, with concentrated hydrochloric acid or below the 80% cricket cape Liang Bamboo H to 3, make unsaturated fatty acids again by telling in the water.Make unsaturated fatty acids after the oily water separation.
4, the heating for dissolving preparation contains the alcoholic solution of 10-20% urea.Above-mentioned unsaturated fatty acids is dissolved in the alcoholic solution of urea, the latter's consumption is a per kilogram unsaturated fatty acids 0.5-2 kilogram urea.Mix and make it to cool to 30-50 ℃, this moment, saturated or low unsaturated fatty acids and the formed inclusion compound crystallization of urea were separated out, and it is the alcoholic solution of the high unsaturated fatty acid of major ingredient that the elimination crystallization just obtains with EPA and DHA.
5, with the alcoholic solution thin up of above-mentioned high unsaturated fatty acid, oily water separation, tell high unsaturated fatty acid, and wash with water and remove remaining urea, and then decolour with adsorbents adsorb such as acidic white earth or silicic acid or activated carbon, and remove other organic impurity, and carry out deodorizing with steam distillation again, promptly make mixture colourless, that nothing is smelt non-isomerized EPA of high-content and DHA.
As prepare the ester derivative of EPA and DHA, can be in step 4 the high unsaturated fatty acid alcoholic solution of gained, feed HCl gas or add the vitriol oil, make and contain sour 1-10% in the mixture, so under the condition of acid as catalyst, esterification takes place, and does not need before and after urea is handled lipid acid esterification separately, thereby saved pure consumption greatly, made cost reduction, simplified control.
For preventing EPA, DHA deterioration by oxidation, logical as far as possible nitrogen protection in the whole process of preparation.
Embodiment 1
Get 320 kilograms in fresh mackerel internal organ, water Zhu formulation makes 54 kilograms in fish oil in nitrogen atmosphere, adds 0.1% vitamin-E, and in 0 ℃ of airtight storage, measuring its saponification value is 185.Through gas chromatography determination.Contain 7.3% EPA in its lipid acid, 15.5% DHA.0.15 kilogram NaOH put into 7 liter 95% ethanol, heating makes the NaOH dissolving, and add 1 kilogram of above-mentioned mackerel oil, 70 ℃ of saponification are 30 minutes in nitrogen atmosphere, stirring is cooled to 10 ℃, the saturated fatty hydrochlorate sufficient crystallising of generation is separated out, remove by filter crystallization, and use the small amount of ethanol wash crystallization, washing water and filtrate are merged concentrating under reduced pressure, add 2 liters of water dilutions of degassing, use 1 liter of n-hexane extraction unsaponifiable matter then, divide water outlet liquid, add dilute sulphuric acid (H
2SO
4: H
2O=4: 1, down together), transfer PH to 2, use 1.5 liters of n-hexane extractions again, steam and remove hexane, obtain 340 gram unsaturated fatty acidss, use gas chromatography determination, contain EPA20.2% in the lipid acid, DHA44.9% amounts to 65.1%.
510 gram urea are put into 2700ml ethanol, heating for dissolving, add above-mentioned unsaturated fatty acids 340 grams, 70 ℃ were stirred 10 minutes, be chilled to 30-35 ℃, the inclusion compound that low unsaturated fatty acids of filtering and urea form, in gained alcohol filtrate, feed 100gHCl gas, stir, place more than 6 hours, then reaction solution is concentrated, and add 5 liters of water dilutions of degassing, with 5 liters of n-hexane extractions high unsaturated fatty acid ester wherein, with 45 ℃ of warm water washings three times, add acidic white earth 170 grams, stir decolouring, the filtering carclazyte, steam and remove normal hexane, with enriched material under 5mmHg column pressure and 170 ℃, carry out steam distillation deodorization in 3 hours, obtain the flaxen nothing of 174 grams and smell, the ethyl ester enriched material of tasteless EPA and DHA consists of EPA31.7% by gas chromatography determination lipid acid, DHA54.1%, total amount reaches 85.8%.Confirm that by ultraviolet detection EPA wherein, DHA component do not have obvious absorption at 233mm wavelength place, therefore wherein be substantially devoid of the conjugated isomers of EPA and DHA.
Embodiment 2
Get example 1 described mackerel oil kg, make unsaturated fatty acids and handle according to the method identical with urea with example 1, the ethanol filtrate of filtering urea inclusion, concentrate and reclaim ethanol, add 5 liters of water dilutions of degassing, with 5 liters of n-hexane extractions high unsaturated fatty acid wherein, the gained hexane solution, decolour according to the method identical with example 1, deodorizing is handled, make the flaxen nothing of 163 grams and smell tasteless EPA and the enriched material of DHA, its lipid acid of gas chromatography determination consists of EPA31.2%, DHA53.7%, and total amount reaches 84.9%.Ultraviolet detection is confirmed, does not wherein contain the conjugated isomers of EPA and DHA substantially.
Separate preparation eicosapentaenoic acid and DHA and ester class thereof by technology of the present invention from the marine growth grease, consumption and the reaction temperature of alkali and alcohol have been reduced, shortened the reaction time, effectively reduced cost, and suppressed the isomerization of EPA and DHA, increased significantly the content of non-conjugated EPA and DHA. Process equipment of the present invention is simple in addition, and is easy to operate.
| Title | Page or leaf | OK | Before the revisal | After the revisal |
| The specification specification | 2 2 3 3 | 15 22 1 6-7 | The 100-125 of the alcoholic solution molal quantity of alkali metal crystallisation alkali metal hydroxide is alcohol organic solvent, for example hexane extraction doubly | The 1000-1250 of the ethanolic solution mole number of alkali metal salt crystallisation alkali metal hydroxide doubly; Ethanol is with conventional methods such as organic solvent extraction or freezing precipitations |
| Specification | 3 3 3 3 4 | 7 10 20 23 14 | Alcoholic solution except lipoduria elements such as de-cholesterols The mixture of DHA. Contain sour 1-10% in the mixture, With washings | Remove the solution of the low carbon number straight chain alcohols such as the ethanol of lipoduria element or methyl alcohol. The mixture of DHA. The adsorption refining step is not limited to prepare carries out latter stage. Other process in the preparation also can be inserted and contain sour 1-10% (g/v) in the mixture, with washing lotion |
Claims (2)
1, a kind of method for preparing timnodonic acid, docosahexenoic acid or its ester class of from the marine life grease, separating, it is characterized in that earlier making fat saponification, use the resulting unsaturated fatty acidss of low carbon number straight chain alcohol solution-treated such as the ethanol of urea or methyl alcohol again with the ethanolic soln of alkali metal hydroxide.Directly the alcoholic solution of the high unsaturated fatty acid of gained adds mineral acid and carries out catalysis fatization after removing urea inclusion.
2, method for separating and preparing as claimed in claim 1, it is characterized in that described saponification condition is: the mole number of the alkali metal hydroxide that per 1 kilogram of grease is used is 1000-1250 times of its saponification value institute reduced mole number, temperature of reaction is 60-70 ℃, and the reaction times is 10-50 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88101811 CN1013858B (en) | 1988-03-26 | 1988-03-26 | Preparation of eicosapentaenoic acid (epa), docosahexenoic acid (dha) and their esters by separation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88101811 CN1013858B (en) | 1988-03-26 | 1988-03-26 | Preparation of eicosapentaenoic acid (epa), docosahexenoic acid (dha) and their esters by separation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1036008A true CN1036008A (en) | 1989-10-04 |
| CN1013858B CN1013858B (en) | 1991-09-11 |
Family
ID=4831887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88101811 Expired CN1013858B (en) | 1988-03-26 | 1988-03-26 | Preparation of eicosapentaenoic acid (epa), docosahexenoic acid (dha) and their esters by separation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1013858B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058776B (en) * | 2007-05-24 | 2010-06-02 | 西北民族大学 | Method of removing erucic acid in grease obtained from descurainia sophia seed |
| CN102311882A (en) * | 2011-08-11 | 2012-01-11 | 青岛农业大学 | Extraction method for unsaturated fatty acid |
| CN103281910A (en) * | 2010-12-27 | 2013-09-04 | 金欧米茄公司 | Omega-3 concentrate |
| CN103848734A (en) * | 2014-01-14 | 2014-06-11 | 中国科学院海洋研究所 | Method for extracting natural EPA (eicosapentaenoic acid) and DHA (eicosapentaenoic acid) |
| CN105693538A (en) * | 2016-02-23 | 2016-06-22 | 国家海洋局第三海洋研究所 | Solvent-free method of preparing unsaturated fatty acyl ethanol amine compound |
| CN101463371B (en) * | 2000-01-19 | 2016-12-14 | Dsm Ip资产公司 | Solventless extraction process |
| CN107927536A (en) * | 2017-12-01 | 2018-04-20 | 江彩莲 | Health products containing n-octacosanol |
| CN116023265A (en) * | 2022-12-22 | 2023-04-28 | 仲恺农业工程学院 | Oleate, preparation method thereof and skin care product |
-
1988
- 1988-03-26 CN CN 88101811 patent/CN1013858B/en not_active Expired
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101463371B (en) * | 2000-01-19 | 2016-12-14 | Dsm Ip资产公司 | Solventless extraction process |
| CN101058776B (en) * | 2007-05-24 | 2010-06-02 | 西北民族大学 | Method of removing erucic acid in grease obtained from descurainia sophia seed |
| CN103281910A (en) * | 2010-12-27 | 2013-09-04 | 金欧米茄公司 | Omega-3 concentrate |
| CN103281910B (en) * | 2010-12-27 | 2015-04-15 | 金欧米茄公司 | Omega-3 concentrate |
| CN102311882A (en) * | 2011-08-11 | 2012-01-11 | 青岛农业大学 | Extraction method for unsaturated fatty acid |
| CN102311882B (en) * | 2011-08-11 | 2012-12-26 | 青岛农业大学 | Extraction method for unsaturated fatty acid |
| CN103848734A (en) * | 2014-01-14 | 2014-06-11 | 中国科学院海洋研究所 | Method for extracting natural EPA (eicosapentaenoic acid) and DHA (eicosapentaenoic acid) |
| CN103848734B (en) * | 2014-01-14 | 2016-03-16 | 中国科学院海洋研究所 | A kind of method extracting natural EPA and DHA |
| CN105693538A (en) * | 2016-02-23 | 2016-06-22 | 国家海洋局第三海洋研究所 | Solvent-free method of preparing unsaturated fatty acyl ethanol amine compound |
| CN107927536A (en) * | 2017-12-01 | 2018-04-20 | 江彩莲 | Health products containing n-octacosanol |
| CN107927536B (en) * | 2017-12-01 | 2021-09-03 | 广州玉婷阁医药科技有限公司 | Health product containing octacosanol |
| CN116023265A (en) * | 2022-12-22 | 2023-04-28 | 仲恺农业工程学院 | Oleate, preparation method thereof and skin care product |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1013858B (en) | 1991-09-11 |
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