CN1160706A - Extraction method of unsaturated fatty acid from fish oil - Google Patents
Extraction method of unsaturated fatty acid from fish oil Download PDFInfo
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- CN1160706A CN1160706A CN96109525A CN96109525A CN1160706A CN 1160706 A CN1160706 A CN 1160706A CN 96109525 A CN96109525 A CN 96109525A CN 96109525 A CN96109525 A CN 96109525A CN 1160706 A CN1160706 A CN 1160706A
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- docosahexaenoic acid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The extraction method belongs to the field of chemical modification of fish oil to obtain polyenic aliphatic ester and it includes saponification, esterification and supercritical fluid extraction to produce brain gold docosahexenoic acid (DHA) and eicosapentaenoic acid (EPA). The brain gold product extracted in the said method has high purity, high yield and no harmful solvent and the said method is suitable for industrialized production.
Description
The present invention relates to a kind of from fish oil concentration extraction lipid acid, obtain the field of polyene fatty acid ester class again through chemical modification.
(JP 60-170700 in the prior art, JP 59-172596, JP 58-15598, JP 60217299 etc.) adopt the urea clathration partition method, the hexane extraction method, high performance liquid chromatography, silver resin chromatography, metal salt precipitate method, rectification under vacuum and traditional crystallization process, concentrate the purification polyunsaturated fatty acid, in the above technology since raw material in longer chain fatty acid and oxygen, light, polymerization easily takes place in heat and oxygenant contact, degraded, qualitative changes such as oxidation reaction, the productive rate of product and purity drop, and stench flavor is big, and the residual solvent in the product is difficult to remove, and has limited the application of product.
31 pages of " chemical industry progress " 92 year 6 phases disclose with supercritical fluid extraction extracts docosahexenoic acid (DHA) technology, but owing to adopt alternating temperature return-flow type, alternating temperature transformation return-flow type supercritical fluid extraction technology, make its complex process, the cost height, complex operation is difficult to popularize.
The present invention has overcome that the prior art moderate purity is low, stench flavor is arranged in the product and the shortcoming of residual organic solvent is arranged, and provide a kind of in-30-20 ℃ temperature range preliminary purification, the method that under high pressure is further purified then, the technology of docosahexenoic acid ester (DHA) and eicosa-pentaenoic acid esters (EPA) in the extraction fish oil.
It is that step realizes in the following order that the present invention extracts the method for DHA (docosahexaenoic acid) in the fish oil:
1, starting material:
Adopting the cold water deep sea fish oil is raw material.Docosahexenoic acid in this fish oil (DHA) and the highest weight percentage of timnodonic acid (EPA) mixture are 18%.The fish oil look is orange red, is lower than 15 ℃ and is solid-state.Strong stench flavor is arranged.
2, the preparation of DHA (docosahexaenoic acid):
Fish oil is a class mixed fatty glycerides, and wherein lipid acid is of a great variety, and major part is an omega-fatty acid, as C18:4, and C20:4, C20:5, C22:4, C22:5, C22:6 and low-carbon (LC) saturated fatty acid.
The processing of crude fish oil at first is with the fish oil saponification, ester bond on the triglyceride level is destroyed, then according to the difference of long-chain unsaturated fatty acid salt solubleness under differing temps, in-30-20 ℃ temperature range, remove portion C 18:4, C20:4, C22:4, C22:5 and low-carbon (LC) saturated fatty hydrochlorate, obtaining weight percentage is methyl alcohol (ethanol) solution of 30-45% docosahexenoic acid (DHA) and timnodonic acid (EPA) salt.With above-mentioned salts solution through acidification, become docosahexenoic acid and timnodonic acid after, directly first (second) esterification is purified esterification products with the high pressure extraction method under strong acid or alkali catalyst.Extraction agent is ethane, carbonic acid gas or ethane-CO
2, ethane-propane mixture, and cooperate and to make entrainment agent with the water of an amount of 0.5-5% (weight percent) ethanol or 0-0.5%.When adopting the high pressure extraction method, extraction agent is CO
2, when entrainment agent is the ethanol of 0.5-5% (weight percent), control CO
2Temperature be 35-45 ℃, pressure is 70-150bar, pressure is the scope of 90-120bar preferably, temperature range is 35-40 ℃ preferably.Extraction product sprays in the collector through the decompression throttling valve, obtains faint yellow clear, docosahexenoic acid that viscosity is low and methyl eicosapentaenoic acid or ethyl ester product.
Product of the present invention is analyzed through GC-MS, and testing identity wherein contains docosahexenoic acid and EPA-EE mixture purity is 65-75%.Purity apparently higher than the obtained product of other method.Can prepare light weight, the medicine that particle is little.In addition, this product fishy smell is little, and color and luster is pure, clarifies brightly, does not contain any residual hazardous solvent.To can be used as protective foods or foodstuff additive and be applied in the daily breads such as bread, milk, dessert, sausage, put on market.This technical matters flow process and operating process are simple, and rate of extraction is fast, the productive rate height.CO
2Can be recycled, it is low, pollution-free to consume energy, and can make full use of fish stock, is suitable for industrialized production.
Embodiment 1:
The 7.0 gram crude fish oils of in there-necked flask, packing into, 2.0 gram NaOH and 100ml ethanol.At N
2Protection is heated down, carries out the saponification of fish oil.Reflux and stop heating after 1 hour.-20-10 ℃ temperature range internal cooling 1 hour, cross and filter out solid matter.Filtrate uses the 30-40% sulfuric acid acidation to PH3-4.At N
2Protection is reflux down, ethyl esterization 5 hours, and underpressure distillation removes and desolvates.Obtain oily mater.The oily product is put into autoclave, use CO
2As extraction agent, the ethanol of weight percent 1% carries out supercritical fluid extraction as entrainment agent.In the pressure range of 35-40 ℃ and 70-80bar, extract the light component of 10% (weight) in the portion of product earlier.In the pressure range of 90-115bar, extract then.Collect extraction product, obtain faint yellowly, clarify bright oily liquids, stench distinguish the flavor of less.Analyze through GC-MS, recording wherein, DHA and EPA ethyl ester mixture content are 72%.Embodiment 2:
With 10.0 gram crude fish oils, 2.5 gram NaOH and 120ml ethanol are at N
2Under the protection, reflux, saponification 1 hour.-15-0 ℃ temperature range internal cooling 1 hour, cross and filter out solid matter.Filtrate is 3-4 with 30-40% sulfuric acid acidation to pH value.The oily matter that collection is separated out (A).With oily matter (A) and 13ml methanol solution at N
2Protection down, with highly basic NaOH as catalyzer, reflux, esterification five hours.Product (B) after the collection esterification.(B) puts into autoclave with product, uses CO
2As extraction agent, 2% (weight) ethanol is as entrainment agent, and 45 ℃ of light components that extract 10% (weight) in the product B in the 70-80bar pressure range carry out supercritical CO then in the scope of 90-115bar
2Extraction.Collect extraction product.Obtain faint yellowly, clarify bright oily liquids, stench flavor is less.Through the GC-MS analysed preparation, recording wherein, DHA and EPA mixtures of methyl esters content are 70%.Embodiment 3:
In there-necked flask, pack into 7.0 the gram crude fish oils, 2.0 the gram NaOH, 100ml ethanol.At N
2Protection is reflux down, saponification 1 hour.0-20 ℃ temperature range internal cooling 1 hour, cross and filter out solid matter.Filtrate is 3-4 with 30-40% sulfuric acid acidation to pH value, at N
2Reflux is 6 hours under the protection.Product (B) after the collection esterification.Product is put into autoclave, use CO
2As extraction agent, 1% ethanol is as entrainment agent, and in the scope of 45 ℃ and 70-80bar, the light component with 10% (weight) in the product B extracts earlier.In the 90-100bar pressure range, carry out supercritical CO then
2Extraction.Collect extraction product.Obtain yellow, clarify bright oily liquids, stench flavor is big than example 1, example 2.Product is analyzed through GC-MS, and recording wherein, DHA and EPA ethyl ester mixture content are 65%.
Claims (6)
1, a kind of method of extracting DHA (docosahexaenoic acid) in the fish oil comprises saponification, and esterification and extraction process is characterized in that step is carried out in the following order:
(1) be raw material with the cold water deep sea fish oil, after saponification, carry out separation and purification, remove C18:4 at-30-20 ℃, C20:4, C22:4, C22:5 and low-carbon (LC) saturated fatty hydrochlorate obtain docosahexenoic acid and timnodonic acid.
(2) docosahexenoic acid and timnodonic acid are refluxed under strong acid or alkali catalyst esterification.
(3) adopt the high pressure extraction method to purify, extraction agent is ethane, carbonic acid gas or ethane-carbonic acid gas, and ethane-propane, entrainment agent are alcohol or water.
2, a kind of method of extracting DHA (docosahexaenoic acid) in the fish oil according to claim 1 is characterized in that described separation and purification temperature is-20-10 ℃.
3, DHA (docosahexaenoic acid) method in a kind of extraction fish oil according to claim 1 is characterized in that described high pressure extraction process is to adopt supercritical fluid extraction, and extraction agent is CO
2, extraction temperature is 35-45 ℃, extracting pressure is 70-150bar.Entrainment agent is alcohol or water.
4, a kind of method of extracting DHA (docosahexaenoic acid) in the fish oil according to claim 3 is characterized in that described extraction temperature is 35-40 ℃.
5, a kind of method of extracting DHA (docosahexaenoic acid) in the fish oil according to claim 3 is characterized in that described pressure is 90-120bar.
6,, it is characterized in that described entrainment agent is weight percentage and be the ethanol of 1-3% according to the method for DHA (docosahexaenoic acid) in any extraction fish oil described in the claim 1,2,3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109525A CN1055079C (en) | 1996-08-23 | 1996-08-23 | Extraction method of unsaturated fatty acid from fish oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109525A CN1055079C (en) | 1996-08-23 | 1996-08-23 | Extraction method of unsaturated fatty acid from fish oil |
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| Publication Number | Publication Date |
|---|---|
| CN1160706A true CN1160706A (en) | 1997-10-01 |
| CN1055079C CN1055079C (en) | 2000-08-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96109525A Expired - Fee Related CN1055079C (en) | 1996-08-23 | 1996-08-23 | Extraction method of unsaturated fatty acid from fish oil |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109549C (en) * | 2000-07-12 | 2003-05-28 | 刘玉 | Soft concentrated fish oil capsule and its supercritical CO2 extraction and rectification process |
| CN101851155A (en) * | 2010-03-12 | 2010-10-06 | 浙江大学 | Method for separating octadecadienoic acid from mixed long-chain fatty acid |
| CN102391111A (en) * | 2011-10-24 | 2012-03-28 | 赵永俊 | Method for producing docosahexaenoic acid ethyl ester (DHA-EE) |
| CN102964249A (en) * | 2012-11-16 | 2013-03-13 | 成都圆大生物科技有限公司 | Process capable of simultaneously producing and separating high-purity EPA (eicosapentaenoic acid) ethyl ester and high-purity DHA (docosahexaenoic acid) ethyl ester |
| CN103086873A (en) * | 2013-01-11 | 2013-05-08 | 国家***第三海洋研究所 | Preparation method of high-purity DHA (Docosahexaenoic Acid) by means of high-speed counter-current chromatography separation |
| CN103396310A (en) * | 2013-07-25 | 2013-11-20 | 浙江大学 | Method for separating and purifying eicosapentaenoic acid ester and docosahexenoic acid ester from micro-algal oil or fish oil |
| 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) |
| CN104478694A (en) * | 2014-12-02 | 2015-04-01 | 东莞市荷花食品有限公司 | Method for extracting docosahexenoic acid and eicosapentaenoic acid from seriola quinqueradiata |
| CN105384635A (en) * | 2014-09-09 | 2016-03-09 | 浙江医药股份有限公司新昌制药厂 | Separation and purification method for Omega-3 fatty acid ethyl ester from fish oil |
| CN108201135A (en) * | 2018-01-17 | 2018-06-26 | 广东长兴生物科技股份有限公司 | A kind of fish oil soft capsule and preparation method thereof |
| CN110872540A (en) * | 2019-12-25 | 2020-03-10 | 四川欣美加生物医药有限公司 | Method for extracting unsaturated fatty acid |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6025478B2 (en) * | 1977-03-17 | 1985-06-18 | 花王株式会社 | Production method of fatty acid lower alcohol ester |
| IT1205043B (en) * | 1987-05-28 | 1989-03-10 | Innova Di Ridolfi Flora & C S | PROCEDURE FOR THE EXTRACTION OF POLYUNSATURATED FATTY ACID ESTERS FROM FISH OILS AND PHARMACEUTICAL AND DIETARY COMPOSITIONS CONTAINING SUCH ESTERS |
-
1996
- 1996-08-23 CN CN96109525A patent/CN1055079C/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109549C (en) * | 2000-07-12 | 2003-05-28 | 刘玉 | Soft concentrated fish oil capsule and its supercritical CO2 extraction and rectification process |
| CN101851155A (en) * | 2010-03-12 | 2010-10-06 | 浙江大学 | Method for separating octadecadienoic acid from mixed long-chain fatty acid |
| CN101851155B (en) * | 2010-03-12 | 2013-08-28 | 浙江大学 | Method for separating octadecadienoic acid from mixed long-chain fatty acid |
| CN102391111A (en) * | 2011-10-24 | 2012-03-28 | 赵永俊 | Method for producing docosahexaenoic acid ethyl ester (DHA-EE) |
| CN102964249B (en) * | 2012-11-16 | 2015-03-11 | 成都圆大生物科技有限公司 | Process capable of simultaneously producing and separating high-purity EPA (eicosapentaenoic acid) ethyl ester and high-purity DHA (docosahexaenoic acid) ethyl ester |
| CN102964249A (en) * | 2012-11-16 | 2013-03-13 | 成都圆大生物科技有限公司 | Process capable of simultaneously producing and separating high-purity EPA (eicosapentaenoic acid) ethyl ester and high-purity DHA (docosahexaenoic acid) ethyl ester |
| CN103086873A (en) * | 2013-01-11 | 2013-05-08 | 国家***第三海洋研究所 | Preparation method of high-purity DHA (Docosahexaenoic Acid) by means of high-speed counter-current chromatography separation |
| CN103086873B (en) * | 2013-01-11 | 2015-09-16 | 国家***第三海洋研究所 | High speed adverse current chromatogram is separated preparation high purity DHA method |
| CN103396310A (en) * | 2013-07-25 | 2013-11-20 | 浙江大学 | Method for separating and purifying eicosapentaenoic acid ester and docosahexenoic acid ester from micro-algal oil or fish oil |
| 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 |
| CN105384635A (en) * | 2014-09-09 | 2016-03-09 | 浙江医药股份有限公司新昌制药厂 | Separation and purification method for Omega-3 fatty acid ethyl ester from fish oil |
| CN105384635B (en) * | 2014-09-09 | 2018-03-09 | 浙江医药股份有限公司新昌制药厂 | A kind of method that the fatty-acid ethyl esters of Omega 3 are isolated and purified from fish oil |
| CN104478694A (en) * | 2014-12-02 | 2015-04-01 | 东莞市荷花食品有限公司 | Method for extracting docosahexenoic acid and eicosapentaenoic acid from seriola quinqueradiata |
| CN108201135A (en) * | 2018-01-17 | 2018-06-26 | 广东长兴生物科技股份有限公司 | A kind of fish oil soft capsule and preparation method thereof |
| CN110872540A (en) * | 2019-12-25 | 2020-03-10 | 四川欣美加生物医药有限公司 | Method for extracting unsaturated fatty acid |
| CN110872540B (en) * | 2019-12-25 | 2024-02-06 | 四川欣美加生物医药有限公司 | Method for extracting unsaturated fatty acid |
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| Publication number | Publication date |
|---|---|
| CN1055079C (en) | 2000-08-02 |
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