CN1055079C - 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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- CN1055079C CN1055079C CN96109525A CN96109525A CN1055079C CN 1055079 C CN1055079 C CN 1055079C CN 96109525 A CN96109525 A CN 96109525A CN 96109525 A CN96109525 A CN 96109525A CN 1055079 C CN1055079 C CN 1055079C
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- acid ester
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- docosahexenoic
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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 present invention relates to a method for extracting DHA from fish oil, which belongs to the field of extracting polyunsaturated fatty acid ester from fish oil via chemical modification. The method comprises DHA and EPA prepared via fish oil sponification and esterification and by a supercritical fluid extraction method. The method has the advantages of high extracted DHA purity, high yield, no harmful solvent, simple technical process and high extraction speed and is suitable for commercial 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 60-217299 etc.) adopt the urea clathration partition method, the hexane extraction method, high performance liquid chromatography, resin chromatography, metal salt precipitate method, rectification under vacuum and traditional crystallization process, concentrate the purification unsaturated fatty acids, 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 residual solvent is difficult to remove in the product, has limited the application of product.
31 pages of " chemical industry progress " 92 year 6 phases disclose with supercritical fluid extraction extracts docosahexenoic acid and eicosa-pentaenoic technic acid, but, make its complex process, the cost height owing to adopt alternating temperature return-flow type supercritical extraction process, operate loaded down with trivial detailsly, be 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 and timnodonic acid ester mixture in the extraction fish oil.
The present invention extracts that the method for docosahexenoic acid ester and timnodonic acid ester mixture is that step realizes in the following order in the fish oil:
1. starting material:
Adopting the cold water deep sea fish oil is raw material.Docosahexenoic acid and the highest weight percentage of eicosa-pentaenoic acid mixture are 18% in this fish oil.It is orange red that fish oil is, and is lower than 15 ℃ and is solid-state.Strong stench flavor is arranged.
2. the preparation of docosahexenoic acid ester and timnodonic acid ester mixture
Fish oil is a class mixed fatty glycerides, and wherein glyceride is of a great variety, and major part is an omega-fatty acid, as C18: 4, C20: 4, C20: 5, C22: 4, C22: 5, C22: 6 and the 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 is destroyed, then according to the difference of long-chain unsaturated fatty acid salt solubleness under differing temps, in-30-20 ℃ temperature range, removed portion C 22: 4, C18: 4, C20: 4, C22: 5 and low-carbon (LC) saturated fatty hydrochlorate, obtain the methyl alcohol that weight percentage is 30-45% docosahexenoic acid and eicosa-pentaenoic hydrochlorate (ethanol) solution.With above-mentioned salts solution through acidification, become docosahexenoic acid and timnodonic acid after, directly first (second) esterification is purified esterification products with supercritical extraction under strong acid or alkali catalyst.Extraction agent is ethane, carbonic acid gas or ethane-carbonic acid gas, ethane-propane mixture, and makes entrainment agent with the ethanol of 0.5-5% (weight percent) or the water of 0-0.5%.When adopting the high pressure extraction method, extraction agent is a carbonic acid gas, when entrainment agent is the ethanol of 0.5-5% (weight percent), the temperature of control carbonic acid gas is 35-45 ℃, pressure is 70-150bar, and pressure is the scope of 90-120bar preferably, and temperature range is 35-40 ℃ preferably.Extraction product through the decompression throttling valve spray in the collector, obtain 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 healthcare products 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.Carbonic acid gas can be recycled, and it is low, pollution-free to consume energy, and can make full use of fish stock, is suitable for suitability 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
2The saponification of fish oil is carried out in protection heating down.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, and obtains oily mater.The oily product is put into autoclave, and as extraction agent, the ethanol of weight percent 1% carries out supercritical fluid extraction as entrainment agent with carbonic acid gas.In the pressure range of 35-40 ℃ and 70-80bar, extract the light constituent of 10% (weight) in the 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, the content of docosahexenoic acid ethyl ester and EPA-EE mixture is 72% in the product.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), oily matter (A) and 13ml methanol solution are at N
2Protection down, with highly basic NaOH as catalyzer, reflux, esterification 5 hours.Product (B) after the collection esterification.(B) puts into autoclave with product, with carbonic acid gas as extraction agent, 2% (weight) ethanol is as entrainment agent, extracts the light constituent of 10% (weight) in the product B in 45 ℃, 70-80bar pressure range, carries out supercritical carbon dioxide extraction then in the scope of 90-115bar.Collect extraction product.Obtain faint yellowly, clarify bright oily liquids, stench flavor is less.Analyze through GC-MS, recording wherein, Methyl docosahexaenoate and methyl eicosapentaenoic acid mixture 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 uses the 30-40% sulfuric acid acidation to pH3-4, at N
2Reflux is 6 hours under the protection.Product (B) after the collection esterification.Product is put into autoclave, and as extraction agent, 1% ethanol is as entrainment agent with carbonic acid gas, carries out supercritical carbon dioxide extraction in 45 ℃ and 70-80bar scope.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, docosahexenoic acid ethyl ester and EPA-EE mixture content are 65%.
Claims (6)
1. a method of extracting docosahexenoic acid ester and timnodonic acid ester mixture in the fish oil comprises saponification, and esterification and extraction process is characterized in that step is carried out in the following order:
(1). with the cold water deep sea fish oil is raw material, after saponification, carries out separation and purification at-30-20 ℃, removes C22: 4, C18: 4, C20: 4, C22: 5 and low-carbon (LC) saturated fatty hydrochlorate, obtain being rich in the mixture of docosahexenoic acid and timnodonic acid,
(2). with docosahexenoic acid and timnodonic acid under strong acid or alkali catalyst with methyl alcohol or alcohol reflux esterification,
(3). adopt supercritical extraction to purify, extraction agent is ethane, carbonic acid gas or ethane-carbonic acid gas, ethane-propane, and entrainment agent is ethanol or water.
2. a kind of method of extracting docosahexenoic acid ester and timnodonic acid ester mixture in the fish oil according to claim 1 is characterized in that described separation and purification temperature is-20-10 ℃.
3. a kind of method of extracting docosahexenoic acid ester and timnodonic acid ester mixture in the fish oil according to claim 1 is characterized in that described high pressure extraction process is to adopt supercritical extraction, and extraction agent is CO
2, extraction temperature 35-45 ℃, extracting pressure is 70-150bar, entrainment agent is ethanol or water.
4. a kind of method of extracting docosahexenoic acid ester and timnodonic acid ester mixture in the fish oil according to claim 3 is characterized in that described extraction temperature 35-40 ℃.
5. a kind of method of extracting docosahexenoic acid ester and timnodonic acid ester mixture in the fish oil according to claim 3 is characterized in that described extracting pressure is 90-120bar.
6. according to claim 1,2 or 3 described a kind of methods of extracting docosahexenoic acid ester and timnodonic acid ester mixture in the fish oil, it is characterized in that described entrainment agent is the ethanol of 0.5-5% or the water of 0-0.5%.
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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1160706A CN1160706A (en) | 1997-10-01 |
| CN1055079C true CN1055079C (en) | 2000-08-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| 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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Families Citing this family (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 |
| 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 |
| CN103086873B (en) * | 2013-01-11 | 2015-09-16 | 国家海洋局第三海洋研究所 | High speed adverse current chromatogram is separated preparation high purity DHA method |
| CN103396310B (en) * | 2013-07-25 | 2015-02-25 | 浙江大学 | Method for separating and purifying eicosapentaenoic acid ester and docosahexenoic acid ester from micro-algal oil or fish oil |
| 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 |
| 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 |
| CN104478694B (en) * | 2014-12-02 | 2016-03-16 | 东莞市荷花食品有限公司 | A kind of method extracting docosahexenoic acid and timnodonic acid from Yellowtail fish |
| 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 |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4164506A (en) * | 1977-03-17 | 1979-08-14 | Kao Soap Co., Ltd. | Process for producing lower alcohol esters of fatty acids |
| EP0292846A2 (en) * | 1987-05-28 | 1988-11-30 | Star Oil Ltd | A process for the extraction of docosahexaenoic acid ethyl ester from fish oils and pharmaceutical and/or dietetic compositions containing a mixture of docosahexaenoic and eicosapentaenoic acid ethyl esters |
-
1996
- 1996-08-23 CN CN96109525A patent/CN1055079C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4164506A (en) * | 1977-03-17 | 1979-08-14 | Kao Soap Co., Ltd. | Process for producing lower alcohol esters of fatty acids |
| EP0292846A2 (en) * | 1987-05-28 | 1988-11-30 | Star Oil Ltd | A process for the extraction of docosahexaenoic acid ethyl ester from fish oils and pharmaceutical and/or dietetic compositions containing a mixture of docosahexaenoic and eicosapentaenoic acid ethyl esters |
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| CN1160706A (en) | 1997-10-01 |
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