CN102320953A - Method for preparing natural alpha-linolenic acid from crude oil of idesia polycarpa var.vestita diels - Google Patents
Method for preparing natural alpha-linolenic acid from crude oil of idesia polycarpa var.vestita diels Download PDFInfo
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- CN102320953A CN102320953A CN201110208499A CN201110208499A CN102320953A CN 102320953 A CN102320953 A CN 102320953A CN 201110208499 A CN201110208499 A CN 201110208499A CN 201110208499 A CN201110208499 A CN 201110208499A CN 102320953 A CN102320953 A CN 102320953A
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Abstract
The invention discloses a method for preparing natural alpha-linolenic acid from crude oil of idesia polycarpa var.vestita diels and belongs to the fields of medicines, food and feed. The technology mainly comprises the technical processes of preparing mixed fatty acid, preparing fatty acid ethyl ester, performing urea clathration, performing silica gel column chromatography, drying under reduced pressure and the like. The method is characterized in that: enrichment is performed by a urea clathration method, so the improvement on alpha-linolenic acid content is facilitated, impurities are removed, loss is reduced, yield is increased and the burden of the subsequent operation is reduced; the clathration technical process is optimized by substituting ethanol for methanol, so toxic reagents such as methanol and the like are not used; purification is performed by a silica gel column chromatographic technology, so purity and quality of products are improved; the technical process is simple, convenient and economic, and is high in operability; the requirement on equipment is not high; most of the used reagents can be recycled, so cost is obviously reduced and the method is economic and environment-friendly; and the method is suitable for production of enterprises with different scales and has wide application prospect in the production of high-quality alpha-linolenic acid.
Description
Technical field
The invention belongs to medicine, food and field of fodder, particularly a kind of Idesia polycarpa crude oil that uses is the linolenic method of the natural a-of raw material production.
Background technology
Idesia polycarpa is the distinctive woody oleiferous plants plant variety of China, has to distribute extensively, and is less demanding to soil, weather etc.; The characteristics that flexibility is stronger; Be suitable for low quality, barren hill, beach, mountain planting has the characteristics of " be prone to cultivation, be prone to promote, be prone to popularize ".The cash crop that it is a kind of high yield, economic worth is high have great using value and potentiality to be exploited.According to document announcement: Idesia polycarpa reaches 70～100 years the period of growth of the crop; Its fruit oleaginousness is higher, and (the individual plant produce oil can reach 200～300kg); Especially its oily unsaturated fatty acids is up to more than 82%; And be rich in linolic acid (up to 68～80%) and a-linolenic acid (in the fruit oil up to 2.0%, in the seed oil up to 2.5%).
The a-linolenic acid is the necessary unsaturated fatty acids of human body normal physiological activity (PUFAs); It can change into needed by human but can not self synthesize EPA and DHA; Have total cholesterol and the physiological function that improves HDL-SUV/LDL cholesterol ratio in the obvious reduction serum; The immunizing power of ability enhances human body; Cancer cells such as mammary cancer, colorectal carcinoma, lung cancer and cancer of the stomach there is certain restraining effect, can also prevents skin aging, delaying human body caducity, anti-inflammatory antianaphylaxis, the health of human body is had very important positive effect.Its preparation often is added among medicine or the health food, or is used for the rat chow animal.But the a-linolenic acid generally lacks in human body, lack in China the general population colony at present alpha-linolenic acid ratio greater than 95%, intake is less than half of world health organisation recommendations amount 1g/d per capita.Particularly the Along with people's health care consciousness strengthens in recent years, and natural alpha-linolenic acid product is just demonstrating the development trend that increasing demand rises.
The plantation Idesia polycarpa not only can improve the ecological environment, and its product can also be used for the machining of special nutrient health care edible oil and extract natural alpha-linolenic acid, is a kind of ideal high-quality oil crops and natural alpha-linolenic acid source.Can predict, the natural alpha-linolenic acid of preparation has important practical significance from Idesia polycarpa, and its market and development prospect are very wide.
At present; The method of the natural alpha-linolenic acid of preparation mainly contains in the industry: urea adduct method; Its technology comparative maturity, equipment are simple relatively, operation is also uncomplicated, be easy to promotion and application; But its can not be with the carbon chain lengths difference and the identical or close lipid acid of saturation ratio separately, title product purity is lower; Silica gel column chromatography, its separate targets degree of purity of production is higher, is a kind of effective ways of purifying polyunsaturated fatty acid; Molecular distillation method; Its efficient is high, distillation temperature is low, heated time is short, can effectively prevent the oxygenolysis of pufas; But be difficult to carbon number and boiling point and alpha-linolenic acid quite or close lipid acid separate the final purity of product lower (about 70%), and apparatus expensive; The silver ion complexation method, this method is isolating effective and product purity is very high, but output is little, cost is high and the easy polluted product of some eluent; The crystallizing process under low temperature, method is simple, be easy to realize, but isolating effect is bad; The fat enzyme process, catalytic condition is gentle, quality product is very stable, but reaction environment is complicated, the difficult control of the Direction of Reaction, can only improve certain concentration relatively; Also has supercritical flow CO in addition
2Extraction process etc.
This patent is to be raw material with the Idesia polycarpa crude oil; Adopt the urea clathration enrichment to combine with purification by silica gel column chromatography; Prepare the method for natural alpha-linolenic acid; Overcome single method deficiency separately, explored a kind of novel process of efficient, the low-cost natural alpha-linolenic acid that the separation and purification relative content is lower from be rich in linoleic Idesia polycarpa oil, separation back alpha-linolenic acid quality is greatly improved.It will realize effectively developing Idesia polycarpa oil; Increase the market supply of natural alpha-linolenic acid; Satisfy people's productive life demand, will bring higher production added value and economic benefit to plantation peasant household and enterprise simultaneously, have very important realistic meaning and strategic importance.
Summary of the invention
The objective of the invention is to utilize Idesia polycarpa crude oil after the squeeze and filter removal of impurities to prepare the method for natural alpha-linolenic acid.This method utilizes the Idesia polycarpa crude oil to be raw material; The method that adopts the urea clathration enrichment to combine with purification by silica gel column chromatography prepares natural alpha-linolenic acid, has higher alpha-linolenic acid yield and sample purity; Low for equipment requirements; Technology can be operated by force, and production cost is lower, is fit to large-scale production.
The present invention realizes through following technical proposals.This scheme mainly comprises technological processs such as preparation mixed fatty acid, preparation lipid acid second fat, urea clathration, silica gel column chromatography, drying under reduced pressure.It is characterized in that:
(1) preparation mixed fatty acid.An amount of crude oil is added the ethanolic soln that contains KOH; Cooling rapidly after backflow for some time in 90 ℃ water-bath; Remove unsaponifiables with organic solvent extractions such as suitable quantity of water and sherwood oils, again with organic solvent extractions such as sherwood oils, washing was to neutral after water layer was handled with an amount of inorganic acid solution; Reclaim organic solvent through low-temperature reduced-pressure behind the anhydrous sodium sulfate dehydration then, obtain Idesia polycarpa oil mixed fatty acid.
(2) preparation lipid acid second fat.80 ℃ of for some time postcooling that reflux of ethanol water-bath with mixed fatty acid and hydrochloric 3%; Add suitable quantity of water, with organic solvent extractions such as sherwood oils, washing is to neutral; Reclaim organic solvent through low-temperature reduced-pressure behind the anhydrous sodium sulfate dehydration then, obtain lipid acid second fat.
(3) urea clathration.The lipid acid second fat for preparing is joined the urea ethanolic soln of certain proportioning, and 80 ℃ of for some time of refluxing are to clear, again explosive decompression suction filtration behind the crystallization inclusion certain hour at a certain temperature; Washing with alcohol xln with 95%; Add an amount of sherwood oil in the filtrating, and with adding the water extraction after the acidifying of proper inorganic acid solution, the organic phase washing is extremely neutral; Reclaim organic solvent through low-temperature reduced-pressure behind the anhydrous sodium sulfate dehydration then, obtain the alpha-linolenic acid bullion.
(4) silica gel column chromatography.Through the silica gel column chromatography top, (acetone: sherwood oil=85: 15), wash-out under the flow conditions of 2～5mL/min is collected the effluent that contains title product with acetone-sherwood oil system with the alpha-linolenic acid bullion.
(5) drying under reduced pressure.The collection effluent to there not being moving phase, obtains highly purified alpha-linolenic acid product in 20～40 ℃ of water-bath drying under reduced pressure.
The method that Idesia polycarpa crude oil provided by the invention prepares alpha-linolenic acid has following remarkable advantage: utilize the Idesia polycarpa crude oil after the squeeze and filter removal of impurities to be raw material; The method that adopts the urea clathration enrichment to combine with purification by silica gel column chromatography can obtain high-quality natural alpha-linolenic acid, and preparation process employing ethanol is the inclusion solvent; Avoided the toxic reagent use; The preparation process is easy, and is workable, not high to equipment requirements; The agents useful for same major part can recycling, economic environmental protection; The product of producing is suitable for application such as medicine, healthcare products; The preparation result shows that natural alpha-linolenic acid yield and purity are higher, is fit to the enterprise production of different scales, has the good application and the market requirement.
Down in the face of the detailed description of the invention:
Gordian technique of the present invention have following some: the one, in the urea clathration process, urea is suitable with the ratio of oil, otherwise can influence the direction of reaction, influences the yield of target compound.The 2nd, it is the inclusion solvent that ethanol is adopted in the urea clathration reaction, has avoided the toxic reagents such as methyl alcohol of conventional employing.The 3rd, ethanol will suit with oily ratio, the temperature and time of inclusion reaction, otherwise can influence urea dissolving, influence preparation effect, or the efficient and the energy consumption of influence production, causes certain influence and increases cost to follow-up work.The 4th, adopt acetone-the sherwood oil system is suitable, otherwise separating effect is bad, purity is low, yield is low, foreign matter content is high.
Embodiment
Following instance will further be explained method provided by the invention.
Examples of implementation
(1) take by weighing 50g Idesia polycarpa crude oil in the 500ml there-necked flask, add again and contain 15gKOH ethanolic soln 200mL, be put in the 1h that refluxes in 90 ℃ the water-bath then, during the backflow otherwise the time shake Erlenmeyer flask.Saponification is complete, after the solution clarification, rapidly with it cooling, then adds a certain amount of water and sherwood oil continuous extraction twice, removes unsaponifiables.The lower floor of extraction liquid is that water layer uses 10% HCI to be acidified to pH to be 2～3, to transfer to then in the separating funnel, use petroleum ether extraction; Standing demix removes lower floor, and the upper organic phase washing is extremely neutral; Through the funnel of SODIUM SULPHATE ANHYDROUS 99PCT is housed; 40 ℃ of water-baths decompression rotary evaporations of filtrating reclaim sherwood oil, promptly get the oily mixed fatty acid of Idesia polycarpa.
(2) get the ethanol that adds 15g mixed fatty acid and 150ml hydrochloric 3% in the 500ml three-necked bottle, 80 ℃ of backflow 90min of water-bath; Take out cooling, move in the separating funnel, add 150mL water; With sherwood oil 100mL extraction fatty-acid ethyl ester twice, merge extraction liquid twice, water is washed till neutrality; Through the funnel of SODIUM SULPHATE ANHYDROUS 99PCT is housed, the reduction vaporization in 40 ℃ of water-baths of filtrating reclaims sherwood oil.The lipid acid second fat of promptly making.
(3) 30g urea and 90g ethanol are inserted in the there-necked flask in the lump, be back to urea in 80 ℃ of water-baths and fully dissolve, add the lipid acid second fat that 10g has prepared again, continue to be back to clear.After being cooled to 5 ℃ of following crystallization inclusion 14h, the explosive decompression suction filtration is washed xln with 95% ethanol. add an amount of sherwood oil in the filtrating; Use 10% HCl solution acidifying filtrate to pH be 2～3, add suitable quantity of water and fully extract, remove the water layer of sub-cloud; The organic phase washing is extremely neutral; Add anhydrous sodium sulfate dehydration, the intact sherwood oil of filtrating rotary evaporation promptly gets alpha-linolenic acid content and reaches 5% sample separation.
(4) with the alpha-linolenic acid bullion, place the silicagel column top after activation, the balance, (acetone: sherwood oil=85: 15), wash-out under the flow conditions of 3～4mL/min is collected the effluent that contains title product with acetone-sherwood oil system.
(5) drying under reduced pressure.The collection effluent to there not being moving phase, obtains the natural alpha-linolenic acid product of high purity, high quality of content 92.2% in 20～40 ℃ of water-bath drying under reduced pressure.
Claims (3)
1. the preparation method of a natural alpha-linolenic acid, it is characterized in that utilizing Idesia polycarpa crude oil after the squeeze and filter removal of impurities for basic raw material prepares natural alpha-linolenic acid, preparation process comprises:
(1) the Idesia polycarpa crude oil through saponification, acidifying, washing, dewater, remove organic solvent, obtain mixed fatty acid.
(2) mixed fatty acid through acidifying Ethanol Treatment, extraction, washing, dewater, remove organic solvent, obtain lipid acid second fat.
(3) lipid acid second fat passes through urea adduct method, and after extracting after the acidifying, wash, dewater, removing organic solvent, obtains the alpha-linolenic acid bullion.
(4) the alpha-linolenic acid bullion with acetone-sherwood oil system wash-out, obtains high-purity alpha-linolenic acid solution through silica gel column chromatography.
(5) high-purity alpha-linolenic acid solution obtains highly purified alpha-linolenic acid product through the low-temperature reduced-pressure drying.
2. according to the urea adduct method preparation technology described in claim 1 step (3); It is characterized in that the mixed fatty acid second fat that the Idesia polycarpa crude oil makes is 1: 2～4 with the urea ratio, with the alcoholic acid ratio be 1: 7～10; Crystallization inclusion temperature is-5～5 ℃, and the inclusion time is 10～16 hours.
3. according to adopting ethanol in claim 1 step (3) as urea clathration solvent treatment Idesia polycarpa crude oil lipid acid second fat.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529739A (en) * | 2014-12-25 | 2015-04-22 | 北京阳光基业药业有限公司 | Purification method of unsaturated fatty acid |
| CN105837430A (en) * | 2016-05-04 | 2016-08-10 | 罗江县德金种植协会 | Method for extracting linoleic acid from idesia polycarpa crude oil |
| CN107698444A (en) * | 2017-03-03 | 2018-02-16 | 四川森迪科技发展股份有限公司 | One kind extracts linolenic method from Idesia polycarpa oil cake |
| CN110075012A (en) * | 2019-05-20 | 2019-08-02 | 湖北大学 | The application of idesia oil and cosmetics and tyrosinase activity inhibitor |
| CN110699185A (en) * | 2019-10-10 | 2020-01-17 | 齐鲁工业大学 | Method for refining fatty acid from oil and fat such as testa oryzae oil, quinoa bran oil, peony seed oil, fish oil, krill oil, bee pollen oil, etc |
| CN111635308A (en) * | 2020-06-20 | 2020-09-08 | 四川中海茂农业开发有限公司 | Method for co-producing and preparing linoleic acid and alpha-linolenic acid from idesia polycarpa seed oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1837179A (en) * | 2005-12-30 | 2006-09-27 | 安阳化学工业集团有限责任公司 | Process for preparing alpha-linolenic acid with purity more than 80% |
| CN101337880A (en) * | 2007-07-06 | 2009-01-07 | 通渭县晓铃商贸有限责任公司 | Process for extracting alpha-linolenic acid |
| CN101381298A (en) * | 2008-10-21 | 2009-03-11 | 四川省国政生物质能源科技发展股份有限公司 | Method for preparing conjugate linolic acid using idesia polycarpa maxim. var. vestita diels oil |
-
2011
- 2011-07-25 CN CN2011102084991A patent/CN102320953B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1837179A (en) * | 2005-12-30 | 2006-09-27 | 安阳化学工业集团有限责任公司 | Process for preparing alpha-linolenic acid with purity more than 80% |
| CN101337880A (en) * | 2007-07-06 | 2009-01-07 | 通渭县晓铃商贸有限责任公司 | Process for extracting alpha-linolenic acid |
| CN101381298A (en) * | 2008-10-21 | 2009-03-11 | 四川省国政生物质能源科技发展股份有限公司 | Method for preparing conjugate linolic acid using idesia polycarpa maxim. var. vestita diels oil |
Non-Patent Citations (2)
| Title |
|---|
| 《中国生化药物杂志》 20031231 张岫美等 蚕蛹油alpha-亚麻酸提取工艺研究和成分分析 第222-223页 1-3 第24卷, 第5期 * |
| 张岫美等: "蚕蛹油α-亚麻酸提取工艺研究和成分分析", 《中国生化药物杂志》, vol. 24, no. 5, 31 December 2003 (2003-12-31), pages 222 - 223 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529739A (en) * | 2014-12-25 | 2015-04-22 | 北京阳光基业药业有限公司 | Purification method of unsaturated fatty acid |
| CN105837430A (en) * | 2016-05-04 | 2016-08-10 | 罗江县德金种植协会 | Method for extracting linoleic acid from idesia polycarpa crude oil |
| CN107698444A (en) * | 2017-03-03 | 2018-02-16 | 四川森迪科技发展股份有限公司 | One kind extracts linolenic method from Idesia polycarpa oil cake |
| CN110075012A (en) * | 2019-05-20 | 2019-08-02 | 湖北大学 | The application of idesia oil and cosmetics and tyrosinase activity inhibitor |
| CN110699185A (en) * | 2019-10-10 | 2020-01-17 | 齐鲁工业大学 | Method for refining fatty acid from oil and fat such as testa oryzae oil, quinoa bran oil, peony seed oil, fish oil, krill oil, bee pollen oil, etc |
| CN111635308A (en) * | 2020-06-20 | 2020-09-08 | 四川中海茂农业开发有限公司 | Method for co-producing and preparing linoleic acid and alpha-linolenic acid from idesia polycarpa seed oil |
| CN111635308B (en) * | 2020-06-20 | 2023-04-07 | 四川中海茂农业开发有限公司 | Method for co-producing and preparing linoleic acid and alpha-linolenic acid from idesia polycarpa seed oil |
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