CN1186307C - Method for preparing high-content alpha-linolenic acid - Google Patents
Method for preparing high-content alpha-linolenic acid Download PDFInfo
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- CN1186307C CN1186307C CNB021408491A CN02140849A CN1186307C CN 1186307 C CN1186307 C CN 1186307C CN B021408491 A CNB021408491 A CN B021408491A CN 02140849 A CN02140849 A CN 02140849A CN 1186307 C CN1186307 C CN 1186307C
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Abstract
The present invention relates to a method for separating and extracting high content alpha-linolenic acid from alpha-linolenic acid ester with the content larger than 45%. The raw oil of the alpha-linolenic acid ester with the content larger than 45% is processed via sponification acidolysis, polar solvent freezing separating, complexing, solvent gradient freezing and dewatering so as to prepare the alpha-linolenic acid with the content larger than 90%. The method has the advantages of low process temperature, good separation effect, stable reliability, simple operation, easy operation and simple device and is suitable for industrial scaled production.
Description
Technical field: the present invention relates to the preparation method of unsaturated fatty acids, particularly by content greater than separating, extract high content of alpha-linolenic method in 45% the alpha-linolenic acid ester (raw material).
Background technology: alpha-linolenic acid is 18 carbon polyenoic acids, and molecular formula is C
18H
30O
2It is universally acknowledged, " indispensable fatty acid " that can only lean on feed to replenish.It all has certain effect to people's early nutrition, baby's brain development, cardiovascular and cerebrovascular diseases, malignant tumour inhibition, hyperlipidemia etc.So each state of the world is all being studied its high-content product, for using at aspects such as medicament, life sciences.Other material of separating in preparation process simultaneously also has utility value, and they are all used in foodstuff additive, high-effect dispersion agent, makeup, senior siccative oil and oil production technology effectively.
Up to now, a lot of to high content of alpha-linolenic preparation research both at home and abroad.The CN1062897C patent disclosure a kind of supercritical extraction, rectificating method, this method extraction yield and purity are all higher, but need higher pressure (150-250atm); The CN1235956A patent application discloses a kind of floating method isolation technique that goes up, and this method production cost is low, but the purity of product is the highest by only 90%; The CN1317477A patent application discloses a kind of molecular distillation method, though this method finished product purity height, preparation process needs to finish under protection of inert gas, and is not easy to operate, needs evaporation to remove and desolvates, and carry out molecular distillation, the processing condition height.
The present invention be directed to the problem that above-mentioned prior art exists, improved, a kind of method that can the suitability for industrialized production high-purity alpha-linolenic acid is provided.
Summary of the invention: at first content is carried out the saponification acidolysis greater than 45% alpha-linolenic acid ester, extract free fatty acids, carry out subzero fractionation then, can get content at 70～75% alpha-linolenic acid, carry out Separation by Complexation and gradient freezing again, carry out molecular sieve dehydration at last, promptly get content greater than 90% alpha-linolenic acid finished product.
Preparation method provided by the invention comprises following process:
1, saponification acidolysis: 1 weight part alpha-linolenic acid ester content is mixed greater than 45% stock oil and 1～2 weight part, 10～15%NaoH solution, under 70 ℃～90 ℃ conditions, reacted 1～2 hour, reduce to the ethanol that adds 0.5 weight part after 65 ℃～70 ℃ when reacting liquid temperature, reacted 3 hours, after the question response liquid temp is lower than 60 ℃, slowly splash into an amount of 1: 1～1.5 sulfuric acid, make solution pH value to 2～3, isolate upper strata fluid with separating funnel.
This step makes all fatty acid triglycercides such as alpha-linolenic acid be converted into free fatty acids.
2, subzero fractionation: with the isolated upper strata of 1 weight part step 1 fluid, wash 2～4 times, add the bigger organic solvent of 1～1.5 weight part polarity, descended freezing 7～10 hours at 0 ℃ ± 2 ℃, filter, filtrate water is washed 3 times, and upper strata fluid is dry with 40～60 mol sieves, promptly gets content at 70～75% alpha-linolenic acid.
This step is based on dissolubility difference, makes saturated fatty acid and a small amount of alkene, diolefinic acid change solid phase over to, separates with alpha-linolenic acid.
3, Separation by Complexation: with 1 weight part step 2 gained alpha-linolenic acid fluid, with the ethanol that contains 0.5～0.75 weight part urea: methyl alcohol=1: 1～0.5 mixed solvent, 2～3 weight parts mix, following freezing 5-8 hour respectively at 5 ℃ ± 2 ℃ ,-6 ℃ ± 2 ℃ ,-12 ℃ ± 2 ℃ successively, filter washing liquid phase three times fast.
4, dehydration: step 3 gained liquid phase substance with 40-60 mol sieve adsorption dewatering, is promptly got content greater than 90% alpha-linolenic acid finished product.
Advantage of the present invention:
The present invention makes alpha-linolenic acid separate the saturated fatty acid of removing with desire owing to adopt mixed solvent freezing and crystallizing operation, and 18 carbon, one alkene, diolefinic acid etc. separate with liquid/solid phase, and alpha-linolenic acid purity is improved.Liquid phase is repeated freezing, the complexing of mixed solvent, can make alpha-linolenic acid content reach 85～92%.This technology has been saved Ag
+The gel chromatography operation is greatly simplified and easy to implement technology, still can obtain series product.Simultaneously, owing to adopt the back extraction desolventizing, molecular sieve dehydration carries out full technology at a lower temperature, is unlikely making the alpha-linolenic acid oxidation, thereby guarantees quality product.Method provided by the invention is reliable and stable, and is easy to operation, and cost is low, suitability for industrialized production.
The invention will be further described below by embodiment.
Embodiment:
Embodiment 1, be the there-necked flask that 49.6% alpha-linolenic acid stock oil places 1000ml with 250ml content, stir and add 10%NaOH solution 350ml down, reacted one hour down at 75 ℃, after being lower than 70 ℃, reacting liquid temperature adds ethanol 150ml, continue reaction three hours, after reacting liquid temperature is lower than 60 ℃, slowly be added dropwise to 1: 1 H
2SO
4Make solution pH value to 2～3, isolate upper strata fluid with separating funnel, wash three times, add methyl alcohol: the mixed solvent 250ml of acetone=2: 1,0 ℃～-2 ℃ freezing 8 hours down, filter, filtrate water is given a baby a bath on the third day after its birth time, and upper strata fluid is with 50 mol sieve drying, promptly gets content and be 72.6% alpha-linolenic acid.Get the above-mentioned alpha-linolenic acid fluid of 250ml, add the ethanol contain 150 gram urea: the mixing solutions 200ml of methyl alcohol=1: 0.5, successively freezing 6 hours of 5 ℃ ,-6 ℃ ,-12 ℃ difference, filter, washing liquid phase three times is dewatered with 50 mol sieve, promptly gets content greater than 90% alpha-linolenic acid.
Embodiment 2, be that 58.4% alpha-linolenic acid stock oil places the 1000ml there-necked flask with 250ml content, stir add down 10%NaOH solution 350ml in 65 ℃ down reaction add ethanol 100ml after 1 hour, continue reaction 3 hours, slowly add 1: 1 H
2SO
4Solution makes pH value to 2～3, isolates upper strata fluid with separating funnel, washes 3 times, add methyl alcohol: the mixed solution 300ml of ethanol=1: 1,0 ℃～-2 ℃ freezing 8 hours down, filter, wash three times filtrate, upper strata fluid is with the sieve dehydration of 50 mol, promptly gets content and be 74% alpha-linolenic acid.Get the above-mentioned alpha-linolenic acid fluid of 250ml, add the ethanol contain 150 gram urea: the mixing solutions 200ml of methyl alcohol=1: 0.5, successively freezing 6 hours of 5 ℃ ,-6 ℃ ,-12 ℃ difference, filter, washing liquid phase three times is dewatered with 50 mol sieve, promptly gets content greater than 90% alpha-linolenic acid.
Embodiment 3, be that 61.1% alpha-linolenic acid stock oil places the 1000ml there-necked flask, stir and add 10%NaOH solution 370ml down 200ml content, in 65 ℃ down reaction add ethanol 100ml after one hour, continue reaction three hours, slowly add 1: 1 H
2SO
4Solution makes pH value to 2～3, isolates upper strata fluid, washes 3 times, adds methyl alcohol 200ml, 0 ℃～-2 ℃ freezing 8 hours down, filter, wash 3 times filtrate, upper strata fluid sieves with 50 mol and dewaters that promptly to get content be 74.5% alpha-linolenic acid.Get this alpha-linolenic acid fluid of 200ml and add the ethanol that contains 120 gram urea: the mixed solution 200ml of methyl alcohol=1: 1, descended freezing 6 hours respectively at 5 ℃ ,-6 ℃ ,-12 ℃ successively, filter washing liquid phase three times, with the sieve dehydration of 50 mol, promptly get content greater than 90% alpha-linolenic acid.
Claims (2)
1, a kind of by the alpha-linolenic acid ester content greater than separating, extract the method for content in 45% the stock oil greater than 90% alpha-linolenic acid, it is characterized in that sepn process may further comprise the steps:
(1) saponification acidolysis: 1 weight part alpha-linolenic acid ester content is mixed greater than 45% stock oil and 1～2 weight part, 10～15%NaoH solution, under 70～90 ℃ of conditions, reacted 1～2 hour, reduce to the ethanol that adds 0.5 weight part after 65～70 ℃ when reacting liquid temperature, reacted 3 hours, after the question response liquid temp is lower than 60 ℃, slowly splash into an amount of sulfuric acid, make solution pH value to 2～3, isolate upper strata fluid with separating funnel;
(2) subzero fractionation: with the isolated upper strata of 1 weight part step 1 fluid, wash 2～4 times, the organic solvent that adds 1～1.5 weight part, described organic solvent is methyl alcohol and acetone mixed solvent, methyl alcohol and alcohol mixed solvent or alcohol solvent, descended freezing 7～10 hours at 0 ℃ ± 2 ℃, filter, filtrate water is washed 3 times, upper strata fluid is dry with 40～60 mol sieves, promptly gets content at 70～75% alpha-linolenic acid;
(3) Separation by Complexation: with 1 weight part step 2 gained alpha-linolenic acid fluid, mix with the mixed solvent of methyl alcohol with urea-containing ethanol, wherein the volume ratio of ethanol and methyl alcohol is 1: 1～0.5 in the mixed solvent, the weight part of urea is 0.5～0.75, the weight part of mixed solvent is 2～3, successively 5 ℃ ± 2 ℃ ,-6 ℃ ± 2 ℃ ,-12 ℃ ± 2 ℃ freezing 5～8 hours down respectively, filter washing liquid phase three times fast;
(4) dehydration: the liquid phase substance of step 3 gained is sieved adsorption dewatering with 40～60 mol, promptly get content greater than 90% alpha-linolenic acid finished product.
2, method according to claim 1 is characterized in that: the described methyl alcohol of step 2 and its volume ratio of acetone mixed solvent are 2: 1～0.5, and its volume ratio of methyl alcohol and alcohol mixed solvent is 1: 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021408491A CN1186307C (en) | 2002-07-10 | 2002-07-10 | Method for preparing high-content alpha-linolenic acid |
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| CNB021408491A CN1186307C (en) | 2002-07-10 | 2002-07-10 | Method for preparing high-content alpha-linolenic acid |
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| CN1467193A CN1467193A (en) | 2004-01-14 |
| CN1186307C true CN1186307C (en) | 2005-01-26 |
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| CN104672081B (en) * | 2015-03-17 | 2016-08-24 | 北京阳光基业药业有限公司 | A kind of linolenic method of purification a- |
| CN105413596A (en) * | 2015-11-03 | 2016-03-23 | 中科田园(北京)农业科技有限公司 | Peony seed oil, high-purity alpha-linolenic acid microcapsule and co-production method thereof |
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