CN1162009A - Separation extraction of alpha-linolenic acid from linseed oil - Google Patents
Separation extraction of alpha-linolenic acid from linseed oil Download PDFInfo
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- CN1162009A CN1162009A CN 97101925 CN97101925A CN1162009A CN 1162009 A CN1162009 A CN 1162009A CN 97101925 CN97101925 CN 97101925 CN 97101925 A CN97101925 A CN 97101925A CN 1162009 A CN1162009 A CN 1162009A
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Abstract
A method for separating and extracting alpha-linolenic acid from linseed oil features that at first the saponification method is used to extract and prepare mixed fatty acid from linseed oil, then the urea adduct method is used to separate saturated and unsaturated fatty acids to obtain the mixture of alpha-linolenic acid and linolic acid. This invented method has the advantages of low cost, simple equipment and convenient operation, by using one urea adduct method, the total recovery rate reaches 60.4%, the enrichment rate reaches over 95%, and after separation, the various components can be further comprehensively used.
Description
The present invention relates to the method for a kind of separation from oleum lini, enrichment, extraction alpha-linolenic acid and linolic acid mixing unsaturated fatty acids.
α---linolenic acid (Linolenic acid) is the Z.Z.Z-9.12.15-punicic acid at chemical name, and molecular structure is:
And the chemical name of linolic acid (Linoleic acid) is the Z.Z-9.12-octadecadienoic acid, and molecular structure is:
Both claim indispensable fatty acid (EFA on biological chemistry, essential fatty acid), point out on the biological chemistry that linolic acid, linolenic acid are the necessary lipid acid of human body, can not synthesize in the human body self, must be by food supply, they all belong to the novel oil plant of discovered in recent years.Linolic acid and lipid metabolism, the formation of sperm is relevant, and the skin lesion that X ray is caused has provide protection.It still is a prostaglandin(PG) synthetic raw material in vivo.Prostaglandin(PG) has antiinflammation, and can reduce hematoblastic gathering, make pharmacological actions such as blood vessel expansion, before synthesis of prostaglandins, linolic acid is converted into gamma-linolenic acid through body metabolism and also has anti thrombotic action, and reducing blood-fat is arranged, reduce cholesterol and reduce atherosclerotic effect.And alpha-linolenic acid (being that we test isolated linolenic acid) also is the new medicinal plant unit of rising, through clinical trial, α-tight numb acid has reducing blood-fat, prolongs the clotting time, and antithrombotic forms, the functions such as arteriosclerosis that disappear can directly be absorbed by human body.Therefore, will cause many shortage diseases if lack.Taiwan pharmacopeia record, the purposes of alpha-linolenic acid also can be nutritional tonics.Alpha-linolenic acid is just in the ascendant as the research of fodder additives simultaneously.Japan report, alpha-linolenic acid is just favored as the moiety of changing the shape product, and alpha-linolenic acid is the necessary material of maintenance balance between healthy skin cell and the normal skin film, is to be used to the cosmetic additive that keeps skin tender.
Enrichment, isolate polyene unsaturated fatty acid---linolic acid, linolenic test, domestic literature is not reported at present.External great majority report is from animal grease and is rich in that separation and Extraction obtains the Vegetable oil lipoprotein of alpha-linolenic acid.
The separation of lipid acid in the grease, early stage separation mainly is to separate saturated and unsaturated fatty acids, and enrichment degree is lower.Separation method has fractionating process, contains the crystallization process of wetting agent, with the crystallization process of fractionation solvent and hydrophilization process etc., because it is bigger to separate monoene and polyene unsaturated fatty acid difficulty, so new selective absorption absorption method of separation method of excavating, cation zeolites method, sieve method, these methods still are in the developing test stage.
With urea bag method (being urea adduct method) separating saturated fatty acid, monoene and polyene unsaturated fatty acid, commercialization already, and update in recent years.The compound of different content can be enriched to separately on the higher level, so method can be with the above oleic acid of oleic acid rich to 90% that contains about 70%, the linolic acid that will contain 78% enrichment of linoleic acid to 95%, to contain 47% linolenic acid and be enriched to 85% linolenic acid, principle forms adducts by excessive urea with lipid acid exactly in methyl alcohol---and be urea cage shape thing, then, the stable difference of heat is carried out separation and concentration, carry out the acid of vacuum distilling corps then according to urea cage shape thing.
Substep separates, in methyl alcohol, form the principle of urea cage shape thing according to lipid acid and excessive urea, saturated fatty acid with do not wrap the thermostability that forms urea cage shape thing with lipid acid and improve with degree of unsaturation and lower, so the selection amount of urea than with separation temperature be separate, the essential condition of enrichment.
Purpose of the present invention is exactly the resource that fully develops the wild oil plant of China's abundant, in conjunction with traditional separating and extracting method, find suitable processing condition, separation from the oleum lini of the plant flax of being rich in alpha-linolenic acid, enrichment, extraction alpha-linolenic acid and linolic acid mixing unsaturated fatty acids are for comprehensive utilization is supplied raw materials.
The selected plant flex seed oil length of the present invention is 40-50%, physicochemical constant: proportion (15 °/15 ℃) 0.9325, and refractive index (40 ℃) 1.4748, saponification value: 192.3, iodine number: 177.Lipid acid is formed saturated acid (palmitinic acid, stearic acid, eicosanoic acid) 9-11%, oleic acid 13-29%, linolic acid 15-30%, linolenic acid 44-61%.At first it is refined into oleum lini.Physical constant is as follows:
Saponification value: 193.03 iodine numbers: 176 acid numbers: 1.61
Analyze with GC, fatty acid oil is composed as follows:
Palmiticacid (C
16: 0) 6.0-6.5%, stearic acid (C
18: 0) 3.2-3.8%, oleic acid (C
18: 1) 21.0-21.5%, linolic acid (C
18: 2) 15.4-16.0%, linolenic acid (C
18: 3) 53.8-54.2%.Get the purified oleum lini, add a certain amount of dense rare NaOH liquid that crosses to 20-30%, oleum lini is 1 with the NaOH ratio: 1-3.Be heated to 90-100 ℃, the limit heating connects and stirs, and mixed fatty acid is produced in saponification, and the time is about 14-16 hour, and the saponification terminal point determines that with saponification value and saponification degree saponification value is defined as 193.03, and saponification degree is 87%, and iodine number is 167.Use rare H then
2SO
4Liquid is acidified to acidity, and is extremely neutral with saturated NaCl liquid washing in separating funnel, isolates the upper strata oil reservoir, obtains mixed fatty acid, and the fatty acid component of making is identical with the oil sample component.
Get a large amount of methyl alcohol of a adding of urea, urea is 1: 2～5 with the methanol quality ratio, stir, reflux is got a certain amount of mixing and is referred to that fat acid adds wherein to all dissolvings, lipid acid, urea, methanol quality ratio are 1: 2-5: 3-7, continue to stir, be heated to uniform state after, be transferred in the conical vessel of band plug, under 28 ° of-30 ℃ of room temperatures, leave standstill a night, obtain the urea cage shape thing precipitation of lipid acid.Suction filtration is isolated filter cake, filtrate, behind the dry cake, pour in the container as far as possible, add 50-60 ℃ of hot water dissolving's filter cake, decompose cage shape thing, be transferred to then in the separating funnel, isolate oil reservoir, with hot wash 2-3 time, obtain saturated fatty acid and add oleic pure cake, filtrate is transferred on the rotatory evaporator vacuum fractionation methyl alcohol, temperature is controlled at 50-60 ℃, and pressure is 10mmHg.Till steaming several minutes and no longer including methyl alcohol and distillate, take out excess, with the excessive urea that contains in the HCl acid heat water decomposition filtrate, extremely neutral with hot water wash, reduction vaporization under the condition of logical nitrogen once more, remove a spot of water, obtaining orange-yellow transparent liquid linolic acid and alpha-linolenic acid is main mixing unsaturated fatty acids.
The present invention prepares the saponification method that mixed fatty acid adopts, and cost is low, and equipment is simple, and is easy to operate, and the fatty acid component difference of fatty acid component of making and oil sample is little.The ratio of component of lipid acid concentrates on the unsaturated fatty acids in the oleum lini that the present invention selects, especially outstanding with alpha-linolenic acid, content surpasses 50%, so remove saturated fatty acid and oleic acid with a urea Bao Fake separation earlier, obtain the higher linolic acid and the mixture of alpha-linolenic acid, can under logical nitrogen condition, vacuum fractionation further obtain then than purified linolic acid and alpha-linolenic acid mixture.Linoleic acid content reaches 23.2%, and alpha-linolenic acid content reaches 72.8%, and total accumulation rate reaches more than 95%.Total yield reaches 60.4%, and by urea bag method repeatedly, the rate of recovery is higher.Each composition after the separation can fully utilize, as: but saponification byproduct glycerine purifying, the oleic acid component is hydrogenated into saturated fatty acid and can makes perfumed soap or do the raw material that other changes the shape product, and oleic acid is main also can be used for light industry and foodstuffs industry.Linolic acid and alpha-linolenic acid can be used clinically at medicine, and application on the shape product is being changed in lipopenicillinase etc., and skin care etc. are used in feed etc.
Embodiment 1
The 50g oleum lini is used in test, adds certain 25% NaOH liquid 40ml in beaker, is heated to 90 ℃, and H is used in the saponification 16 hours that heats while stirring then
2SO
4Liquid is acidified to acidity, and is extremely neutral with saturated NaCl liquid washing in separating funnel, isolates the upper strata oil reservoir, gets mixed fatty acid 42g, and measuring saponification value is 193.03, and iodine number is 167.
Table 1 GC analyzes mixed fatty acid
Outside testing oneself, surveys the title composition Palmiticacid (brown eleostearic acid) C
16: 07.83 6.3 stearic acid C
18: 05.45 0 oleic acid C
18: 125.31 25.2 linolic acid C
18: 215.24 16.0 linolenic acid C
18: 346.16 52.5
Get 40g urea and add 120ml chemical pure methyl alcohol in three mouthfuls of beakers, stirring heating is back to whole dissolvings, getting the 20g mixed fatty acid adds wherein, after the continuation stirring heating is back to uniform state, be transferred in the Erlenmeyer flask of band plug, under 28 ℃ of room temperatures, leave standstill a liquid, get the urea cage shape thing precipitation of lipid acid.Oil is filtered, and isolates filter cake and filtrate, pours in the beaker behind the dry cake as far as possible, adds hot water dissolving's filter cake, decomposes cage shape thing, is transferred in the separating funnel, isolates oil reservoir, with hot wash 2-3 time, gets the heavy 5.8g of pure cake, the rate of recovery about 29%.Cake is that saturated fatty acid adds oleic acid, and surveying iodine value is 101.Filtrate is transferred on the rotatory evaporator, and methyl alcohol is steamed in decompression, and temperature is controlled at 50 ℃, pressure is 10mmHg, till steaming several minutes and no longer including methyl alcohol and distillate, take out excess, with the excessive urea that contains in the HCl acid heat water decomposition filtrate, extremely neutral with hot water wash, under logical nitrogen condition, reduction vaporization removes a spot of water once more, get orange-yellow transparent liquid 7.3g, the rate of recovery 36.5%.
Table 2 GC analyzes cake and liquid
Title composition cake content % liquid hold-up %
The sour C of palm fibre
16: 011.5 0.208
Oleic acid C
18: 143.5 2.472
Linolic acid C
18: 212.7 20.174
Linolenic acid C
18: 332.3 77.137
Iodine number 132 219.6 accumulation rate of alpha-linolenic acid as can be seen from the table can reach more than 77%.
Embodiment 2
Get 100 gram oleum lini, the NaOH liquid 80ml of concentration 20%, saponification obtain fatty acid 89.0 grams, saponification temperature is 95 ℃, and saponification time is 16 hours, and all the other conditions are identical with embodiment 1.Recording saponification value is 193.03, and iodine number is 167.
GC analyzes mixed fatty acid composition and content such as table one.
Get urea 178 grams, the methyl alcohol that adds 534ml, obtain pure cake 35.8g with the method identical with embodiment 1, processing filtrate obtains alpha-linolenic acid and linoleic mixture is 40.0 grams, dwell temperature is 30 ℃, and the underpressure distillation methanol temperature is 60 ℃, and pressure is 10mmHg, present method alpha-linolenic acid accumulation rate can reach more than 75%, and the rate of recovery is 45%.
Embodiment 3
Get 200 gram oleum lini, add rare NaOH liquid 180ml in container, heating, saponification is 16 hours under 90 ℃ of temperature, and all the other conditions are identical with embodiment 1.Obtain mixed fatty acid 181.5 grams.Get urea 363 gram, methyl alcohol 108.9ml all joins the mixed fatty acid that obtains in the mixed solution of urea and methyl alcohol, adds the methyl alcohol of 534ml, uses the method identical with embodiment 1 to obtain pure cake 72.2 grams, handles the product 80.1 that filtrate obtains and restrains.Dwell temperature is 29 ℃, and the underpressure distillation methanol temperature is 55 ℃, and pressure is 10mmHg, and the alpha-linolenic acid rate of recovery is 44%, and accumulation rate reaches 75%.
Embodiment 4
Get the 15kg oleum lini, add rare NaOH liquid 15L in reactor, 90-100 ℃ of heating saponification, saponification time is 16 hours, all the other conditions are identical with embodiment 1.Obtain mixed fatty acid 13.5kg.Get urea 27kg, 81 liters of methyl alcohol, after the two mixes with it, mixed fatty acid is all added, use the method identical to obtain filter cake 4.5kg with embodiment 1, filtrate 6kg, dwell temperature is 28 ℃, and vacuum distillation temperature is controlled at 50-60 ℃, and pressure is 10mmHg, the alpha-linolenic acid rate of recovery is 44%, and accumulation rate reaches 75%.
Claims (1)
1. the separating and extracting method of an alpha-linolenic acid from oleum lini is characterized in that:
At first extract mixed fatty acid in the oleum lini with saponification method,
(1) the NaOH solution with 20-30% mixes with oleum lini, saponification,
Mixing quality is than being oleum lini: NaOH=1: 1-3
Saponification temperature is 90-100 ℃
Saponification time is 14-16 hour
(2) use rare H then
2SO
4Liquid acidifying saponification liquor is to acid
(3) in separating funnel with saturated NaCl liquid, be washed till neutrality and isolate the upper strata oil reservoir and obtain mixed fatty acid
Use urea adduct method separating saturated fatty acid and unsaturated fatty acids then
(4) get certain amount of urea, methanol mixed is heated to dissolving
Mixing quality is than being urea: methyl alcohol=1: 2-5
(5) get a certain amount of mixed fatty acid and add urea, in the methyl alcohol mixed liquor
The mixing quality ratio is lipid acid: urea: methyl alcohol=1: 2-5: 3-7
(6) in the container of band plug, leave standstill a liquid, get the urea cage shape thing precipitation of lipid acid, dwell temperature is 28-30 ℃,
(7) filter cake and filtrate are isolated in oil filter
(8) filtrate is moved on the rotatory evaporator underpressure distillation methyl alcohol
Temperature is controlled at 50-60 ℃, and pressure is 10mmHg
(9) with the excessive urea in the hot water decomposition filtrate that contains HCl,
(10) extremely neutral with hot water wash, reduction vaporization under the condition of logical nitrogen is removed a spot of water once more, obtains alpha-linolenic acid and linolic acid mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97101925A CN1053010C (en) | 1997-03-20 | 1997-03-20 | Separation extraction of alpha-linolenic acid from linseed oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97101925A CN1053010C (en) | 1997-03-20 | 1997-03-20 | Separation extraction of alpha-linolenic acid from linseed oil |
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| Publication Number | Publication Date |
|---|---|
| CN1162009A true CN1162009A (en) | 1997-10-15 |
| CN1053010C CN1053010C (en) | 2000-05-31 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97101925A Expired - Fee Related CN1053010C (en) | 1997-03-20 | 1997-03-20 | Separation extraction of alpha-linolenic acid from linseed oil |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095824C (en) * | 2000-04-13 | 2002-12-11 | 胡德甫 | Process for preparing high-purity alpha-linolenic acid |
| CN1098072C (en) * | 1998-05-12 | 2003-01-08 | 李文光 | Medicinal products of superfined alpha-linolenic acid, preparing process and preparation thereof |
| CN101845362A (en) * | 2010-06-22 | 2010-09-29 | 中南林业科技大学 | Method for gathering oleic acid from tea-seed oil |
| CN106010798A (en) * | 2016-06-13 | 2016-10-12 | 天津科技大学 | Method for extracting palmitoleic acid from sea buckthorn fruit oil |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5243046A (en) * | 1986-12-17 | 1993-09-07 | Nestec S.A. | Process for the continuous fractionation of a mixture of fatty acids |
-
1997
- 1997-03-20 CN CN97101925A patent/CN1053010C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1098072C (en) * | 1998-05-12 | 2003-01-08 | 李文光 | Medicinal products of superfined alpha-linolenic acid, preparing process and preparation thereof |
| CN1095824C (en) * | 2000-04-13 | 2002-12-11 | 胡德甫 | Process for preparing high-purity alpha-linolenic acid |
| CN101845362A (en) * | 2010-06-22 | 2010-09-29 | 中南林业科技大学 | Method for gathering oleic acid from tea-seed oil |
| CN101845362B (en) * | 2010-06-22 | 2012-07-25 | 中南林业科技大学 | Method for gathering oleic acid from tea-seed oil |
| CN106010798A (en) * | 2016-06-13 | 2016-10-12 | 天津科技大学 | Method for extracting palmitoleic acid from sea buckthorn fruit oil |
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| Publication number | Publication date |
|---|---|
| CN1053010C (en) | 2000-05-31 |
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