CN1235956A - Method for extracting and separating alpha-linolenic acid - Google Patents
Method for extracting and separating alpha-linolenic acid Download PDFInfo
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- CN1235956A CN1235956A CN 99106089 CN99106089A CN1235956A CN 1235956 A CN1235956 A CN 1235956A CN 99106089 CN99106089 CN 99106089 CN 99106089 A CN99106089 A CN 99106089A CN 1235956 A CN1235956 A CN 1235956A
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Abstract
Through the processes of adding separation promoter and anti-oxidant into seeds, extracting fat in inert atmosphere, hydrolysis to produce free fatty acid; separation for three times by adding surfactant, separation promoter and anti-oxidant and to obtain high-concentration alpha-linolenic acid in nitrogen atmosphere; complete esterification by adding anti-oxidant into the high-concentration alpha-linolenic acid in nitrogen atmosphere; complete esterification by adding anti-oxidant into the high-concentration alpha-linolenic acid in nitrogen atmosphere to obtain alpha-linolenic acid product. The said method may be used in large-scale industrial production.
Description
The present invention relates to the material method of purification, the method for particularly a kind of extraction, separating alpha-linolenic acid.
Alpha-linolenic acid [LNA, chemical name: along the suitable 15-punicic acid of the suitable 12-of 9-)] be a kind of essential fatty acid [EFA], be the parent of n-3 system (being once called as ω 3) polyene unsaturated fatty acid [PUFA], it be a kind ofly have specific function, with human existence, multiply, grow, the very close essential nutrients of relation such as anti-disease, anti-aging.But human body is the function of synthetic LNA not, must absorb from food, could obtain by digesting and assimilating.The EFA past attempts is named as vitamin F.
The present invention's purpose is to obtain high-load alpha-linolenic acid, and makes it protected and avoid or alleviate oxidized and failure loss in the extraction separation process all the time.
The method of extraction of the present invention, separating alpha-linolenic acid comprises:
(1) the preceding course of processing: after in seed, adding separation promoter KFH and antioxidant KH1, in inert gas atmosphere, extract fat, as stock oil; In described stock oil, add antioxidant KH2 purifying and get the pure oil that hydrolysis is used; In pure oil, add separation promoter KFJ and antioxidant KH3 again, in nitrogen atmosphere, be hydrolyzed, water is fully reacted with oil, generate free fatty acids.
(2) extraction separation process: in free fatty acids, add separation promoter KFS and antioxidant KH4, in nitrogen atmosphere, at R
1Carry out the first time in the-OH solution and separate, the liquid acid of polyenoic acid that obtained enrichment; In liquid acid, add tensio-active agent KPH, antioxidant KH5 and in nitrogen atmosphere, still in solution, carry out the separation second time, obtain the polyenoic acid of high density; In this polyenoic acid, add tensio-active agent KPH, antioxidant KH5 and separation promoter KFN then and in nitrogen atmosphere and vacuum, at R
2Separate for the third time in the-OH solution, obtain the alpha-linolenic acid of high density.
(3) post-treatment process: add antioxidant KH6 and carry out complete esterification in the alpha-linolenic acid of high density in nitrogen atmosphere, the ester of generation carries out purifying and promptly gets product after adding antioxidant KH7.
Wherein, described seed can be purchase or plantation; Described inert gas can be nitrogen and/or carbonic acid gas; The by product of described hydrolysis reaction is a glycerine, and percent hydrolysis requires more than 99%.
All by-product oleic acid generations are the mixed fatty acids that contains more saturated acid and monoenoic acid in described each separation; In separating for the second time and for the third time, use tensio-active agent and separation promoter, and under certain pressure and temperature state, " the floating method isolation technique that goes up " with chemical process, make the monoenoic acid and the diolefinic acid of a small amount of existence in solution separate out and remove with " on floating " state, solvent also is recovered in the process; In the so-called oleic acid of come-up owing to be mixed with relatively large trienic acid and return preceding operation and separate again.
The purge process of described post-treatment can remove water, alcohol, residual low-carbon ester, pigment, smell impurity such as flavor, inorganics, qualified after testing after, be product.
The method of extraction of the present invention, separating alpha-linolenic acid can also comprise after adding the KHT of 0.7 ‰ KHE and 0.2 ‰ in the products obtained therefrom, be packaged into supply of commodities market.
The not carboxylate of denier and the water of generation in the described esterification process are discharged from and carry out three wastes processing.
The described first time, isolating working conditions was 0mpa, room temperature～78 ℃, solvent: solute is 1: 0.5～1, the time is 4 hours; The described sepn process second time divides three grades: at 0～0.2mpa, 10～78 ℃, solvent: solute is that 1: 1, disengaging time are 2 hours, at 0.2～0.4mpa, 0～10 ℃, solvent: solute is 1: 1～2, disengaging time is 1 hour, in 0.4～0.6mpa, 0～-10 ℃, solvent: solute is 1: 2, and disengaging time is 4 hours; Described isolating for the third time working process branch Pyatyi: in 0～0.2mpa, 0～-10 ℃, solvent: solute is that 1: 1, disengaging time are 1 hour, at 0.2～0.4mpa ,-10～-20 ℃, solvent: solute is 1: 1～2, disengaging time is 1 hour, at 0.4～0.6mpa ,-20～-30 ℃, solvent: solute is 1: 2～5, disengaging time is 2 hours, at 0.6～0mpa ,-30 ℃, solvent: solute is that 1: 5, disengaging time are 1 hour, 0～-0.1mpa ,-30 ℃, solvent: solute is that 1: 5, disengaging time are 2 hours.
The solvent R of described solution
1-OH and R
2-OH is ethanol or methyl alcohol; Its concentration (V/V) is: 35～65 °; 60～90 °; 85～100 °; 94～109 °.Solute is grease, lipid acid and ethyl ester in each technological process of producing or methyl esters, glyceride.
Described tensio-active agent KPH is the KPH aniorfic surfactant that new chemical institute of Zhengzhou market day is produced, and mainly is by R (OCH
2CH
2) nOH, behind oversulfonate, epoxidation and make, in the formula, R is C
12-C
18Hydrocarbon chain, can be not double bond containing alkane, also can be the alkene that contains one or several pair key; N is a 10-18 oxyethylene group polymer.Its raw material and only through oversulfonate or only through epoxidation and tensio-active agent KPH all can in the method for extraction of the present invention, separating alpha-linolenic acid, play activation.
Described antioxidant also is that new chemical institute of Zhengzhou market day is produced from KH1 to KH7, is seven kinds of different prescriptions, and its component and use see the following form.
| Component KH1 KH2 KH3 KH4 KH5 KH6 KH7 KHE KHT material |
| VC-E (ester) 50 20 50 20 20 50 20 100 |
| VE??????????20??????????????????10??700 |
| β-Hu Su 20 20 20 |
| Citric acid 50 10 50 150 |
| Phosphatidase 12 0 10 20 20 20 500 |
| TBHQ???????20??5??5?????????????20??50??????200 |
| Contain B acid 100 200 300 |
| Contain P acid 500 500 500 |
| Cot extract 500 200 200 200 |
| Cot (fragment) 1M |
Antioxidant KHE is to be main prescription with vitamin-E, adds 0.7 ‰ (7/10000ths) of product total content; KHT is that the TBHQ that produces with U.S. Yi Shi Man is the compound antioxidant of main prescription, adds 0.2 ‰ (2/10000ths) of product total content.
Described separation promoter KFH, KFJ, KFS, KFN are four kinds of different prescriptions, also are that new chemical institute of Zhengzhou market day is produced, and concrete component is as follows:
KFH-ROH(300),[COH](1000)
n,HAc(100)。
KFJ-ROH(300),M-OH(100),M-BP(100)。
KFS-ROH(300),M-OH(100),(NH
2)
2-CO(1000)。
KFN-ROH(300),M-OH(100),PO-SA(100)。
The product of the method for extraction of the present invention, separating alpha-linolenic acid is light golden rod yellow, the oily liquids of the good fluidity of fragrant slightly.
The method of extraction of the present invention, separating alpha-linolenic acid is under the effect of specific antioxidant, tensio-active agent, separation promoter; alpha-linolenic acid is protected, on a kind of boundary in the industrial process of the effective ingredient molecularization separation and extraction technology of meticulous oil chemistry and traditional Chinese medical science medicine.It is included under certain pressure and temperature condition, in certain density solution, after adding tensio-active agent, antioxidant, separation promoter, make alpha-linolenic acid protected and progressively be extracted, separate, all take anti-oxidation tech in this process from start to finish, mainly solved two problems: overcome penta carbon diene type polyunsaturated fatty acid along with concentration improves and more serious oxidized breakoff phenomenon; Overcome with being separated from each other difficult situation because of what close physical and chemical index, molecular chain length, chemical structure, especially powerful molecular association power and consistency extremely formed between the multiple class acid of carbon.Its concrete characteristics are:
1, good quality of product: principal constituent alpha-linolenic acid content height reaches 70%-90%; Other remaining component is other lipid acid of linolic acid and a small amount of oleic acid and trace, does not have not principal component, does not contain harmful impurity component; Sanitary index is qualified, can be used as the raw material of foodstuff additive, healthcare products and medicine; Mouthfeel and good colour; Long preservative period.
2, extract in plant, separate and get, raw material sources are extensive.
3, technology is simple, and production cost is low, can realize large-scale industrial production.
The alpha-linolenic acid content height that the present invention produces is 70-91.2%, and the test preservation period reached more than 2 years.
Further describe the present invention below in conjunction with embodiment
Embodiment
The method of a kind of extraction, separating alpha-linolenic acid, it comprises
1, the preceding course of processing:
Plantation or purchase contain the seed of fat of a certain amount of alpha-linolenic acid, evenly add separation promoter KFH and antioxidant KH1 after, at nitrogen (N
2) in the atmosphere, extruding leaches vegetables oil, heavyly is called " crude oil " after clear, is the stock oil of this technology; Store temporarily after in stock oil, adding KH2, added ingredients pasture capable of using as feed of the seed dregs of rice and poultry, crude oil is pure oil after removing impurity; Pure oil and water reaction hydrolysis are at N
2In, after adding KFJ and KH3, hydrolysis is abundant, generates free fatty acids.
Hydrolytic accelerating agent reaches more than 99% percent hydrolysis, and byproduct glycerine can be processed into industrial chemicals outward.
2, extraction separation process:
Free fatty acids is at N
2In, after adding KFS and KH4, dissolve in the ethanol with 1: 0.5, and be heated to 78 ℃, stirring and dissolving, cooling returns to normal temperature and strength of solution is increased by 1: 1 then, carries out the first time and separates, and leaves standstill 4 hours, saturated acid is separated out, with the part monoenoic acid, make byproduct for treatment, partial solvent carries out secondary separation after reclaiming.
Removed the mixed fatty acid behind most of saturated acid and the part monoenoic acid, after adding KH5 still at N
2In, change SOLUTION PROPERTIES with tensio-active agent KPH, in 1: 1 solution, after the heated and stirred dissolving, cooling solution cools to 10 ℃, and pressure is added to 0.2mpa, leaves standstill 2h, and part monoenoic acid and a small amount of diolefinic acid are separated out; Make pressure be added to 0.4mpa, temperature drops to 0 ℃, and strength of solution increases gradually by 1: 2, and a large amount of monoenoic acids and diolefinic acid are separated out; Make pressure be added to 0.6mpa again, temperature drops to-10 ℃, keeps 4h, and monoenoic acid and diolefinic acid are further separated out; The mixture of the acid that all are separated out is made byproduct for treatment; Adopt " the floating method that goes up " technology then, keep temperature-10 ℃, control pressure, diolefinic acid crystallite remaining in the solution is the come-up state and leaves solution under Action of Surfactant.Owing to be mixed with many trienic acids (alpha-linolenic acid) in this part, therefore return the flash liberation process and deal with.Removed the lipid acid of saturated acid, monoenoic acid and most of diolefinic acid, wherein the concentration of alpha-linolenic acid is higher, after solvent recuperation finishes, carries out three times and separates.
After adding KPH and KH5, still at N
2In the atmosphere, cooperate KPH that lipid acid is further separated with separation promoter KFN, solvent is a methyl alcohol, solution with 1: 1 concentration after stirring, pressure step by step from 0mpa to 0.2mpa, 0.4mpa and 0.6mpa; Temperature drops to-10 ℃ ,-20 ℃ and-30 ℃ from 0 ℃ step by step; It is 1: 1 that strength of solution changes rank, 1: 2 and 1: 5; Periods at different levels are 1h, and 1h and 2h make in the solution remaining a small amount of monoenoic acid and most of diolefinic acid separate out, and this mixed fatty acid is also made byproduct for treatment.And then adopt the floating law technology of going up, the diolefinic acid come-up state of residue trace is left; Afterwards, further come-up is isolated remaining diolefinic acid when decompression, further floats under vacuum condition at last, reclaims alcoholic solvent, and supernatant returns last time repeated isolation.Obtain the higher alpha-linolenic acid of content like this.
3, post-treatment is handled:
This is the esterification of a lipid acid and the process of purifying.Alpha-linolenic acid is at N
2In, carry out esterification with ethanol behind the interpolation KH6.At any time from system, tell the water that reaction generates, also take various impurity soluble in water simultaneously out of.The waste water of these discharges carries out the three wastes to be handled.Carry out purifying add KH7 in resultant of reaction Alpha-ethyl linolenate [LNA-E] after, make wherein water, alcohol, residual low-carbon ester, pigment, smell impurity removals such as flavor and inorganics, pure product are product through being up to the standards.After adding antioxidant KHE 0.7 ‰ and KHT 0.2 ‰ again, be packaged into supply of commodities market.
Product is with KOH-CH
3OH and BF
3-CH
3Detect with vapor-phase chromatography after the OH pre-treatment, the result reaches more than 90% for alpha-linolenic acid content.
Claims (9)
1, the method for a kind of extraction, separating alpha-linolenic acid is characterized in that may further comprise the steps:
(1) the preceding course of processing: after in seed, adding separation promoter KFH and antioxidant KH1, in inert gas atmosphere, extract fat, as stock oil; In described stock oil, add antioxidant KH2 purifying and get the pure oil that hydrolysis is used; In pure oil, add separation promoter KFJ and antioxidant KH3 again, in nitrogen atmosphere, be hydrolyzed, water is fully reacted with oil, generate free fatty acids;
(2) extraction separation process: in free fatty acids, add separation promoter KFS and antioxidant KH4, in nitrogen atmosphere, at R
1Carry out the first time in the-OH solution and separate, the liquid acid of polyenoic acid that obtained enrichment; In liquid acid, add tensio-active agent KPH, antioxidant KH5 and in nitrogen atmosphere, still in solution, carry out the separation second time, obtain the polyenoic acid of high density; In this polyenoic acid, add tensio-active agent KPH, antioxidant KH5 and separation promoter KFN then and in nitrogen atmosphere and vacuum, at R
2Separate for the third time in the-OH solution, obtain the alpha-linolenic acid of high density;
(3) post-treatment process: add antioxidant KH6 and carry out complete esterification in the alpha-linolenic acid of high density in nitrogen atmosphere, the ester of generation carries out purifying and promptly gets product after adding antioxidant KH7.
2, the method for claim 1 is characterized in that described seed is purchase or plants; Described inert gas is nitrogen and/or carbonic acid gas; The by product of described hydrolysis reaction is a glycerine, and percent hydrolysis requires more than 99%.
3, the method for claim 1 is characterized in that all by-product oleic acid generations in described each separation, is the mixed fatty acid that contains more saturated acid and monoenoic acid; In separating for the second time and for the third time, use tensio-active agent and separation promoter, and under certain pressure and temperature state, " the floating method isolation technique that goes up " with chemical process, make the monoenoic acid and the diolefinic acid of a small amount of existence in solution separate out and remove with " on floating " state, solvent also is recovered in the process; In the so-called oleic acid of come-up owing to be mixed with relatively large trienic acid and return preceding operation and separate again.
4, the method for claim 1 is characterized in that comprising with after adding the KHT of 0.7 ‰ KHE and 0.2 ‰ in the products obtained therefrom, is packaged into supply of commodities market.
5, the method for claim 1 is characterized in that the described first time, isolating working conditions was 0mpa, room temperature～78 ℃, solvent: solute is 1: 0.5～1, the time is 4 hours; The described sepn process second time divides three grades: at 0～0.2mpa, 10～78 ℃, solvent: solute is that 1: 1, disengaging time are 2 hours, at 0.2～0.4mpa, 0～10 ℃, solvent: solute is that 1: 1 ￣ 2, disengaging time are 1 hour, at 0.4 ￣ 0.6mpa, 0 ￣-10 ℃, solvent: solute is 1: 2, and disengaging time is 4 hours; Described isolating for the third time working process branch Pyatyi: in 0～0.2mpa, 0～-10 ℃, solvent: solute is that 1: 1, disengaging time are 1 hour, at 0.2～0.4mpa ,-10～-20 ℃, solvent: solute is 1: 1～2, disengaging time is 1 hour, at 0.4～0.6mpa ,-20～-30 ℃, solvent: solute is 1: 2～5, disengaging time is 2 hours, at 0.6～0mpa ,-30 ℃, solvent: solute is that 1: 5, disengaging time are 1 hour, 0～-0.1mpa ,-30 ℃, solvent: solute is that 1: 5, disengaging time are 2 hours.
6, the method for claim 1 is characterized in that the solvent R of described solution
1-OH and R
2-OH is ethanol or methyl alcohol; Its concentration (V/V) is: 35～65 °; 60～90 °; 85～100 °; 94～109 °.
7, the method for claim 1 is characterized in that described tensio-active agent KPH is the KPH aniorfic surfactant that new chemical institute of Zhengzhou market day is produced.
8, the method for claim 1 is characterized in that described antioxidant is that new chemical institute of Zhengzhou market day is produced from KH1, KH2, KH3, KH4, KH5, KH6, KH7.
9, the method for claim 1 is characterized in that described separation promoter KFH, KFJ, KFS, KFN are that new chemical institute of Zhengzhou market day is produced.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99106089 CN1235956A (en) | 1999-05-04 | 1999-05-04 | Method for extracting and separating alpha-linolenic acid |
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|---|---|---|---|
| CN 99106089 CN1235956A (en) | 1999-05-04 | 1999-05-04 | Method for extracting and separating alpha-linolenic acid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348568C (en) * | 2005-10-18 | 2007-11-14 | 中国人民解放军第四军医大学药物研究所 | Process for extracting high purity alpha-linolenic acid from pepper category and medicine application thereof |
| CN101646644A (en) * | 2007-07-30 | 2010-02-10 | Hrd有限公司 | Produce the system and the processing method of lipid acid and wax alternatives from triglyceride level |
| CN101643402B (en) * | 2008-08-10 | 2013-03-27 | 赵荣林 | Method for preventing oxidation rancidity and color recovery of oleic acid |
-
1999
- 1999-05-04 CN CN 99106089 patent/CN1235956A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348568C (en) * | 2005-10-18 | 2007-11-14 | 中国人民解放军第四军医大学药物研究所 | Process for extracting high purity alpha-linolenic acid from pepper category and medicine application thereof |
| CN101646644A (en) * | 2007-07-30 | 2010-02-10 | Hrd有限公司 | Produce the system and the processing method of lipid acid and wax alternatives from triglyceride level |
| US8491856B2 (en) | 2007-07-30 | 2013-07-23 | H R D Corporation | System and process for production of fatty acids and wax alternatives from triglycerides |
| CN101643402B (en) * | 2008-08-10 | 2013-03-27 | 赵荣林 | Method for preventing oxidation rancidity and color recovery of oleic acid |
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