CN1266259C - Carbon dioxide supercritical extracting method of fatty acid separation and extraction from microporous grass seed - Google Patents
Carbon dioxide supercritical extracting method of fatty acid separation and extraction from microporous grass seed Download PDFInfo
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- CN1266259C CN1266259C CN 02137347 CN02137347A CN1266259C CN 1266259 C CN1266259 C CN 1266259C CN 02137347 CN02137347 CN 02137347 CN 02137347 A CN02137347 A CN 02137347A CN 1266259 C CN1266259 C CN 1266259C
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Abstract
The present invention provides a method for separating and extracting fatty acid from Microula sikkimensis (Clarke)hemsl. seeds by a supercritical carbon dioxide extraction method, which comprises the following steps: Microula sikkimensis (Clarke)hemsl. seeds are mixed with supercritical carbon dioxide under a certain condition, thereby dissolving the fatty acid of Microula sikkimensis (Clarke)hemsl. seeds in the carbon dioxide; the pressure of the carbon dioxide dissolved by the fatty acid is changed, so that the fatty acid is precipitated from the carbon dioxide, and precipitated fatty acid is obtained. Microula sikkimensis (Clarke)hemsl. seed fatty acid containing polyunsaturated fatty acid with a high content can be extracted effectively by using the present invention.
Description
Technical field
The present invention relates to chemical field, relate more specifically to the carbon dioxide supercritical extraction method of separation and Extraction lipid acid from microporous grass seed.
Background technology
Micropore grass (microula) is that Boraginaceae (Boraginaceoa) micropore grass belongs to (Microula Benth) 2 years these wild oilseed plants of sward, whole world micropore grass genus has 30 kinds and 8 mutation, in China distribution is arranged all, wherein 26 kinds is China endemic species, mainly is distributed in the meadow, mountain valley of Qinghai-Tibet Platean and the height above sea level 1900-3700 of neighboring region rice thereof.
The content of unsaturated fatty acids is near 90% in the microporous grass seed oil, the above polyene unsaturated fatty acid of trienic acid wherein, as gamma-linolenic acid, alpha-linolenic acid, 6,9,12,15, the content of-therapic acid etc. reaches more than 30%, the ω of the high level that it contained-3 polyene unsaturated fatty acid alpha-linolenic acid particularly, and 6,9,12,15 ,-therapic acids etc. are extremely rare in other plant oil.Polyene unsaturated fatty acids such as linolenic acid are essential fatty acids.They can not be changed during metabolism in vivo mutually, and have special physiological properties separately.
Though microporous grass seed oil has very big application and development value and potentiality, at present except common oil expression method, also there is not the technology of lipid acid in the separation and Extraction micropore grass effectively.The shortcoming of common oil expression method is that the unsaturated fatty acids that contains in the seed is easily oxidized, and dissolvent residual is arranged easily.
Therefore, this area presses for new, the technology of lipid acid in the separation and Extraction microporous grass seed effectively of exploitation.
Summary of the invention
Purpose of the present invention just provides the technology of lipid acid in a kind of microporous grass seed of separation and Extraction effectively.
The invention provides the method for a kind of carbon dioxide supercritical extraction method separation and Extraction lipid acid from microporous grass seed, comprise step:
(a) microporous grass seed is mixed with supercritical co, thereby make the lipid acid in the microporous grass seed be dissolved in carbonic acid gas, wherein, extraction temperature is 35-60 ℃, and extracting pressure is 20-40Mpa;
(b) change the described pressure that is dissolved with the carbon dioxide of lipid acid, lipid acid is separated out from described carbon dioxide, thus the lipid acid that obtains separating out, wherein separation temperature is 35-60 ℃, separating pressure is 1-5Mpa.
In a preference of the present invention, described extraction and separation temperature are 45-50 ℃.
In another preference, described extracting pressure is 25-30Mpa.
In another preference, described extracting pressure is 28-30Mpa.
In another preference, described lipid acid comprises saturated fatty acid and unsaturated fatty acids, and more preferably, described unsaturated fatty acids comprises polyene unsaturated fatty acid.
In another preference, the described extractive reaction time is 8-10 hour.
In another preference, carbon dioxide is recycled.
In another preference, total abstraction reaction time is 4-24 hour.
Description of drawings
Fig. 1 has shown the equipment of a kind of supercritical carbon dioxide extraction microporous grass seed oil that uses in example of the present invention.
Fig. 2 has shown under the different extracting pressure that lipid acid is at CO in the microporous grass seed
2In dissolution rate and the relation of temperature.
Fig. 3 has shown that microporous grass seed oil is at CO in the unit time
2In solubleness, product yield and extraction time relation (extracting pressure is 30Mpa, the extraction and separation temperature be 45 ℃, separating pressure is 2Mpa).
Fig. 4 has shown that microporous grass seed oil is at CO
2In solubleness, product yield and extraction time relation (extracting pressure is 30Mpa, the extraction and separation temperature be 45 ℃, separating pressure is 2Mpa).
Embodiment
The inventor has developed the novel process of utilizing carbon dioxide upercritical fluid extraction technology separation and Extraction lipid acid from microporous grass seed through extensive and deep research, has finished the present invention on this basis.
As used herein, term " polyene unsaturated fatty acid " refers to trienic acid or the above unsaturated fatty acids of trienic acid.
Supercritical extraction (SFE) technology is a kind of novel separation and extraction technology, has at low temperatures to extract, do not have dissolvent residual and advantage that can selective separation.Supercutical fluid (Supercritical Fluid SF) is to be in critical temperature (Tc) and more than the emergent pressure (Pc), the fluid between gas and liquid.This fluid has the dual nature of gas and liquid simultaneously: its density and liquid are close, and viscosity and gas are close, and its spreading coefficient is bigger approximately 100 times than liquid.Owing to comprise intermolecular interaction and diffusion in the dissolution process, thereby supercutical fluid has very strong dissolving power to many materials.
CO
2Supercritical extraction has the characteristics of selective dissolution.Under supercritical state, CO
2Dissolving power difference to different solutes is very big, and this polarity, boiling point, molecular weight and density with solute is relevant.Near stagnation point, obviously influence all takes place to physical propertiess such as the viscosity of supercutical fluid, density in the subtle change of temperature and pressure.Work as homo(io)thermism, change extracting pressure, will inevitably influence the dissolving power of supercutical fluid consumingly various compositions.From emergent pressure, intensified pressure progressively, because the supercutical fluid different in kind of each pressure gradient, thereby also different to the dissolving power of solute, be extracted out successively according to the polarity size that is extracted composition, boiling point height and the big I of molecular weight.For a certain composition in the extract, when extracting pressure reaches a certain threshold value, the pressure that raises again, its solubleness no longer increases.
The technology of carbon dioxide supercritical extraction method of the present invention separation and Extraction lipid acid from microporous grass seed may further comprise the steps:
(1) extraction step
In this step, microporous grass seed is mixed with supercritical co, thereby make the lipid acid in the microporous grass seed be dissolved in carbonic acid gas.
For this step, extraction temperature and extracting pressure are vital.Usually, extraction temperature is 35-60 ℃, preferably is 40-55 ℃, more preferably is 45-50 ℃.Extracting pressure is 20-40Mpa, preferably is 25-30Mpa, more preferably is 28-30Mpa.
(2) separating step
In this step, change the described pressure that is dissolved with the carbon dioxide of lipid acid, lipid acid is separated out from described carbon dioxide.The lipid acid of separating out taken out from separator can obtain fatty acid product.
For this step, separation temperature and separating pressure are vital.Usually, separation temperature corresponds to extraction temperature, is 35-60 ℃, preferably is 40-55, more preferably is 45-50 ℃.Separating pressure is 1-5Mpa, preferably is 1-4Mpa, more preferably is 1-3Mpa.
Whole extractive reaction (comprise extraction and the separate) time, be extracted substantially with lipid acid in the seed and get final product.Usually the extraction time is 4-24 hour or longer, preferably is 6-12 hour, more preferably is 8-10 hour.
In preference of the present invention, particularly preferred extraction process condition is: (1) extracts and separation temperature: 45-50 ℃; (2) extracting pressure: 28-30Mpa; (3) abstraction reaction time: 8-10 hour.
Of the present invention from microporous grass seed the technology of separation and Extraction lipid acid, can carry out continuously, also can carry out by intermittent type.
The present invention also provides and has been used for the equipment of carbon dioxide supercritical extraction method from microporous grass seed separation and Extraction lipid acid, and it comprises:
(a) extractor, described extractor have carbon dioxide inlet, microporous grass seed feed(raw material)inlet and carbonic acid gas outlet;
(b) carbon dioxide source, described carbon dioxide source links to each other with the carbon dioxide inlet of extractor, and the carbon dioxide of certain pressure is provided;
(c) reextraction jar, described reextraction jar has carbon dioxide inlet, microporous grass seed oil export and carbonic acid gas outlet, the carbon dioxide inlet of the described jar of stripping links to each other by pipeline with the carbonic acid gas outlet of extractor, and on described pipeline a valve is arranged.
A kind ofly be used for carbon dioxide supercritical extraction method as shown in Figure 1 from the particularly preferred equipment of microporous grass seed separation and Extraction lipid acid.It comprises following assembly: 1-CO
2Steel cylinder; 2-compressor and pressure control system; 3-1 is a stopping valve; 4-interchanger (assembly 1-4 constitutes carbon dioxide source); 5-extractor (being extractor); 6-1 and 6-2 are micrometering valve; 7-separator (jar of promptly stripping); The 8-spinner-type flowmeter; The 9-wet flow indicator.
Below in conjunction with Fig. 1, technological process of the present invention is described:
Be placed in the extractor 5 through the microporous grass seed of pulverizing.Close micrometering valve and stopping valve, open the thermostatic bath switch.When the temperature indication of thermostatic bath reaches preset value, open CO
2Steel cylinder, CO
2Enter compressor, open valve 3-1 simultaneously, CO
2Enter extractor.Open compressor, when the pressure for the treatment of extractor 5 reached predetermined extracting pressure value, open valve 6-1 slowly was dissolved with the CO of microporous grass seed oil
2Enter separator, because decompression makes oil from CO
2Separate out, make reach predetermined separating pressure in the separator 7 after, slowly open valve 6-2 makes CO
2By spinner-type flowmeter and wet flow indicator emptying (CO on the industrial production
2Can be recycled).Spinner-type flowmeter shows instantaneous delivery, and wet flow indicator shows CO
2Integrated flow.
In a preferable example, the pressure of extractor 5 maintains preset value all the time after reaching predetermined extracting pressure value, be dissolved with the CO of microporous grass seed oil simultaneously
2Enter separator 7, and the separating pressure in the separator 7 also maintains preset value all the time, thereby obtain running balance.Like this, be dissolved with the CO of microporous grass seed oil
2Just enter separator continuously, and in separator, separate out and separate.
Through certain reaction times, when not having product to separate out in the separator, extraction is finished.Close compressor and CO
2The steel cylinder valve, the CO of device to be separated
2When pressure is shown as zero, unload extractor, open the extractor lid and take out extracted residues, and take out the product in the separator.The new raw material of packing in extractor carries out the extraction of a new round.
The major advantage of technology of the present invention is:
(1) supercritical co has unique extraction effect to comprising the microporous grass seed grease.Because carbonic acid gas itself is nontoxic, and critical temperature is near normal temperature, so can make product exempt from the influence of unfavorable factors such as being heated.Therefore, the micropore grass effective constituent with supercritical carbon dioxide extraction has wide application prospect in the production of food and healthcare products etc.
(2) lipid acid that extracts in the micropore grass with the carbon dioxide upercritical fluid extraction technology can prevent effectively that polyene unsaturated fatty acid wherein is oxidized, therefore polyene unsaturated fatty acid content height in the microula oil that extracts.With technology of the present invention can separation and Extraction contain polyene unsaturated fatty acid (unsaturated fatty acids that trienic acid is above comprises trienic acid) up to the microporous grass seed oil more than 30%.
(3) extraction efficiency height, product yield are about 26%.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.
Embodiment 1
Under the different extracting pressure in the microporous grass seed lipid acid at CO
2In dissolution rate and the relation of temperature
Adopt device shown in Figure 1.Be raw material with the microporous grass seeds of 120 grams respectively, under 45 ℃ and 50 ℃ (extracting and separation temperatures) and different extracting pressure, extract through pulverizing.Lipid acid is at CO in the microporous grass seed under the mensuration different condition
2In solubleness (g/cm
3CO
2).Wherein, total abstraction reaction time is 10 hours.
The result as shown in Figure 2.Fig. 2 has provided the relation of extraction temperature, pressure and product (microporous grass seed lipid acid) solubleness, and by experimental result as can be seen: microporous grass seed oil is at CO
2In solubleness increase along with the increase of pressure, when pressure is increased to 28Mpa when above, the ascendant trend of solubility curve is slack-off.Temperature is less relatively to the influence of solubleness.
Unit time, (extraction and separating reaction time are 1 hour) interior microporous grass seed oil was at CO
2In the relation of solubleness, product yield and extraction time
Adopt device shown in Figure 1.Being raw material with the microporous grass seeds of 120 grams through pulverizing respectively, is 30Mpa in extracting pressure, and extraction and separation temperature are 45 ℃, and separating pressure is to extract under the condition of 2Mpa.Lipid acid is at CO in the microporous grass seed under the mensuration different condition
2In the solubleness (g/cm of unit time
3CO
2) and the product yield (%) of unit time, and total solubleness (g/cm
3CO
2) and product yield (%).
The result as shown in Figure 3 and Figure 4.Fig. 3 is the relation of solute solubility and product yield in the different unit time of extraction process, as seen, after extracting through 8 hours, and though the unit time interior be that product yield or microporous grass seed oil are at CO
2In dissolution rate all decline to a great extent.
Fig. 4 has shown the relation of interior solute solubility of different time of extraction process and product yield.Through 8 hours extraction, CO
2The concentration of middle oil reduces, and during by 10 hours, product oil extracts fully substantially in the raw material, and yield is about 26%.
Embodiment 3
Composition measurement in the microporous grass seed oil that carbon dioxide supercritical extraction method is extracted
To the microporous grass seed lipid acid that obtains among the embodiment 2, according to GB/T17376-1998 " preparation of animal-plant oil fatty acid methyl ester " (National Quality ﹠ Technology Inspection Bureau's issue on May 8th, 1998, China Standard Press publishes) and GB/T17377-1998 " gas chromatographic analysis of animal-plant oil fatty acid methyl ester " (National Quality ﹠ Technology Inspection Bureau's issue on May 8th, 1998, China Standard Press's publication) method described in is carried out composition measurement, and the result is as shown in the table:
| Composition | Content (%) | Composition | Content (%) |
| C14：0 | 0.1 | γ-C18：3 | 9.1 |
| C16：0 | 7.3 | α-C18：3 | 15.0 |
| C16：1 | 0.2 | C18：4 | 4.8 |
| C18：0 | 2.1 | C20：4 | 7.6 |
| C18：1 | 32.0 | C22：4 | 1.9 |
| C18：2 | 19.9 |
Therefore, in the microula oil that extracts with method of the present invention the content of polyene unsaturated fatty acid greater than 30% (9.1+15.0+4.8+7.6+1.9=38.4%).
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (9)
1. the method for carbon dioxide supercritical extraction method separation and Extraction lipid acid from microporous grass seed is characterized in that, comprises step:
(a) microporous grass seed is mixed with supercritical co, thereby make the lipid acid in the microporous grass seed be dissolved in carbonic acid gas, wherein, extraction temperature is 35-60 ℃, and extracting pressure is 20-40Mpa;
(b) change the described pressure that is dissolved with the carbon dioxide of lipid acid, lipid acid is separated out from described carbon dioxide, thereby the lipid acid that obtains separating out, wherein separation temperature is 35-60 ℃, separating pressure is 1-5Mpa, and described lipid acid is selected from therapic acid, eicosatetraenoic acid, docosatetratenoic acid.
2. the method for claim 1 is characterized in that, described extraction and separation temperature are 45-50 ℃.
3. the method for claim 1 is characterized in that, described extracting pressure is 25-30Mpa.
4. the method for claim 1 is characterized in that, described extracting pressure is 28-30Mpa.
5. the method for claim 1 is characterized in that, described lipid acid comprises eicosatetraenoic acid.
6. method as claimed in claim 5 is characterized in that described unsaturated fatty acids comprises therapic acid.
7. the method for claim 1 is characterized in that, the described extractive reaction time is 8-10 hour.
8. the method for claim 1 is characterized in that, carbon dioxide is recycled.
9. the method for claim 1 is characterized in that, total abstraction reaction time is 4-24 hour.
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| CN 02137347 CN1266259C (en) | 2002-10-09 | 2002-10-09 | Carbon dioxide supercritical extracting method of fatty acid separation and extraction from microporous grass seed |
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| CN1266259C true CN1266259C (en) | 2006-07-26 |
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| CN101273689B (en) * | 2007-03-31 | 2010-12-22 | 中国科学院西北高原生物研究所 | Method of Microula sikkimensis (Clarke) Hemsl. bionic cultivation |
| CN110122216A (en) * | 2019-05-07 | 2019-08-16 | 山东省农业科学院玉米研究所 | A kind of corn and oat strip cropping implantation methods |
| IL266991B (en) * | 2019-05-29 | 2020-09-30 | Avomed Ltd | Method of extracting polyhydroxylated fatty alcohols using supercritical co2 |
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Owner name: SHANGHAI INST. OF LIFE SCIENCE, CAS Free format text: FORMER NAME OR ADDRESS: SHANGHAI INST. OF PLANT PHYSIOLOGY, CHINESE ACADEMY OF SCIENCES |
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