CN101290277B - Rapid extraction method utilizing microwave radiation - Google Patents

Rapid extraction method utilizing microwave radiation Download PDF

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CN101290277B
CN101290277B CN2007100981892A CN200710098189A CN101290277B CN 101290277 B CN101290277 B CN 101290277B CN 2007100981892 A CN2007100981892 A CN 2007100981892A CN 200710098189 A CN200710098189 A CN 200710098189A CN 101290277 B CN101290277 B CN 101290277B
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extraction
raw material
solvent
microwave radiation
water
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CN101290277A (en
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林福文
陈昭平
黄荣丞
杨炳辉
蔡维钟
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FOODSTUFF INDUSTRIAL DEVELOPMENT INST OF FINANCIAL GROUP LEGAL PERSONS
Food Industry Research and Development Institute
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Priority to JP2007207428A priority patent/JP5398967B2/en
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Abstract

The invention provides a quick extraction method, wherein, raw materials are extracted through microwave radiation treatment before the process of solvent extraction, so as to accelerate the extraction speed.

Description

Utilize the rapid extracting method of microwave radiation
Technical field
The present invention relates to a kind of microwave treatment of utilizing to shorten extraction time even to promote extracted amount and reduce the method for extracting the solvent use amount.
Background technology
In today of great attention speed and efficient, efficient, convenient extraction method has become the important research direction.The extracting method that extensively utilizes comprises methods such as soxhlet extraction, ultrasonic extraction, super critical extraction at present.These extracting method all have the place that they are good on different extraction raw materials and sample.Yet soxhlet extraction and ultrasonic extraction all need to use a large amount of solvents and expend the long period; Though time and solvent that super critical extraction is required are less, its equipment is complicated, and running cost is higher, thereby its application also is restricted.
The Microwave Extraction method applies to the extraction of metallic element in trace element or the environmental contaminants in early days.Yang Su really waits people's (emerging large-engineering academic periodical, the 14th volume, the 1st phase, the 39-40 page or leaf, 2003), people (Jilin University's journal, the 42nd volume such as Wang Minjing, the 2nd phase, 278-282 page or leaf (2004)) and people (Organic Geochemistry, 34,1517-1523 (2003)) such as K.Oksana microwave technology is applied to the extraction of food.US2004/0187340, US7,001,629 and people (Journal of Chromatography A such as Vongsangnak, 1054 (2004) 95-111) apparatus and method that disclosed all merely replace thermal source in traditional leaching process with microwave, because the thermal loss that heat conduction (being heat radiation) is caused, and then promote the efficiency of heating surface to improve in the general heating process.Yet that above-mentioned technology all can't solve is consuming time in the traditional extraction process, complicated operation and need to use shortcoming such as a large amount of solvents.Thereby, still need provide more efficient method at present at the shortcoming in the traditional extraction process.The present invention finds to use microwave treatment thing to be extracted earlier before extraction, can significantly shorten extraction time, even can promote extracted amount, and can reduce the use amount of extracting solvent.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing Microwave Pretreatment to shorten extraction time.Method of the present invention can and then promote extracted amount, even reduces and extract the solvent use amount.
Because microwave has through characteristic, thereby can directly provide heat energy to article inside, and composition wherein is activated because of absorbing energy, and then accelerates extraction rate.Method of the present invention is compared with traditional extracting method, because extraction rate is higher, but thereby within a short period of time and the desirable extract of the following acquisition of less extraction solvent.Cooperate heating if desired, owing to extract the minimizing of solvent volume, can accelerate the rate of heat addition so and shorten heat time heating time again, preventing from long heat time heating time to cause the oxidation or the degraded of compound, thereby can further promote extraction effect.
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Embodiment
The invention provides a kind of method of utilizing Microwave Pretreatment to shorten extraction time and promoting extraction rate, it is characterized in that before will extracting raw material and the extraction solvent contacts, handling the extraction raw material with microwave radiation earlier.
" extraction raw material " among the present invention refers to the raw material that is used to extract, it comprises non-biological material and the biological material that drying is handled or undried is handled, wherein non-biological material includes, but is not limited to mineral (as ore), soil or synthetic material (as high molecular polymer and plastic products etc.), and it is preferably mineral or soil; And biological material includes, but is not limited to animal specimen, plant sample or microorganism are (as bacterium, Mushrooms, fungi and actinomyces) culture, it is preferably plant sample, described plant sample can be and anyly can obtain therefrom to wish that composition is (as active constituents of medicine, spices, edible oil, vitamin and amino acid etc.) plant sample, for example Chinese medicinal herbs is (as Asiatic plantain, lotus leaf, the fruit of Chinese magnoliavine, glossy ganoderma, rhodiola root, four things and mixing medicinal material etc.), fruit, flower is (as rose, lavender, tea tree, Roselle, pot marigold and chamomile etc.), rice bran and seed are (as soya bean (claiming soybean again), peanut, sesame, rapeseed, coconut and palm, sunflower seed, corn, milk thistle and rice etc.).
" microwave " used in the present invention refers to the electromagnetic wave of spectral range between radiowave and infrared ray, and its frequency range is preferably 915MHz and 2450MHz for about 300MHz arrives between about 300GHz.
" radiation " in the inventive method refers to and is exposed in the environment that contains microwave extracting raw material, and wherein the power of microwave radiation and time can be done suitably to adjust according to the kind of the kind of extracting raw material and weight and desirable extraction composition.The microwave irradiation power that is applicable to the inventive method is preferably about 1 to about 100 watts/gram and extracts raw material, and more preferably about 1 to about 20 watts/gram extracts raw material, most preferably is about 5 to about 10 watts/gram and extracts raw material; Microwave irradiation time is preferably about 1 to about 60 minutes, more preferably about 1 to about 30 minutes, most preferably is about 1 to about 1.5 minutes.
" extraction solvent " in the inventive method comprises the various organic and inorganic liquids that extract of conventionally being used to.Described extraction solvent species can be done suitably to adjust according to the kind of the kind of extracting raw material and desirable extraction composition.The preferred extraction solvent that is applicable to the inventive method is water, methyl alcohol, ethanol, ethyl acetate, normal hexane, acetone, tetrahydrofuran (tetrahydrofuran) or its potpourri, more preferably water, methyl alcohol, ethanol, normal hexane, acetone or its potpourri most preferably are water, ethanol or normal hexane.Extracting the weight ratio of raw material and described extraction solvent can do suitably to adjust according to the kind of the kind of extracting raw material and desirable extraction composition, and the preferred weight ratio (extracting raw material: extract solvent) that is applicable to the inventive method arrives about 1:10 for about 1:0.5, more preferably about 1:4 most preferably is about 1:8 to about 1:10 to about 1:10.
In the method for the invention, extracting raw material can contact with wetting solvent earlier according to circumstances, uses microwave radiation processing again.Described wetting solvent can be any organic or inorganic liquid of extracting of conventionally being used to.Described wetting solvent species can be done suitably to adjust according to the kind of the kind of extracting raw material and desirable extraction composition.The preferred moistening solvent that is applicable to the inventive method is water, methyl alcohol, ethanol, ethyl acetate, normal hexane, nitric acid or its potpourri, and more preferably water, methyl alcohol, ethanol, normal hexane or nitric acid most preferably are water.Described wetting solvent can be identical or inequality with described extraction solvent.Extracting the weight ratio of raw material and described wetting solvent can do suitably to adjust according to the kind of the kind of extracting raw material and desirable extraction composition, and the preferred weight ratio that is applicable to the inventive method (extracts raw material: wetting solvent) arrive about 1:5 for about 1:0.2, its more preferably about 1:0.5 most preferably is about 1:1 to about 1:3 to about 1:4.
Extraction raw material in the extracting method of the present invention with extract solvent and contact after, can optionally combine with further lifting extraction ratio with various conventional extracting method, wherein said conventional extracting method includes, but is not limited to stir and extracts, heats extraction, soxhlet extraction, Extraction by Ultrasound, super critical extraction, enzyme extraction method, semi-bionic extraction or its combination.
The following example is used for the present invention is further illustrated, but is not in order to restriction the present invention, the teaching of any persond having ordinary knowledge in the technical field of the present invention instructions according to the present invention and the modification of reaching and use and all belong to scope of the present invention.
Experimental technique:
1. Microwave Pretreatment method: after the extraction raw material pulverizing with drying or undried, add wetting solvent according to circumstances, carry out microwave radiation with different power and time, after adding extraction solvent carries out the stirring (heat/not heating) of blink again, to extract solvent and filter also concentrate drying, to obtain dry extract.
2. stirring extraction method: after the extraction raw material pulverizing with drying or undried, add 10 times to the extraction solvent that extracts raw material (w/w), after a period of time, solvent filters and concentrate drying to extracting, to obtain dry extract in reflux.
3. ultrasonic extraction: after the extraction raw material pulverizing with drying or undried, add 10 times to the extraction solvent that extracts raw material (w/w), again with after Extraction by Ultrasound device concussion a period of time (not calculating temperature variation in the process), solvent filters and concentrate drying to extracting, to obtain dry extract.
If certain illustrated not, the ratio of extraction raw material/the extractions solvent that is added in the experiment and extraction raw material/wetting solvent is weight ratio so.
Plant equipment:
1. microwave treater: Milestone Microsynth, ATC-FO300 CEM Discover
2. ultrasound wave generator: Bandelin Sonorex Digital 10P
3. spectrophotometer: Beckman Coulter DU800
4. high-performance liquid chromatograph (HPLC): Amersham Biosciences 900 series, analytical column: Luna 5u C18 (2) 100A (Phenomene Co., American)
Example 1: Asiatic plantain
Table 1 shows Asiatic plantain after Different Extraction Method is handled, the amount of the ursolic acid that is extracted from the per kilogram Asiatic plantain.The amount of ursolic acid is analyzed dose thing dissolving back in the Asiatic plantain with HPLC, wherein with the light absorption value of UV detecting device test sample at the 205nm place, mobile phase adopts the gradient mode, initial concentration is 50% methyl alcohol, flow velocity is 1 ml/min, stream was washed 68 minutes, and final concentration is 100% methyl alcohol.The content of ursolic acid calculates after comparing with standard items in the extract.
Table 1
Experiment Extraction conditions The ursolic acid extracted amount
1-1 10 times of hydro-thermals reflux 100 ℃ and extracted 2 hours 24.02mg
1-2 10 times of water Extraction by Ultrasound 2 hours 5.65mg
1-3 10 times of alcohol hot refluxs were extracted 2 hours for 65 ℃ 114.75mg
1-4 10 times of alcohol Extraction by Ultrasound 2 hours 86.98mg
1-5 The 1:1 water-wet, 25 watts of microwave radiations 1 minute are used not heated and stirred 5 minutes of 10 times of alcohol again 149.08mg
As shown in table 1, because ursolic acid is pure dissolubility, it is better as the effect of extracting solvent with alcohol, no matter thereby be to extract or Extraction by Ultrasound with hot reflux, when the extraction solvent is alcohol (experiment 1-3,1-4), the ursolic acid content that it extracted all is higher than the ursolic acid content when extracting solvent and being water (experiment 1-1,1-2), and it is better wherein to extract the effect of (experiment 1-3) with the alcohol hot reflux.Yet the result of experiment 1-5 shows, will extract raw material and use 25 watts of microwave radiations after 1 minute again with the 1:1 water-wet, stirs the amount of the ursolic acid that extracts 5 minutes gained even extracts the taller of (experiment 1-3) than alcohol hot reflux with alcohol.Moreover, the microwave radiation that the Microwave Pretreatment method was only carried out 1 minute was used alcoholic extraction 5 minutes again, compare with the long-time extraction that experiment 1-3 went through 2 hours, method of the present invention not only can be saved extraction time, more can reach the purpose of saving the energy owing to shortening heat time heating time.
Example 2: lotus leaf
Table 2 shows lotus leaf after Different Extraction Method is handled, the amount of the Nuciferine that is extracted from the per kilogram lotus leaf.The amount of Nuciferine is analyzed dose thing dissolving back in the lotus leaf with HPLC, and wherein with the light absorption value of UV detecting device test sample at the 265nm place, mobile phase adopts the gradient mode, initial concentration is 100% water, flow velocity is 1 ml/min, and stream was washed 20 minutes, and final concentration is 100% methyl alcohol.Nuciferine content is that (Area Under Curve AUC) represents the HPLC area under curve of using Nuciferine in the extract.
Table 2
Experiment Extraction conditions The Nuciferine extracted amount
2-1 10 times of alcohol hot refluxs were extracted 30 minutes for 65 ℃ 0.30AUC
2-2 10 times of hydro-thermals reflux 100 ℃ and extracted 1 hour 27.70AUC
2-3 Not heated and stirred 5 minutes of 10 times of water was used in 1:3 water-wet, 50 watts of microwave radiations in 1 minute again 27.71AUC
2-4 The 1:3 water-wet, 50 watts of microwave radiations stirred 5 minutes down for 50 ℃ with 10 times of water in 1 minute again 52.30AUC
Nuciferine is a water-soluble substances, thereby water is better as the effect of extracting solvent.Find that by experiment 2-1 and 2-2 under the same conditions, when using alcohol and water as the extraction solvent respectively, the difference of its extraction effect is very big.2-3 is with the 1:3 water-wet in experiment, and 50 watts of microwave radiations are after 1 minute, blunge 5 minutes (not heating) again, though the amount of gained Nuciferine is suitable with experiment 2-2 heat reflow method, but can significantly shorten extraction time, owing to do not need the step of long-time heating, also can save the energy again.2-4 further finds from experiment, after Microwave Pretreatment method and heating extraction combination, can significantly promote the extracted amount of Nuciferine.
Example 3: the fruit of Chinese magnoliavine
Table 3 shows the fruit of Chinese magnoliavine after Different Extraction Method is handled, the amount of the schizandrin that is extracted from the per kilogram fruit of Chinese magnoliavine.The amount of the schizandrin in the fruit of Chinese magnoliavine is analyzed dose thing dissolving back with HPLC, wherein with the light absorption value of UV detecting device test sample at the 280nm place, mobile phase adopts three sections gradient modes, and initial concentration is 60% methyl alcohol, and flow velocity is 1 ml/min, stream was washed 20 minutes, improve methanol concentration to 100% in the gradient mode again, keep 100% methyl alcohol stream afterwards and washed 12 minutes, wash through 12 minutes stream again, in the gradient mode methanol concentration is reduced to 60%, ultimate density is got back to 60% methyl alcohol.The content of schizandrin is compared afterwards by calculating with standard items in the extract.
Table 3
Experiment Extraction conditions The schizandrin extracted amount
3-1 10 times of hydro-thermals reflux 100 ℃ and extracted 2 hours 6.59mg
3-2 10 times of alcohol hot refluxs were extracted 1 hour for 65 ℃ 42.70mg
3-3 1:1.4 not heated and stirred 5 minutes of 10 times of alcohol was used in water-wet, 100 watts of microwave radiations in 1 minute again 216.06mg
3-4 10 times of normal hexanes do not heat extraction 5 minutes 104.13mg
3-5 10 watts of microwave radiations 1 minute are used not heated and stirred 5 minutes of 10 times of normal hexanes again 168.84mg
Contained schizandrin is oil-soluble in the fruit of Chinese magnoliavine, and experiment 3-1 is that the effect of extracting solvent is compared with 3-2 extracts solvent (as: water and alcohol) extraction with high polarity effect with experiment 3-4 normal hexane, and its extracted amount is more bad.Experiment 3-3 earlier with fruit of Chinese magnoliavine dried powder with the 1:1.4 water-wet, after 100 watts of microwave radiations 1 minute, stirred (not heating) 5 minutes with alcohol again; It found that it is the amount of extracting the hot reflux extraction of solvent with alcohol that the extracted amount of schizandrin is higher than same far away.In addition, the extracted amount of experiment 3-3 Microwave Pretreatment method also is higher than the experiment 3-4 extracted amount of normal hexane as the extraction solvent.Experiment 3-5 did not carry out radiation 1 minute with 10 watts of microwave radiations with fruit of Chinese magnoliavine dried powder down moistening earlier, stirred (not heating) 5 minutes with normal hexane again, the extracted amount height that its extracted amount also only extracts with normal hexane than experiment 3-4.
Example 4: rose
Table 4 shows the extraction ratio of rose gained after Different Extraction Method is handled.The extraction ratio of rose extract refers to extract and the weight ratio of extracting raw material.
Table 4
Experiment Extraction conditions Extraction ratio (%)
4-1 10 times of hydro-thermals reflux 100 ℃ and extracted two hours 27.3
4-2 Not heated and stirred 5 minutes of 10 times of water was used in 25 watts of 1:3 water-wets, microwave radiation in 1 minute again 27.6
4-3 50 watts of 1:3 water-wets, microwave radiation were stirred 5 minutes down for 37 ℃ with 10 times of water in 1 minute again 28.2
4-4 25 watts of 1:3 water-wets, microwave radiation were stirred 5 minutes down for 65 ℃ with 10 times of water in 1 minute again 29.8
The result of table 4 shows, experiment 4-1 hot reflux is extracted suitable with the extraction ratio of the Microwave Pretreatment method of testing 4-2,4-3 and 4-4, but the Microwave Pretreatment method not only extraction time much shorter relatively, thereby and can not need high temperature heating to prevent that high temperature from causing obtaining under the condition of the oxidation of compound or degraded the extract of a great deal of.
Example 5: rice bran oil
Rice bran oil is called " heart oil " again, mainly be because contain the unsaturated fatty acid more than 80% and the neutral lotion fiber of 72% high concentration in the rice bran oil, in addition, because rice bran oil contains a large amount fat-soluble A, D, E, K, the excellent extraction raw material of cosmetology product especially, thereby can be used for making shampoo, rice bran frost and rice bran perfumed soap etc.
Table 5 shows the rice bran oil extraction ratio of rice bran gained after Different Extraction Method is handled.The extraction ratio of rice bran oil refers to extract (rice bran oil) and the weight ratio of extracting raw material (rice bran).
Table 5
Experiment Extraction conditions Extraction ratio (%)
5-1 10 times of normal hexanes stir not heat and extracted 4 hours 0.1462
5-2 10 times of normal hexane ultrasound waves stir and extracted 1 hour 0.1430
5-3 75 watts of microwave radiations 30 seconds, 10 times of normal hexanes be heated and stirred 5 minutes not 0.1712
5-4 The 1:1 water-wet, 50 watts of microwave radiations 90 seconds, 10 times of normal hexanes are heated and stirred 5 minutes not 0.1623
By found that of table 5, it is suitable with 1 hour resulting rice bran oil extraction ratio of experiment 5-2 Extraction by Ultrasound that experiment 5-1 stirred extraction 4 hours; And use the Microwave Pretreatment method, no matter be to extract raw material not in advance through wetting (experiment 5-3) or in advance through wetting (experiment 5-4), its extraction ratio all is higher than the extraction ratio of experiment 5-1 and 5-2.In general, the time of stirring extraction is long more, and the extraction ratio of rice bran oil is also high more.And can find that from table 5 the Microwave Pretreatment method can reach higher extraction ratio at short notice.Method of the present invention even can be applicable to the extraction of soya bean (claiming soybean again) oil, peanut oil, sesame oil, rapeseed oil, coconut oil and palm oil, sunflower oil, corn wet goods vegetable oil.
Though the present invention discloses as above with preferred embodiment; yet it is not in order to restriction the present invention; the those skilled in the art can make under the situation that does not break away from the spirit and scope of the present invention and changing and retouching, thus protection scope of the present invention should with appended claims the person of being defined be as the criterion.

Claims (39)

1. extracting method, it comprises the following steps: that (1) extract raw material with microwave radiation, wherein said raw material is not moistening in advance; And (2) will contact with the extraction solvent through the extraction raw material of microwave radiation.
2. method according to claim 1, wherein said extraction raw material is a plant sample.
3. method according to claim 2, wherein said plant sample are Chinese medicinal herbs.
4. method according to claim 2, wherein said plant sample are fruit, flower or seed.
5. according to the described method of arbitrary claim in the claim 1 to 4, the power of wherein said microwave radiation is 1 to 100 watt/gram.
6. method according to claim 5, the power of wherein said microwave radiation are 1 to 20 watt/gram.
7. method according to claim 6, the power of wherein said microwave radiation are 5 to 10 watts/gram.
8. method according to claim 5, the time of wherein said microwave radiation is 1 to 60 minute.
9. method according to claim 8, the time of wherein said microwave radiation is 1 to 30 minute.
10. method according to claim 9, the time of wherein said microwave radiation is 1 to 1.5 minute.
11. according to the described method of arbitrary claim in the claim 1 to 3, wherein said extraction solvent is an organic or inorganic liquid.
12. method according to claim 11, wherein said extraction solvent are water, methyl alcohol, ethanol, ethyl acetate, normal hexane, acetone, tetrahydrofuran or its potpourri.
13. method according to claim 11, wherein said extraction solvent are water, methyl alcohol, ethanol, normal hexane, acetone or its potpourri.
14. method according to claim 11, wherein said extraction solvent is water, ethanol or normal hexane.
15. according to the described method of arbitrary claim in the claim 1 to 4, the weight ratio of wherein said extraction raw material and described extraction solvent is 1: 0.5 to 1: 10.
16. method according to claim 15, the weight ratio of wherein said extraction raw material and described extraction solvent is 1: 4 to 1: 10.
17. method according to claim 16, the weight ratio of wherein said extraction raw material and described extraction solvent is 1: 8 to 1: 10.
18., wherein further comprise the extracting method of the group that is formed by stirring extraction, heating extraction, soxhlet extraction, Extraction by Ultrasound, super critical extraction, enzyme extraction method, semi-bionic extraction and its combination according to the described method of arbitrary claim in the claim 1 to 4.
19. an extracting method, it comprises the following steps: that (1) will extract raw material and contact with moistening solvent; (2) extract raw material with microwave radiation; Reaching (3) will contact with extracting solvent through the extraction raw material of microwave radiation, and wherein said moistening solvent is a water.
20. method according to claim 19, wherein said extraction raw material is a plant sample.
21. method according to claim 20, wherein said plant sample are Chinese medicinal herbs.
22. method according to claim 21, wherein said plant sample are fruit, flower or seed.
23. according to the described method of arbitrary claim in the claim 19 to 22, the weight ratio of wherein said extraction raw material and described wetting solvent is 1: 0.2 to 1: 5.
24. method according to claim 23, the weight ratio of wherein said extraction raw material and described wetting solvent are 1: 0.5 to 1: 4.
25. method according to claim 24, the weight ratio of wherein said extraction raw material and described wetting solvent are 1: 1 to 1: 3.
26. according to the described method of arbitrary claim in the claim 19 to 22, the power of wherein said microwave radiation is 1 to 100 watt/gram.
27. method according to claim 26, the power of wherein said microwave radiation are 1 to 20 watt/gram.
28. method according to claim 27, the power of wherein said microwave radiation are 5 to 10 watts/gram.
29. method according to claim 26, the time of wherein said microwave radiation is 1 to 60 minute.
30. method according to claim 29, the time of wherein said microwave radiation is 1 to 30 minute.
31. method according to claim 30, the time of wherein said microwave radiation is 1 to 1.5 minute.
32. according to the described method of arbitrary claim in the claim 19 to 22, wherein said extraction solvent is an organic or inorganic liquid.
33. method according to claim 32, wherein said extraction solvent are water, methyl alcohol, ethanol, ethyl acetate, normal hexane, acetone, tetrahydrofuran or its potpourri.
34. method according to claim 32, wherein said extraction solvent are water, methyl alcohol, ethanol, normal hexane, acetone or its potpourri.
35. method according to claim 32, wherein said extraction solvent is water, ethanol or normal hexane.
36. according to the described method of arbitrary claim in the claim 19 to 22, the weight ratio of wherein said extraction raw material and described extraction solvent is 1: 0.5 to 1: 10.
37. method according to claim 36, the weight ratio of wherein said extraction raw material and described extraction solvent is 1: 4 to 1: 10.
38. according to the described method of claim 37, the weight ratio of wherein said extraction raw material and described extraction solvent is 1: 8 to 1: 10.
39., wherein further comprise the extracting method of the group that is formed by stirring extraction, heating extraction, soxhlet extraction, Extraction by Ultrasound, super critical extraction, enzyme extraction method, semi-bionic extraction and its combination according to the described method of arbitrary claim in the claim 19 to 22.
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