CN103408538A - Method for extracting silymarin - Google Patents
Method for extracting silymarin Download PDFInfo
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- CN103408538A CN103408538A CN201310377707XA CN201310377707A CN103408538A CN 103408538 A CN103408538 A CN 103408538A CN 201310377707X A CN201310377707X A CN 201310377707XA CN 201310377707 A CN201310377707 A CN 201310377707A CN 103408538 A CN103408538 A CN 103408538A
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Abstract
The invention discloses a method for extracting and separating silymarin. The method comprises the following steps of: carrying out organic solvent extraction on silybum marianum meal generated by carrying out oil squeezing on silybum marianum seeds to obtain an extracting solution A, and concentrating to obtain a paste B; then adding normal hexane, and extracting fat to obtain an oil-free paste C; dissolving the oil-free paste C by using ethyl acetate, and then separating and purifying through simulated moving bed chromatography to obtain a component D rich in silychristin and silydianin, a component E rich in silibinin and a component F rich in isosilybin; carrying out concentration, crystallization and vacuum drying methods on the component E to obtain a final product, wherein the content of the silibinin reaches more than 98%. The method disclosed by the invention is simple in process step and easy and convenient to operate and greatly increases the separating and purifying efficiency of a silymarin extracting solution.
Description
Technical field
The present invention relates to a kind of from silybum marianum seed, extracting the method for silymarin.
Background technology
Silymarin is the natural active matter obtained from extracting the dry fruit of feverfew Silymarin, main component is silibinin (Silybin), Silydianin (Silydianin), Silychristin (Silychristin), the mixture of flavanolignan's compounds such as silybonol (Silybonol).Silymarin is the splendid natural medicine of a kind of anti-liver and gall diseases effect; can remove the hepatocellular free radical of infringement; liver cell is formed to protective membrane; can repair impaired liver cell; simultaneously to prostate cancer; growth and the differentiation of mammary cancer and uterus carcinoma cell have restraining effect, and psoriasis, allergic, arteriosclerosis, hypercholesterolemia are all had to good curative effect.
In prior art, the extracting method of common silymarin is mainly first Silymarin to be deoiled, then, with organic solvent reflux such as ethanol, methyl alcohol, acetone, ethyl acetate, separates and obtain the silymarin product through repeatedly extraction, wash-out, extraction.Because on the Herba Silybi mariani flavone class formation, phenolic hydroxyl group being arranged, have certain slightly acidic, can be combined with alkali, improve the water dissolution ability, but be insoluble in acidic solution, therefore the method for extracting with alkali extraction and acid precipitation in recent years is also more common.In addition, utilize that microwave-assisted extracts, ultrasonic assisted extraction silymarin report also arranged; A kind of silymarin extraction process of ethanol as single organic solvent of usining disclosed in CN1560046A; The method that adopts subcritical fluids butane extraction silymarin is disclosed in CN102924438A.
In prior art, the separating and purifying method of common silymarin is mainly to adopt the methods such as column chromatography, macroporous adsorbent resin separation, recrystallization.
The simulated moving bed chromatography technology is that simulation moving-bed design philosophy is introduced in liquid phantom preparing chromatogram, both kept the consumption of liquid phantom preparing chromatogram little, separation purity is high, and the advantage such as temperature-changeable operation, overcome again the shortcoming that common liquid phantom preparing chromatogram can not operate continuously, make it have separating power strong, equipment volume is little, and cost of investment is low, and is particularly conducive to the characteristics such as system of separating the high and difficult separation of thermo-sensitivity.
Summary of the invention
Method from extraction separation silymarin silybum marianum seed involved in the present invention comprises the following steps:
(1) any in ethanol, acetone or ethyl acetate is as extracting solvent, and the Herba Silybi mariani meal that oil expression produces to silybum marianum seed extracts, and obtains extracting solution A;
(2) extracting solution A is concentrated, obtain paste B;
(3) in paste B, adding must be without oily paste C after n-hexane extraction fat;
(4) without oily paste C acetic acid ethyl dissolution, carry out separating-purifying through simulated moving bed chromatography, obtain being rich in Silychristin and Silydianin component D, be rich in silibinin component E, be rich in the component F of Isosilybin;
(5) after component E concentration and recovery solvent, obtain the finished product by crystallization, vacuum-drying, wherein silibinin content is more than 98%;
(6) component D, F reclaim solvent, can obtain other corresponding Silymarin series products.
(1) middle etoh solvent, ethyl acetate or the acetone content of extracting is all more than 95% for step of the present invention, and extracting method can be heated and stirred, microwave-assisted, ultrasonic auxiliary or diacolation extraction.
The normal hexane that step of the present invention adds in (3) and the mass ratio of paste B are 0.5～2:1, add normal hexane to stir, and pour out afterwards solvent, and the remaining thickness throw out of container bottom is without oily paste C.
Step of the present invention (4) in the mass ratio of ethyl acetate and paste C be 20～30:1, the sorbent material that simulated moving bed chromatography is filled is silica gel, eluting solvent is normal hexane and ethyl acetate, the volume ratio of normal hexane and ethyl acetate is 1～2:1, separation temperature is room temperature, absorption and elution flow rate are 2～3BV/h, and be 700～900s switching time, simulation moving-bed column pressure 0.3～0.5Mpa.
Step of the present invention (5) in component E to be concentrated into solid content be 20%～50%, reclaim simultaneously solvent, place crystallization, centrifugally afterwards go out crystallization, then carry out vacuum-drying with 50 ℃～60 ℃.
Further, described step is preferably used in (1) 95% ethanolic soln as extracting solvent.
Further, described step (4) in simulated moving bed chromatography preferred switching time be 700～800s, simulation moving-bed column pressure 0.5Mpa.
Further, preferably component E to be concentrated into to solid content in (5) be 30% to described step.
Processing step of the present invention is simple, easy and simple to handle, has greatly improved the separating-purifying efficiency of silymarin extracting solution.The silibinin total recovery that described method obtains reaches more than 80%, and purity reaches more than 90%.
The accompanying drawing explanation
Fig. 1 is the HPLC spectrogram of silibinin standard substance.
Fig. 2 is the HPLC spectrogram of embodiment 2 extracting solution A.
Fig. 3 is the HPLC spectrogram of embodiment 2 product silibinins.
Embodiment
Embodiment 1
High performance liquid chromatography is adopted in the detection of silymarin composition.Chromatographic condition: chromatographic column is the C18 post, 250 * 4.6mm, 5 μ m; Mobile phase A is that 80% methyl alcohol, B are 20% methyl alcohol, flow velocity: 1.0ml/min, gradient elution; Detect wavelength 280nm; Sample size 10 μ l.By silibinin standard substance external standard method, calculated the content of silibinin.
Take the 10kg Herba Silybi mariani meal, using ethyl acetate as extraction agent, quality of material, than being solvent: Herba Silybi mariani meal=5:1, with 60 ℃ of heating 2h, extracts 3 times altogether, merges and obtains extracting solution A.Paste B by extracting solution A simmer down to 1.2kg.In paste B, add the 1kg normal hexane, stir 30min, pour out after normal hexane 1kg without oily paste C; To without in oily paste C, adding the 20kg ethyl acetate to dissolve, enter afterwards simulated moving bed chromatography and separate.The sorbent material that simulated moving bed chromatography is filled is silica gel, and eluting solvent is normal hexane and the ethyl acetate mixed solvent of volume ratio 1:1, and absorption and elution flow rate are 2BV/h, and be 720s switching time, column pressure 0.5MPa.Obtain being rich in Silychristin and Silydianin component D, be rich in the component E of silibinin and be rich in the component F of Isosilybin.By component D, E, F concentration and recovery solvent respectively, it is 30% that component E is concentrated into the solid quality percentage composition, places crystallization, centrifugally carries out vacuum-drying after going out crystallization again, and the vacuum-drying temperature 50 C, obtain silibinin 0.17kg, content 98.4%, yield 84.9%.
Embodiment 3
Take the 10kg Herba Silybi mariani meal, using 95% ethanol as extraction agent, extraction agent is 10:1 with the ratio of Herba Silybi mariani meal raw materials quality, under room temperature, soaks 1h post-heating backflow 3h, extracts altogether 3 times, and united extraction liquid obtains extracting solution A.By the paste B of extracting solution A simmer down to 1.3kg, in paste B, add the 1kg normal hexane and stir 30min, pour out after normal hexane 1.2kg without oily paste C; To without in oily paste C, adding the 25kg ethyl acetate to dissolve, enter afterwards simulated moving bed chromatography and separate.The sorbent material that simulated moving bed chromatography is filled is silica gel, and eluting solvent is normal hexane and the ethyl acetate mixed solvent of volume ratio 1.5:1, and absorption and elution flow rate are 2BV/h, and be 800s switching time, column pressure 0.5MPa.Obtain being rich in Silychristin and Silydianin component D, be rich in the component E of silibinin and be rich in the component F of Isosilybin.By component D, E, F concentration and recovery solvent respectively, it is 30% that component E is concentrated into the solid quality percentage composition, places crystallization, centrifugally carries out vacuum-drying after going out crystallization again, and the vacuum-drying temperature 50 C, obtain silibinin 0.18kg, content 98.2%, yield 89.7%.
Embodiment 4
Take the 10kg Herba Silybi mariani meal, using acetone as extraction agent, extraction agent is under the 10:1 room temperature, to soak 1h post-heating backflow 3h with the ratio of Herba Silybi mariani meal raw materials quality, extracts altogether 2 times, and united extraction liquid obtains extracting solution A.By the paste B of extracting solution A simmer down to 1.2kg, in paste B, add the 1kg normal hexane, stir 30min, pour out after normal hexane 1kg without oily paste C; To without in oily paste C, adding the 20kg ethyl acetate to dissolve, enter afterwards simulated moving bed chromatography and separate.The sorbent material that simulated moving bed chromatography is filled is silica gel, and eluting solvent is normal hexane and the ethyl acetate mixed solvent of volume ratio 1.5:1, and absorption and elution flow rate are 2BV/h, and be 800s switching time, column pressure 0.5MPa.Obtain being rich in Silychristin and Silydianin component D, be rich in the component E of silibinin and be rich in the component F of Isosilybin.By component D, E, F concentration and recovery solvent respectively, it is 30% that component E is concentrated into the solid quality percentage composition, places crystallization, centrifugally carries out vacuum-drying after going out crystallization again, and the vacuum-drying temperature 50 C, obtain silibinin 0.162kg, content 98.2%, yield 80.8%.
Claims (8)
1. one kind from extract separating the method for silymarin silybum marianum seed, it is characterized in that comprising the following steps:
(1) any in ethanol, acetone or ethyl acetate is as extracting solvent, and the Herba Silybi mariani meal that oil expression produces to silybum marianum seed extracts, and obtains extracting solution A;
(2) extracting solution A is concentrated, obtain paste B;
(3) in paste B, add the n-hexane extraction fat must be without oily paste C;
(4) without oily paste C acetic acid ethyl dissolution, carry out separating-purifying through simulated moving bed chromatography, obtain being rich in Silychristin and Silydianin component D, be rich in silibinin component E, be rich in the component F of Isosilybin;
(5) after component E concentration and recovery solvent, obtain the finished product by crystallization, vacuum-drying, wherein silibinin content is more than 98%;
(6) component D, F reclaim solvent, can obtain other corresponding Silymarin series products.
2. as claimed in claim 1 a kind of from silybum marianum seed, extract separating the method for silymarin, it is characterized in that: described step (1) in, extract the content of etoh solvent, ethyl acetate or acetone all more than 95%; Extracting method can be heated and stirred, microwave-assisted, ultrasonic auxiliary or diacolation extraction.
3. as claimed in claim 1 or 2 a kind of from silybum marianum seed, extract separating the method for silymarin, it is characterized in that: described step (3) in, the mass ratio of the normal hexane added and paste B is 0.5～2:1; Add normal hexane to stir, pour out afterwards solvent layer, the remaining thickness throw out of container bottom is without oily paste C.
4. as claimed in claim 3 a kind of from silybum marianum seed, extract separating the method for silymarin, it is characterized in that: described step (4) in, the mass ratio of ethyl acetate and paste C is 20～30:1; The sorbent material that simulated moving bed chromatography is filled is silica gel, eluting solvent is normal hexane and ethyl acetate, the volume ratio of normal hexane and ethyl acetate is 1～2:1, separation temperature is room temperature, absorption and elution flow rate are 2～3BV/h, be 700～900s switching time, simulation moving-bed column pressure 0.3～0.5Mpa.
5. as claim 1,2 or 4 a kind of described methods of separating silymarin from extraction silybum marianum seed, it is characterized in that: described step (5) in, it is 20%～50% that component E is concentrated into to solid content, reclaim simultaneously solvent, place crystallization, centrifugally afterwards go out crystallization, then carry out vacuum-drying with 50 ℃～60 ℃.
6. as claim 1,2 or 4 described a kind of from extract separating the methods of silymarin silybum marianum seed, it is characterized in that: described step (1) in, using 95% ethanolic soln as extracting solvent.
7. as claimed in claim 6 a kind of from silybum marianum seed, extract separating the method for silymarin, it is characterized in that: described step (4) in, simulated moving bed chromatography switching time is 700～800s, simulation moving-bed column pressure is 0.5Mpa.
8. as described as any one in claim 1,2,4 and 7 a kind of from silybum marianum seed, extracting the method separate silymarin, it is characterized in that: described step (5) in, it is 30% that component E is concentrated into to solid content.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015100524A1 (en) * | 2013-12-30 | 2015-07-09 | 晨光生物科技集团股份有限公司 | Method for producing silymarin |
| CN107805245A (en) * | 2017-12-14 | 2018-03-16 | 湖南千金协力药业有限公司 | A kind of purification process of legalon |
| CN108578263A (en) * | 2018-06-20 | 2018-09-28 | 吉林农业科技学院 | Silymarin Skin whitening care cosmetics |
| CN109362966A (en) * | 2018-11-05 | 2019-02-22 | 华中农业大学 | A kind of plant extract feed additive and application for improving sow milk performance |
| CN109810102A (en) * | 2019-01-29 | 2019-05-28 | 盘锦天源药业有限公司 | A kind of silymarin removes molten residual method |
| CN113045555A (en) * | 2021-03-17 | 2021-06-29 | 山东科技大学 | Method for extracting silymarin by screening ternary eutectic solvent with assistance of theoretical calculation |
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| CN1560046A (en) * | 2004-03-03 | 2005-01-05 | 西安理工大学 | Process for extracting water grind thisvine using alcohole as single organic dissolvent |
| CN101817816A (en) * | 2009-12-23 | 2010-09-01 | 南京泽朗医药科技有限公司 | Method for preparing silybin |
| CN102079745A (en) * | 2009-12-01 | 2011-06-01 | 白心亮 | Production method of silymarin |
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| CN1560046A (en) * | 2004-03-03 | 2005-01-05 | 西安理工大学 | Process for extracting water grind thisvine using alcohole as single organic dissolvent |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015100524A1 (en) * | 2013-12-30 | 2015-07-09 | 晨光生物科技集团股份有限公司 | Method for producing silymarin |
| CN105849103A (en) * | 2013-12-30 | 2016-08-10 | 晨光生物科技集团股份有限公司 | Method for producing silymarin |
| US9765062B2 (en) | 2013-12-30 | 2017-09-19 | Chenguang Biotech Group Co., Ltd. | Method for producing silymarin |
| CN105849103B (en) * | 2013-12-30 | 2019-03-12 | 晨光生物科技集团股份有限公司 | A kind of production method of silymarin |
| CN107805245A (en) * | 2017-12-14 | 2018-03-16 | 湖南千金协力药业有限公司 | A kind of purification process of legalon |
| CN107805245B (en) * | 2017-12-14 | 2020-11-03 | 湖南千金协力药业有限公司 | Method for purifying silybin |
| CN108578263A (en) * | 2018-06-20 | 2018-09-28 | 吉林农业科技学院 | Silymarin Skin whitening care cosmetics |
| CN109362966A (en) * | 2018-11-05 | 2019-02-22 | 华中农业大学 | A kind of plant extract feed additive and application for improving sow milk performance |
| CN109810102A (en) * | 2019-01-29 | 2019-05-28 | 盘锦天源药业有限公司 | A kind of silymarin removes molten residual method |
| CN113045555A (en) * | 2021-03-17 | 2021-06-29 | 山东科技大学 | Method for extracting silymarin by screening ternary eutectic solvent with assistance of theoretical calculation |
| CN113045555B (en) * | 2021-03-17 | 2023-05-30 | 山东科技大学 | Method for extracting silymarin by theoretical calculation assisted screening ternary eutectic solvent |
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