CN103193750B - Method for preparing shikimic acid and anise flavonoid by joint separation of macroporous resin XAD7HP - Google Patents
Method for preparing shikimic acid and anise flavonoid by joint separation of macroporous resin XAD7HP Download PDFInfo
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- CN103193750B CN103193750B CN201310148629.6A CN201310148629A CN103193750B CN 103193750 B CN103193750 B CN 103193750B CN 201310148629 A CN201310148629 A CN 201310148629A CN 103193750 B CN103193750 B CN 103193750B
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- ethanol
- macroporous resin
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Abstract
The invention discloses a method for preparing shikimic acid and anise flavonoid by joint separation of macroporous resin XAD7HP. The method comprises the steps of adding degreased anise powder to an extractor, adding ethanol solution according to a certain liquid-to-solid ratio, extracting at certain temperature, and fully dissolving in ethanol solution to obtain extract solution; distilling and concentrating the extract solution by reduced pressure to recover ethanol; adjusting the concentration of ethanol in concentrated solution to 20-30% by ethanol or water; adjusting the pH value of the solution to be acidic by hydrochloric acid; filtering and removing an insoluble matter to obtain column-loading solution, adsorbing by an XAD7HP macroporous resin column at a certain flow speed, collecting effluent, and distilling at reduced pressure to remove a large part of ethanol and water; then drying to obtain a shikimic acid crude product; rinsing the macroporous resin column by neutral water; eluting flavone on the macroporous resin column by 80-95% of ethanol solution after removing a non-adsorptive substance; and collecting eluate, and distilling at reduced pressure to remove ethanol and a part of water, and then drying to obtain an anise flavone product.
Description
Technical field
The invention belongs to processing of farm products field, mainly a kind of with the star anise powder after degreasing for raw material, the method for the anistree flavones of extraction and isolation, this will improve the utilization ratio of star anise 20 ~ 30.
Background technology
Star anise is one of modal natural flavouring, is the fruit of a kind of " integration of drinking and medicinal herbs ".Star anise contains ethereal oil 5% ~ 12%, containing shikimic acid 5% ~ 10%, containing anistree flavones 8 ~ 14%.Because anistree Flavonoid substances and shikimic acid mix, very difficult separation obtains the higher anistree Flavonoid substances of purity, thus for anistree flavones industrialized preparing process at home and abroad also beyond example.
Containing multiple flavonoid compound in anistree fruit, comprise the flavonoid substance of the types such as flavonoid, flavonols, aurones class.Flavonoid compound is vegitabilia's general large class natural phenolic compound distributed more widely, and because this compounds has various biological activity, and toxicity is lower, is therefore subject to the extensive attention of domestic and international investigator always.Once the composition of investigator to anistree flavonoid glycoside was had to study, isolation identification 7 kinds of flavonoid glycoside compositions from star anise ethanol extraction, be respectively isoquercitrin, Quercetin-3 '-O-methyl-3-O-β-D-glucopyranoside, Quercetin-3-O-α-L-arabinose glycosides, Quercetin-3-O-D-xyloside, Chinese tamarisk element 3-O-orange peel glucosides, 4-methoxyl group rutin, Isorhamnetol-3-O-rutinoside.
The present invention is the degreasing star aniseed powder sloughing star aniseed oil is raw material, the therefrom simple effective method of the highly purified anistree flavones of extraction and isolation.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of method of the anistree flavones of extraction and isolation from degreasing star anise powder, and for solving the problems of the technologies described above, the present invention takes following technical proposal:
(1) will steam distillation, solvent-extraction process or super critical extraction be utilized to extract the degreasing star anise powder after star aniseed oil as raw material, degreasing star anise powder is joined in extractor, the amount being 10 ~ 25 times by liquid ratio adds volume percent 50%-70% ethanolic soln, extract at maintenance temperature is 50 DEG C ~ 80 DEG C, make it fully to be dissolved in ethanolic soln to obtain extracting solution; (2) extracting solution underpressure distillation concentration and recovery ethanol, recycling ethanol or water to regulate in concentrated solution alcohol concn in lower scope, leave standstill and cross to filter insolubles; (3) regulate the pH value of above-mentioned solution, adsorb flavones with certain flow rate by macroporous resin column, collect effluent liquid, after underpressure distillation removes most of second alcohol and water, dry shikimic acid crude product; Rinse macroporous resin column with neutral water again, after removing non-adsorbed thing, then use the flavonoid substance in the ethanolic soln wash-out macroporous resin column of high density, collect elutriant, after underpressure distillation removing ethanol and part water, dry anistree flavones.
Further, in the concentrated solution described in above-mentioned (2), alcohol concn should between 20% ~ 30%, and its density range at 0.973 ~ 0.965g/ml, and is the weakly acidic solution of 3 ~ 5 with salt acid-soluble adjustment PH, and this solution is as upper prop liquid.
Further, described in above-mentioned (3), macroporous resin is XAD7HP resin.
Further, " ethanolic soln of high density " its concentration described in above-mentioned (3) is 80% ~ 95%, in order to the anistree flavones of absorption on wash-out macroporous resin XAD7HP, collects elutriant, after underpressure distillation removes most second alcohol and water, dry anistree flavones.
The applicant studies discovery, and the macroporous adsorbent resin XADHP7 with middle polarity only has good adsorptive power to anistree flavones, and adsorbs hardly shikimic acid, thus reaches the object being separated respectively and preparing shikimic acid and anistree flavones.
Accompanying drawing explanation
Fig. 1 shikimic acid, anistree extracting flavonoids separation process figure.
Embodiment
Performing step of the present invention is as follows:
Degreasing star anise powder after extracting olium anisi by utilizing normal hexane or the method such as sherwood oil or supercritical extraction joins in extractor, the ethanolic soln of 55%-65% is added by the liquid ratio of 15:1-25:1, at the temperature of 60 DEG C ~ 80 DEG C, extract 120 ~ 360min, filtration obtains extracting solution, be evaporated to 1/5 of original volume, then add ethanol or water by the concentration adjustment of ethanol in concentrated solution to 20% ~ 30%, at this moment its density is 0.965 ~ 0.973.Regulate the pH value of above-mentioned concentrated solution to be 3 ~ 5, filter after leaving standstill, filtrate under 40 DEG C ~ 50 DEG C conditions with lower speed by XAD7HP macroporous resin column, collect effluent liquid, after underpressure distillation removes most of second alcohol and water, dry shikimic acid crude product; Then use water rinse resin post, the more anistree flavones using 80% ~ 95% ethanolic soln wash-out macroporous resin to adsorb, collect elutriant, ethanol is reclaimed in underpressure distillation, dry anistree flavones crude product.
Below in conjunction with embodiment, essentiality content of the present invention is further described in detail.
Example 1: 2000 grams, degreasing star anise powder after utilizing normal hexane extraction olium anisi is joined in 20 liters of extractors, add 12 liter of 70% ethanol, 80 DEG C are extracted 120min, suction filtration, collect filtrate, 2 times are extracted by above-mentioned condition respectively again with 7 liter of 70% ethanol, filtrate is merged, filtrate is through vacuum distillation recovered solvent, being concentrated into volume is behind 1/10 of original volume, utilize ethanol or water that the alcohol concn in concentrated solution is adjusted to ethanol content for 30%(W/V), then pH value 3.0 is regulated with hydrochloric acid, leave standstill filtration after 3 hours and obtain upper prop liquid, by upper prop liquid by XAD7HP macroporous resin column, collect effluent liquid, after concentrated, carry out lyophilize again obtain shikimic acid goods 141.06g, the purity of shikimic acid is 78.4%, rinse resin column with neutral water, then use the anistree flavones on 80% ethanolic soln wash-out macroporous resin, collect elutriant, after underpressure distillation removes most ethanol and moisture, lyophilize obtains anistree flavones goods 205g, and the purity of anistree flavones is 88.67%.Again with after the further recrystallization of methyl alcohol, obtain the anistree flavones of high purity that purity is 98.3%.
Degreasing star anise powder double centner after utilizing supercritical extraction olium anisi adds in the reactor with agitator by example 2, add the ethanol of 800 liter 60%, 50 DEG C are extracted 240min, suction filtration, collect filtrate, 2 times are extracted again by above-mentioned condition, filtrate is merged after underpressure distillation is concentrated into 1/8 of original volume, utilize ethanol or water that the alcohol concn in concentrated solution is adjusted to ethanol content for 20%(W/V), density is 0.972 sample liquid, pH value 3.5 is regulated with hydrochloric acid, leave standstill filtration after 5 hours and obtain upper prop liquid, by upper prop liquid by XAD7HP macroporous resin column, collect effluent liquid, after underpressure distillation removes most ethanol and moisture, vacuum-drying is to 9.76 kilograms, shikimic acid goods, the purity of shikimic acid is 81.3%, use the anistree flavones on 90% ethanolic soln wash-out macroporous resin again, collect elutriant, after underpressure distillation removes most ethanol and moisture, the weight that lyophilize obtains anistree flavones is 12.56 kilograms, and the purity of anistree flavones is 85.54%.Again with after the further recrystallization of methyl alcohol, obtain the anistree flavones of high purity that purity is 97.1%.
5000 grams, degreasing star anise powder after utilizing Petroleum ether extraction olium anisi joins in 60 liters of extractors by example 3, add 40 liter of 65% ethanol, 55 DEG C are extracted 260min, suction filtration, collect filtrate, use 65% extraction using alcohol 3 times of 20 liters more respectively, filtrate is merged through vacuum distillation recovered solvent, concentrated most after 8 liters, utilize ethanol that the alcohol concn in concentrated solution is adjusted to ethanol content for 25%(W/V), making density is 0.986 sample liquid, pH value 4.0 is regulated with hydrochloric acid, leave standstill filtration after 12 hours and obtain upper prop liquid, upper prop liquid is adsorbed anistree flavones by XAD7HP macroporous resin column, collect effluent liquid, shikimic acid 375.32g is obtained after drying through vacuum concentration, the purity of shikimic acid is 81.3%, with the anistree flavones on the ethanolic soln wash-out macroporous adsorbent resin of 95%, collect elutriant, underpressure distillation, concentrated and obtain anistree flavones crude product 514.45g after drying, the purity of anistree flavones is 85.12%.Again with after the further recrystallization of methyl alcohol, obtain the anistree flavones of high purity that purity is 96.7%.
Claims (5)
1. the method utilizing macroporous resin XAD7HP combined separation to prepare shikimic acid and anistree flavones, it is characterized in that: utilize the degreasing star anise powder after extracting aniseed essential oil to carry out Extraction and separation and prepare shikimic acid and anistree flavones, degreasing star anise powder is joined in extractor, ethanolic soln is added by certain liquid ratio, extract at a certain temperature, make it fully to be dissolved in ethanolic soln to obtain extracting solution; By extracting solution underpressure distillation concentration and recovery ethanol, recycling ethanol or water regulate alcohol concn in concentrated solution to be volume percent 20% ~ 30%; Utilize the pH value of hydrochloric acid conditioning solution for acidity, leave standstill 2 ~ 12 hours, cross after filtering insolubles and obtain upper prop liquid, with certain flow rate by XAD7HP macroporous resin column absorption flavones, collect effluent liquid, after underpressure distillation removes most of second alcohol and water, dry shikimic acid crude product; Rinse macroporous resin column with neutral water again, after removing non-adsorbed thing, then use the flavones in volume percent 80% ~ 95% ethanolic soln wash-out macroporous resin column, collect elutriant, after underpressure distillation removing ethanol and part water, dry anistree flavones product.
2. method according to claim 1, the ethanol solution concentration of described extracting solution is volume percent 50%-70%.
3. method according to claim 1 and 2, the amount being 10 ~ 25 times by liquid ratio adds ethanolic soln.
4. method according to claim 1 and 2, described Extracting temperature is 50-80 DEG C.
5. method according to claim 1, continues to carry out recrystallization to shikimic acid crude product and anistree flavones crude product.
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| CN103193750B true CN103193750B (en) | 2014-12-31 |
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| CN107158047B (en) * | 2017-05-08 | 2020-10-30 | 甘肃省医学科学研究院 | Method for simultaneously preparing shikimic acid and total flavonoids in cedar needles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250104A (en) * | 2008-03-19 | 2008-08-27 | 广西师范学院 | Method for extracting high-pure shikimic acid from scarlet octagonal fruit |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101250104A (en) * | 2008-03-19 | 2008-08-27 | 广西师范学院 | Method for extracting high-pure shikimic acid from scarlet octagonal fruit |
Non-Patent Citations (1)
| Title |
|---|
| 八角茴香黄酮苷成分研究;袁经权;《2010年中国药学大会暨第十届中国药师周论文集》;20101130;第2-3页 * |
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