CN1807445A - Method for extracting Chinese yam saponin from turmeric - Google Patents
Method for extracting Chinese yam saponin from turmeric Download PDFInfo
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- CN1807445A CN1807445A CNA2006100001616A CN200610000161A CN1807445A CN 1807445 A CN1807445 A CN 1807445A CN A2006100001616 A CNA2006100001616 A CN A2006100001616A CN 200610000161 A CN200610000161 A CN 200610000161A CN 1807445 A CN1807445 A CN 1807445A
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Abstract
A method which extract yam saponin, using supercritical fluid extraction method and carbon dioxide as extraction solvent; firstly, separating pigment of turmeric acid hydrolytic dry matter via 0. 5-2h static extraction of carbon dioxide and 2-6h circulating extraction in the condition of 15-40Mpa extraction pressure, 30-50deg C extraction temperature, 4-8MPa analytical pressure and 35-55deg C analytical temperature; then in the condition of 15-40MPa extraction pressure, 30-70deg C extraction temperature, 4-8MPa analytical pressure and 35-55deg C analytical temperature, getting yam saponin product via 0. 5-2h static extraction of carbon dioxide and 2-6h circulating extraction, centrifuging or filtration; Finally, recovering ethanol; at the same time of extraction, adding ethanol entrainer in circulatory system. The advantages of this invention are the production circle is short, the operation is simple, the separation is easy, no pollution, avoiding inflammability and flammability of organic solvent, the productivity and the purity of product is high.
Description
Technical field
The invention belongs to the method for extracting substance from natural phant, specifically a kind of also method of the luxuriant and rich with fragrance skeleton of (a) hydrogenation and heterocyclic fused steroide-diosgenin of pentamethylene of extracting from the yellow ginger (D.zingiberensis has another name called Rhizome of Peltate Yam).
Background technology
Diosgenin (Diosgenin) has another name called diosgenin, and chemical name is a Δ, the 3-hydroxyl, and the 25R-spirostene, its structural formula is seen Fig. 1.It is to be separated from mountain castor Su (Dioscorea tokoroMakino) by Japanese scholar the earliest the thirties in 20th century to obtain.Existing research report, this compound has haemolysis, reducing blood-fat, antibiotic, anti-inflammatory, antitumor action etc., it is the important medicine chemical material of synthesizing steroid hormones (steroid hormone) medicine and contraceptive steroid, can further process cortin, sexual hormoue, progestogen three major types kind more than 300, be described as " gold in the medicine " by the world.At present, domestic have numerous manufacturer production steroid hormone medicines and a contraceptive steroid, is to be only second to an antibiotic key areas in the pharmaceutical production.
The method of extracting diosgenin in the yellow ginger at present mainly contains: (1) conventional acid hydrolysis method.It is after yellow ginger is soaked, and adds vitriol oil pressurized hydrolysis, and hydrolyzate is washed to neutrality, and dry decolouring is then with sherwood oil or gasoline extraction.The rate of recovery of this class methods diosgenin is lower.(2) fermentation-acid-hydrolysis method.It is that the Petroleum ether extraction diosgenin is used in pressurize then acid hydrolysis post neutralization, filtration again behind the filtration cakes torrefaction with the broken back of yellow ginger rhizome band pigment ferment at constant temperature.These class methods in and the time adopt liming neutral technology, can reduce the saltiness of liquid glucose, but, reduced the extraction yield of sapogenin, and the production cycle be long because filter cake increases.(3) enzymolysis-acid-hydrolysis method.It is to utilize biological method and the chemical process extraction diosgenin that combines.At first the broken back of yellow ginger rhizome band pigment is added amylase enzymolysis, Petroleum ether extraction is used in acid hydrolysis, neutralization, filtration again after the drying; Also have research that filtration cakes torrefaction is placed on and use Petroleum ether extraction in the apparatus,Soxhlet's, extracting solution gets diosgenin through concentrate drying.This method has improved the extraction yield of diosgenin, but extracting cycle is long, needs to use a large amount of organic solvents.
More than a few class technologies all adopt organic solvents such as sherwood oil or gasoline to carry out the extraction of diosgenin, all have following shortcoming, limited the effective extraction and the application of diosgenin to a great extent.(1) be extracted under the normal pressure and carry out, so efficient is on the low side; In order to improve extraction efficiency to greatest extent, then need to adopt the cycling extraction mode, this just makes technological operation loaded down with trivial details, and has prolonged the production cycle greatly.(2) a large amount of organic solvent has caused the pressure and the hidden danger of aspects such as storage, production safety to producer.(3) organic solvent residue has been brought the problem of food safety aspect.
Supercritical fluid extraction is to study very active technology in recent years, generally is used for fields such as medicine, food, spices, petrochemical complex and environmental protection, becomes the effective way that obtains high quality, " green, environmental protection " product.There is the minority report to carry out the trial of supercritical extraction saponin at present, but be that raw material extracts saponin how with other yams (Ningpo Yam Rhizome, Dioscorea panthaica Prain et Burkill etc.), technology is not mature enough, still need with an organic solvent the supercritical extraction product to be carried out subsequent purification, just can reach the ideal quality product.Therefore, still there are above-mentioned food safety and production safety potential problem.
Summary of the invention
The objective of the invention is to overcome the weak point of above-mentioned technology, and a kind of suitable supercutical fluid is provided, optimize processing condition, from yellow ginger, extract the method for diosgenin.
The object of the invention can realize by the following method: this method is to adopt supercritical fluid extraction, makes extraction solvent with supercritical carbon dioxide fluid; At first, the dry thing of a certain amount of yellow ginger acid hydrolysis, extracting pressure 15-40MPa, extraction temperature 30-50 ℃, resolve under pressure 4-8MPa, resolution temperature 35-55 ℃, by static extracting and the cycling extraction of carbonic acid gas 0.5-2h, isolate the pigment in the yellow-ginger hydrolysate; Then, after removing pigment, extracting pressure 15-40MPa, extraction temperature 30-70 ℃, resolve under pressure 4-8MPa, resolution temperature 35-55 ℃, by carbonic acid gas 0.5-2h static extracting and the cycling extraction of 2-6h, centrifugal or filter, obtain the diosgenin product; Then, supernatant liquor with extract after centrifugal or filtered liquid reclaim ethanol by rotary evaporation; When extracting, add the ethanol of volume fraction 70%-100% as entrainment agent to the recycle system.
The material bibliographical information that can be used as supercutical fluid has a lot, as carbonic acid gas, and ethanol, acetone, water, ethene etc. are because carbonic acid gas (CO
2) under supercritical state, have good extraction ability, and nontoxic, tasteless, stability height, wide material sources, cheap, therefore, the present invention preferably extracts diosgenin from yellow ginger, use the supercritical carbon dioxide extraction solvent.
Because the pigment in the yellow ginger is the principal element that influence diosgenin product appearance and quality, so the present invention carries out the extraction of diosgenin again after using supercritical carbon dioxide extraction to go out pigment, further improves the extraction yield and the product purity of diosgenin.
Can effectively extract the diosgenin in the yellow ginger and obtain the purity high product by supercritical co, key be the optimized choice of extraction process.The factor that influences supercritical carbon dioxide extraction efficient mainly contains extracting pressure, extraction temperature, resolution temperature, entrainment agent character, extraction time etc.
In general, extracting pressure is bigger to the extraction efficiency influence.Because fluidic density and pressure are closely related, when other conditions were constant, its density increased with the increase of pressure, the also corresponding increase of the solvency power of supercritical carbon dioxide fluid, and to the solubleness increase of diosgenin, this is favourable for extraction.But after density reached certain value, pressure boost was little to the influence of density again, can reduce the fluidic selectivity on the contrary, extracted more impurity, and extraction cost can obviously rise.The extracting pressure that is suitable for extraction diosgenin of the present invention is 15-40MPa, and preferable pressure is 20-35MPa.
Extraction temperature is also bigger to the extraction efficiency influence.When increasing temperature, on the one hand, strengthened molecular kinetic energy, fluidic rate of mass transfer and material spread coefficient increase, and are beneficial to desorption and the extraction of diosgenin from raw material; On the other hand, the rising of temperature can make the carbon-dioxide flow volume density descend, and causes solvency power to descend, and is unfavorable for extraction.Therefore, the height of yield depends on which kind of state is preponderated under this temperature.The extraction temperature that is suitable for extraction diosgenin of the present invention is 30-70 ℃, and preferable temperature is 45-65 ℃.
The parsing pressure that is suitable for extraction diosgenin of the present invention is 4-8Mpa, and preferable parsing pressure is 4-6MPa.
The influence of resolution temperature is: resolving under the certain condition of pressure, the rising of resolution temperature helps supercutical fluid and changes to gaseous state, thereby realizes itself and the separating and CO of extract
2Circulation in whole loop.But energy consumption increased when temperature was too high, caused the volatilization loss of entrainment agent simultaneously easily, reduced follow-up effect of extracting.The resolution temperature that is suitable for extraction diosgenin of the present invention is 35-55 ℃, and preferable temperature is 35-50 ℃.
The influence of extraction time is: on the one hand, and the static extracting between assurance in case of necessity.In the static extracting process, entrainment agent infiltrates the inside of extracting raw material, the material to be extracted of inside can be carried out.On the other hand, CO
2Flow one regularly, the cycling extraction time is long more, extracts fully more, the yield of diosgenin is high more; But time lengthening, power consumption increases, and extract acquire a certain degree after, continue the increase time, yield improves not obvious.The available extraction time of the present invention is 2-6h, and the preferable extraction time is 3-5h.
In supercritical carbon dioxide extraction system of the present invention, adding an amount of polarity entrainment agent can increase diosgenin greatly at supercritical CO
2Solubleness in the fluid and selectivity increase the sensitivity of solute to temperature, pressure, change the critical parameter of solvent.Common entrainment agent has water, alcohol, ketone, ester etc., and for fear of residues of harmful substances with to the influence of quality product, the present invention selects water or ethanol or the mixture of the two as entrainment agent.Being suitable for alcoholic acid volume fraction of the present invention is 20%-100%, and preferable volume fraction is 70%-100%.Alcoholic acid volume fraction % is meant: the alcoholic acid volume accounts for the per-cent of entrainment agent cumulative volume.
From yellow ginger, extract the method for diosgenin, adopt supercritical carbon dioxide extraction, comprise the static extracting of 0.5-2h.Static extracting is meant: close the valve of supercritical co turnover extraction kettle, keep extraction kettle under the setting pressure state, supercritical co does not carry out the extraction of circulation time.
The present invention through lab scale to pilot scale through facts have proved in a large number, adopt the supercritical carbon dioxide extraction method, be raw material with the dry thing of yellow ginger acid hydrolysis, yield can reach 13.8%-15.6%, and the products obtained therefrom quality is good, mp210-213 ℃, molten apart from≤10 ℃, purity is more than 94.9%.
The present invention compares with the conventional gasoline extracting method has following advantage: the yield of supercritical carbon dioxide extraction and product purity and traditional extraction process are suitable, production cycle shortens greatly, easy and simple to handle, be easy to separate, improve extraction efficiency and product purity, pollution-free, avoided using the inflammable and explosive danger of gasoline, safe.This technology is fully applicable to industrial production, and it can not only effectively extract diosgenin, products obtained therefrom purity height, and, do not exist any objectionable impurities to pollute.
Description of drawings
Fig. 1 is the chemical structural formula of diosgenin
Fig. 2 is the technical process of extracting diosgenin from yellow ginger
Fig. 3 is the device that extracts diosgenin from yellow ginger.
Embodiment
Below in conjunction with accompanying drawing, enumerate 2 embodiment, the present invention is further specified, but the present invention is not only limited to these
Embodiment.
Of the present invention shown in Figure 2: remove main explanation and extract outside the method for diosgenin from yellow ginger (D.zingiberensis has another name called Rhizome of Peltate Yam), the extract that also will obtain diosgenin carries out centrifugal or filtration, promptly obtains the diosgenin product.Simultaneously, supernatant liquor with extract after centrifugal or filtered liquid reclaim ethanol by rotary evaporation.
Shown in the device of Fig. 3 of the present invention: the dry thing of the acid hydrolysis of yellow ginger is carried out appropriate crushing screening, take by weighing a certain amount of powder extraction kettle of packing into, and add entrainment agent.Opening carbon dioxide steel cylinder feeds in the storage tank gas; Set the temperature and the heating of extraction kettle, separating still by operating panel.When reaching design temperature, open the valve that enters extraction kettle, make carbon dioxide enter extraction kettle by mixing tank, cleaner; Opening high-pressure pump pressurizes to extraction kettle.When reaching predetermined pressure, close the valve that enters extraction kettle, carry out static extracting.Open the valve that enters separating still then, by the frequency control of high-pressure pump and the adjusting of valve, the flow of carbonic acid gas in the regulation system carries out cycling extraction; In system, add the ethanol of volume fraction 70%-100% as entrainment agent by the entrainment agent pump in the time of cycling extraction.Discharging valve from separating still after cycling extraction stops picks out extract.According to above operating process, at first remove the materials such as pigment in the dry thing of yellow ginger acid hydrolysis, carry out the extraction of diosgenin then.Carry out extract centrifugal or filtration, promptly obtain the diosgenin product, purity reaches more than 94.9%.
Embodiment 1
(self-control is about to the yellow ginger raw material and isolates Mierocrystalline cellulose through the grinding of band water, removes starch through enzyme process again, and obtains through fermentation acid hydrolysis after drying to take by weighing the dry thing of yellow ginger acid hydrolysis; Wherein saponin content is 13.9%.) 2kg, drop into extraction kettle, add entrainment agent (ethanol of volume fraction 80%), begin after the sealing extraction kettle, separating still heating, opening carbon dioxide steel cylinder simultaneously makes carbonic acid gas enter storage tank, when the temperature of extraction kettle, separating still reaches 50 ℃, 55 ℃ respectively, open the valve that enters extraction kettle and make carbon dioxide enter extraction kettle by mixing tank, cleaner; Opening high-pressure pump pressurizes to extraction kettle.When extracting pressure reaches 15Mpa, close the valve that enters extraction kettle, carry out static extracting.Open the valve that enters separating still then, by the frequency control of high-pressure pump and the adjusting of valve, the flow of carbonic acid gas in the regulation system carries out cycling extraction; In system, add the ethanol of volume fraction 80% as entrainment agent (also claim solubility promoter, be used for regulating the polarity of supercutical fluid) by the entrainment agent pump in the time of cycling extraction.Discharging valve from separating still behind the cycling extraction 1h picks out the extract that mainly contains pigment, reset the temperature of extraction kettle, separating still then, when the temperature of extraction kettle, separating still reaches 60 ℃, 50 ℃ respectively, when extraction kettle static extracting pressure reaches 20Mpa, carry out static extracting according to aforementioned operation, carry out cycling extraction then; In system, add the ethanol of volume fraction 95% as entrainment agent by the entrainment agent pump in the time of cycling extraction.Discharging valve from separating still behind the cycling extraction 2h picks out the extract that mainly contains diosgenin.Carry out extract centrifugal or filtration, promptly obtain diosgenin product 290g, purity is 97.9%, mp212.01 ℃.Compare with the saponin standard substance, mp meets the saponin product standard near (mp211.94 ℃ of saponin standard substance), and product yield is 14.5%.Supernatant liquor with extract after centrifugal or filtered liquid reclaim ethanol by rotary evaporation.
Embodiment 2
With example 1 raw material and operation, entrainment agent all adopts the ethanol of volume fraction 90%, the dry thing of the yellow ginger acid hydrolysis 2kg that feeds intake.Condition during materials such as extraction pigment is the same; The temperature of extraction kettle, separating still is respectively 63 ℃, 45 ℃ when extracting diosgenin, and the pressure of extraction kettle is 25MPa, and the discharging valve from separating still behind the extraction 3h picks out the extract that mainly contains diosgenin.Carry out extract centrifugal or filtration, promptly obtain diosgenin product 302g, purity is 96.5%, and mp210.81 ℃, product yield is 15.1%, meets the saponin product standard.
Claims (3)
1, a kind of method of extracting diosgenin from yellow ginger is characterized in that it being to adopt supercritical fluid extraction, makes extraction solvent with supercritical carbon dioxide fluid; At first, the dry thing of a certain amount of yellow ginger acid hydrolysis, extracting pressure 15-40MPa, extraction temperature 30-50 ℃, resolve under pressure 4-8MPa, resolution temperature 35-55 ℃, by the static extracting of carbonic acid gas 0.5-2h and the cycling extraction of 2-6h, isolate the pigment in the yellow-ginger hydrolysate; Then, after removing pigment, extracting pressure 15-40MPa, extraction temperature 30-70 ℃, resolve under pressure 4-8MPa, resolution temperature 35-55 ℃, by carbonic acid gas 0.5-2h static extracting and the cycling extraction of 2-6h, and the centrifugal or filtration with extract, obtain the diosgenin product; Then, supernatant liquor with extract after centrifugal or filtered liquid reclaim ethanol by rotary evaporation; When extracting, add the ethanol of volume fraction 70%-100% as entrainment agent to the recycle system.
2, the method for from yellow ginger, extracting diosgenin according to claim 1, it is characterized in that removing in the yellow-ginger hydrolysate behind the coloring matter, extracting pressure 20-35MPa, extraction temperature 45-65 ℃, resolve under pressure 4-6MPa, resolution temperature 35-50 ℃, by the supercritical carbon dioxide extraction of 3-5h, obtain the diosgenin in the yellow-ginger hydrolysate.
3, the method for extracting diosgenin from yellow ginger according to claim 1 is characterized in that entrainment agent selection water or ethanol or the mixture of the two.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100001616A CN100494217C (en) | 2006-01-06 | 2006-01-06 | Method for extracting Chinese yam saponin from turmeric |
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| CNB2006100001616A CN100494217C (en) | 2006-01-06 | 2006-01-06 | Method for extracting Chinese yam saponin from turmeric |
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| CN100494217C CN100494217C (en) | 2009-06-03 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101129698B (en) * | 2007-09-18 | 2010-05-19 | 陈苏莉 | Eye drops containing turmeric extractive and preparation method thereof |
| CN101817868A (en) * | 2010-04-23 | 2010-09-01 | 湖北大学 | Process for extracting diosgenine from turmeric by catalytic hydrolysis method |
| CN1970785B (en) * | 2006-11-28 | 2010-12-01 | 周康 | Method for clean production and comprehensive utilization of yam saponin |
| CN101993161A (en) * | 2010-10-26 | 2011-03-30 | 大连博迈科技发展有限公司 | Diosgenin industrial wastewater processing method and new process for co-producing GSH (glutathione) and SAM (methionine) |
| CN112680496A (en) * | 2019-10-18 | 2021-04-20 | 河南度帮中药生物科技股份有限公司 | Production process for extracting diosgenin |
-
2006
- 2006-01-06 CN CNB2006100001616A patent/CN100494217C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1970785B (en) * | 2006-11-28 | 2010-12-01 | 周康 | Method for clean production and comprehensive utilization of yam saponin |
| CN101129698B (en) * | 2007-09-18 | 2010-05-19 | 陈苏莉 | Eye drops containing turmeric extractive and preparation method thereof |
| CN101817868A (en) * | 2010-04-23 | 2010-09-01 | 湖北大学 | Process for extracting diosgenine from turmeric by catalytic hydrolysis method |
| CN101817868B (en) * | 2010-04-23 | 2012-05-23 | 湖北大学 | Process for extracting diosgenine from turmeric by catalytic hydrolysis method |
| CN101993161A (en) * | 2010-10-26 | 2011-03-30 | 大连博迈科技发展有限公司 | Diosgenin industrial wastewater processing method and new process for co-producing GSH (glutathione) and SAM (methionine) |
| CN101993161B (en) * | 2010-10-26 | 2013-12-04 | 大连博迈科技发展有限公司 | Diosgenin industrial wastewater processing method and new process for co-producing GSH (glutathione) and SAM (methionine) |
| CN112680496A (en) * | 2019-10-18 | 2021-04-20 | 河南度帮中药生物科技股份有限公司 | Production process for extracting diosgenin |
| CN112680496B (en) * | 2019-10-18 | 2022-03-08 | 河南度帮中药生物科技股份有限公司 | Production process for extracting diosgenin |
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| CN100494217C (en) | 2009-06-03 |
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