CN101978984B - Method for preparing large-head atractylodes rhizome and sesquiterpene compound - Google Patents
Method for preparing large-head atractylodes rhizome and sesquiterpene compound Download PDFInfo
- Publication number
- CN101978984B CN101978984B CN2010102972103A CN201010297210A CN101978984B CN 101978984 B CN101978984 B CN 101978984B CN 2010102972103 A CN2010102972103 A CN 2010102972103A CN 201010297210 A CN201010297210 A CN 201010297210A CN 101978984 B CN101978984 B CN 101978984B
- Authority
- CN
- China
- Prior art keywords
- supercritical
- sesquiterpene
- volatile oil
- pressure
- rhizoma atractylodis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Medicines Containing Plant Substances (AREA)
Abstract
The invention discloses a method for preparing a large-head atractylodes rhizome and sesquiterpene compound. The method comprises the following steps of: 1) extracting a large-head atractylodes rhizome medicinal material at a set temperature and under a set pressure in a supercritical extractor, and feeding the extract into a fractionating column along with supercritical CO2 fluid; 2) applying a temperature gradient from low to high to the fractionating column under a certain fractionation pressure to ensure that the supercritical CO2 fluid sectionally fractionates volatile oil at a fixed flow rate; and 3) separating the volatile oil subjected to fractionation into two fractionation sections including a monoterpene component and a sesquiterpene compound, performing pressure reduction and feeding into a separator sequentially, collecting the fractionation section of the sesquiterpene compound, metering the CO2 by a rotor meter and emptying. By the method, the supercritical extraction is coupled to fractionation technology, so that the removal of the terpene from the volatile oil of the large-head atractylodes rhizome in the supercritical CO2 medium and the enrichment of the sesquiterpene are continuously finished, and a new way is provided for preparing the monoterpene-free large-head atractylodes rhizome and sesquiterpene compound.
Description
Technical field
The invention belongs to ingredient separation and purification field, be specifically related to the method that supercritical extraction coupled fractionating technology prepares Rhizoma Atractylodis Macrocephalae sesquiterpene complex.
Background technology
Sesquiterpene (sesquiterpenes) is meant the natural terpenes compounds that contains 15 carbon atoms in the molecule.General general formula is C
15H
24, molecular weight is 204.Sesquiterpene often is present in the volatile oil with derivative form such as alcohol, ketone, lactones in plant, is the key component of high-boiling fration in the volatile oil, has stronger fragrance and biological activity more, is the important source material of medicine, food, cosmetics industry.
The Rhizoma Atractylodis Macrocephalae is the dry rhizome of the feverfew Rhizoma Atractylodis Macrocephalae (Atractylodes macrocephala koidz), is clinical practice one of medical material the most widely, and the traditional Chinese medical science thinks that it is warm in nature, acrid in the mouth, hardship, have spleen reinforcing, stomach reinforcing, dampness and in effect.The Rhizoma Atractylodis Macrocephalae mainly contains volatile oil, mainly by monoterpenes compositions (carbon number is usually less than 15 in the molecule, and molecular weight is less than 204) such as myrcene, ocimene, limonene, australenes; Sesquiterpenoids components such as δ-selinene, elemene, cedrene, Flos Caryophylli alkene; And atractylol, atractylone, atractylodes lactone, 3-β-acetoxyl group atractylone, 3-beta-hydroxy atractylone etc. are formed with the sesquiterpene derivative that forms such as alcohol, ketone, lactone exist.Sesquiterpene is the main effective site of Rhizoma Atractylodis Macrocephalae volatile oil, and is wherein the highest with atractylone content again, is often used as the representative index of sesquiterpenoids.Modern pharmacological research shows that Rhizoma Atractylodis Macrocephalae sesquiterpenoid has cytotoxicity, can suppress the destruction of liver poison cell to hepatic tissue, repairs hepatic injury.
The traditional extraction process of Rhizoma Atractylodis Macrocephalae volatile oil adopts the steam distillation preparation more, steam distillation extraction time is long, very easily oxidative degradation of micromolecule monoterpenes material in the volatile oil, produce peroxide, further bring out sesquiterpenoid generation oxidation reactions such as atractylone, have a strong impact on the stability of the sesquiterpene complex that is extracted.For the monoterpene in the Rhizoma Atractylodis Macrocephalae volatile oil is removed, further improve atractylone content, take column chromatography or rectificating method to carry out usually.The column chromatography for separation complex steps will be used a large amount of organic solvents, and environment and health are all had certain adverse effect.And heat-sensitive substance decomposes easily in the conventional distillation process, and especially atractylone although molecular distillation can overcome this defective, because of the expense costliness, is difficult to industrial applications because of long-time heating oxidative degradation.
Along with supercritical CO
2The rise of abstraction technique also is applied in the extraction of Rhizoma Atractylodis Macrocephalae volatile oil gradually.Chinese patent " atractylone, the plant that contains atractylone and atractylone extract are in the purposes of preparation in the anti-influenza virus medicament " (CN1857358A) discloses a kind of employing supercritical CO
2The method of extraction atractylone from the Rhizoma Atractylodis medical material, but wherein monoterpene is not removed.Chinese patent " preparation of the anti-inflammatory component of bighead atractylodes rhizome volatile oil part and in the purposes of preparation anti-inflammatory drug " (CN1682897) adopts supercritical CO
2Extraction obtains bighead atractylodes rhizome volatile oil part, again through silica gel column chromatography, C
18Silica gel reversed phase column chromatography separation and purification obtains atractylenolide and Rhizoma Atractylodis Macrocephalae alkyne component.Although these patents have used supercritical extraction method, because supercritical CO
2In the time of sesquiterpene compositions such as extraction atractylone, also extract some volatile micromolecule monoterpenes compositions, as being further purified, then relate to repeatedly column chromatography, the flow process complexity.
Supercritical CO
2Fractional distillation is according to the alternating temperature principle that refluxes, by changing CO
2Density, make polynary blending ingredients at CO
2In produce dissolubility difference and separate, be particularly suitable for thermal sensitivity, boiling point is close, the separation of the homologue of similar performance.Adopt supercritical CO
2The extraction Rhizoma Atractylodis Macrocephalae volatile oil enters fractional distillation in the supercritical fractionation post again.Because monoterpenes component molecules amount is less, and sesquiterpenoid molecular weight such as atractylone are bigger, at supercritical CO
2Middle different solubility.Based on this, the application makes monoterpene and sesquiterpene produce bigger dissolubility difference by different cut points and fractional distillation pressure are set, and is separated into two fraction sections of monoterpene composition and sesquiterpene complex, regathers the sesquiterpene fraction section that does not contain monoterpene.Supercritical CO
2Extraction is coupled together with fractionating technology, is supercritical CO
2Terpene and the sesquiterpene complex preparation of taking off of Rhizoma Atractylodis Macrocephalae volatile oil provides a new way, the novelty and the creativeness that possess skills and use in the medium.
Summary of the invention
The object of the present invention is to provide a kind of Rhizoma Atractylodis Macrocephalae volatile oil to remove monoterpene and prepare the method for sesquiterpene complex.
According to purpose of the present invention, particularly, adopt supercritical CO
2The extraction Rhizoma Atractylodis Macrocephalae volatile oil, and in conjunction with supercritical CO
2Fractional distillation volatile oil makes the monoterpene composition of Rhizoma Atractylodis Macrocephalae volatile oil separate successively by the molecular weight size with the sesquiterpene complex.This fractional distillation process is different from traditional fractional distillation, is not the boiling point according to blending ingredients, but according to blending ingredients at supercritical CO
2In the dissolubility size separate.Its principle is to adopt supercritical CO earlier
2The extraction Rhizoma Atractylodis Macrocephalae volatile oil enters fractional distillation in the supercritical fractionation post again.Be dissolved with the supercritical CO of Rhizoma Atractylodis Macrocephalae volatile oil
2Along in the dephlegmator uphill process, temperature raises, supercritical CO
2Density reduce because Rhizoma Atractylodis Macrocephalae volatile oil is at supercritical CO
2The difference of mutually middle partition coefficient, the dissolubility of the monoterpene that the dissolubility of the sesquiterpene that molecular weight is bigger is more less than molecular weight descends manyly.The sesquiterpene composition is constantly from supercritical CO
2Separate out, form and reflux, backflow and rising component are carried out heat and mass exchange, and the result constantly falls and enrichment sesquiterpene, and the monoterpene component constantly rises and the derived score fractional distillation column.Based on this principle, intercept lower monoterpene component fraction of molecular weight and the higher sesquiterpene component of molecular weight respectively, the extraction that makes Rhizoma Atractylodis Macrocephalae volatile oil with take off terpene and finish continuously, to solve the loaded down with trivial details weak point of prior art purification step.
Rhizoma Atractylodis Macrocephalae volatile oil of the present invention takes off terpene and prepares the method for sesquiterpene complex, may further comprise the steps:
1) Rhizoma Atractylodis Macrocephalae medical material is put into the supercritical extraction device, extract under the temperature of setting, pressure, extract is with supercritical CO
2Fluid enters in the dephlegmator;
2) under certain fractional distillation pressure, on dephlegmator, apply a thermograde from low to high, the control supercritical CO
2Fluid carries out the segmentation fractional distillation to volatile oil under certain flow rate;
3) volatile oil is separated into monoterpene component and two fraction sections of sesquiterpene complex after fractional distillation, enters separator successively after decompression, collects sesquiterpene complex fraction section, CO
2Emptying after the rotameter metering.
Described Rhizoma Atractylodis Macrocephalae medical material is the dry rhizome of the feverfew Rhizoma Atractylodis Macrocephalae (Atractylodes macrocephala koidz).
Described extracting pressure is 15～30MPa, is preferably 20～30MPa.
Described extraction temperature is 308～348K, is preferably 308～328K.
Described cut point is 313～358K, is preferably 313～343K, is divided into four sections temperature controls, and thermograde is 10K.
Described fractional distillation pressure is 25～30MPa, is preferably the mode of programmed pressure, boosts to 30MPa from 25MPa, and every 20min rising 1MPa, 30MPa keep 20min down.
Described supercritical CO
2Flow velocity is 2～10L/min, preferred CO
2Flow velocity is 2～5L/min.
Described separating pressure is 5MPa, and separation temperature is 323K.
Described sesquiterpene complex is the mixture of sesquiterpene and sesquiterpene derivative, and wherein the mass percent of atractylone is not less than 50%.
Compared with prior art, characteristics of the present invention and advantage are:
(1) adopt thermograde and pressure controlled method, Rhizoma Atractylodis Macrocephalae volatile oil is finished extraction, absorption, fractional distillation, is separated additive process in extractor, dephlegmator, makes sesquiterpene complex and monoterpenes composition realize separating continuously.
(2) acquisition does not contain the sesquiterpene complex of monoterpene, and wherein the mass fraction of atractylone is improved, and reaches the requirement of national five class new Chinese medicines.
(3) the whole extraction and fractionation process of Rhizoma Atractylodis Macrocephalae volatile oil is all at chemically inert supercritical CO
2Finish in the solvent, whole process temperature is low, is difficult for taking place oxidation and degradation reaction, simultaneously do not need to carry out the solvent post processing yet, can not produce dissolvent residual, the sesquiterpene complex that removes behind the monoterpene can keep biological activity fully, meets current medicine and food green and melts the trend of sending out.
Description of drawings
Fig. 1 shows that the present invention prepares a kind of flow chart of embodiment of the method for nanometer liposome, 1CO
2Steel cylinder; 2 heat exchangers 1; 3 cold machines; 4 high-pressure pumps 1; 5 heat exchangers 2; 6 extraction kettles; 7 heat exchangers 3; 8 dephlegmators; 9 heat exchangers 4; 10 separators; 11 graduated cylinders; 12 spinner flowmeters; V1, V2, check-valves; The V3 back pressure regulator; T1～T4: dephlegmator fractional distillation section
Fig. 2 shows supercritical CO
2The mass spectrum total ion current figure of the Rhizoma Atractylodis Macrocephalae volatile oil of extraction.
Fig. 3 shows supercritical CO
2The mass spectrum total ion current figure of the Rhizoma Atractylodis Macrocephalae sesquiterpene complex after the fractional distillation.
The specific embodiment
In order to understand essence of the present invention better, following examples are used to describe in detail technology contents of the present invention, but should not be construed as limiting the scope of the invention.
Embodiment 1 Rhizoma Atractylodis Macrocephalae volatile oil take off the preparation of terpene and sesquiterpene complex
1. the extraction and fractionation process of Rhizoma Atractylodis Macrocephalae volatile oil
The atractylone reference substance, Shenzhen Haiwang Bio-pharmaceuticals joint-stock company provides.
Experimental provision: supercritical CO
2Extraction and fractionation equipment is made by Huaan, Jiangsu supercritical company, and device is by CO
2Compositions such as feed system, extractor, dephlegmator and separator.The extractor volume is 1L, the high 2m of dephlegmator, and internal diameter 20mm is filled with stainless steel foil group in the post, be divided into four sections temperature controls.Valve V1, the pipeline that V2 control extractor, dephlegmator link to each other with separator, valve V3 control dephlegmator pressure.The whole system maximum is born pressure 35MPa, the highest bearing temperature 368K.
Agilent 6890 gas chromatograies: U.S. Agilent company; Tianjin, island GCMS-QP2010Plus gas chromatograph-mass spectrometer (GC-MS), day island proper Tianjin company
Preparation method: in one embodiment, the method for taking off terpene and the preparation of sesquiterpene complex of the Rhizoma Atractylodis Macrocephalae volatile oil that the present invention relates to can be at supercritical CO
2Finish in the extraction and fractionation device, detail flowchart is shown in Fig. 1.
200g Rhizoma Atractylodis Macrocephalae medical material is packed in the extractor inner bag into capping.Open CO
2Steel cylinder, CO
2Gas is after cold machine 3 is cooled to liquid, by entering extractor 6 after high-pressure metering pump 4 pressurizations.Under the extraction conditions of 25MPa, 308K, extract volatile oil.Open valve V2, valve-off V1, supercritical CO
2Carrying volatile oil and entering dephlegmator by the bottom.Control valve V3, control fractional distillation pressure is 25MPa, applying a thermograde from low to high by the bottom to the top on the dephlegmator is 313K～323K～333K～343K.By the programmed pressure mode of every 20min rising 1MPa, improve fractional distillation pressure until 30MPa, and keep 20min.The fractional distillation component from capital with supercritical CO
2Enter into separator 10, at 5MPa, 323K resolves down.CO
2Flow-control is at 5L/min, through spinner flowmeter 12 emptyings.Collect 1h fraction and 2h fraction respectively, the content of monoterpene and atractylone in the employing gas Chromatographic Determination fraction.
2. the mensuration of monoterpene and atractylone
The content of monoterpene and atractylone in the employing gas Chromatographic Determination supercritical fractionation thing.Chromatographic condition is: chromatographic column: HP-5MS, quartz capillary column (30m * 250 μ m * 0.25 μ m); Injector temperature: 250 ℃, fid detector temperature: 280 ℃; Column temperature (temperature programming): 80 ℃ (1min) → (5 ℃/min) → 200 ℃; Split ratio 1: 50; Carrier gas: N
2, flow: 1.0ml/min.
Rhizoma Atractylodis Macrocephalae volatile oil is after fractional distillation, and the content of monoterpene and atractylone is as shown in table 1 in the fraction.
The terpene process is taken off in the fractional distillation of table 1 supercritical extraction
This routine result shows that through supercritical fractionation, Rhizoma Atractylodis Macrocephalae volatile oil is two fraction sections by the molecular weight size separation, first fraction section mainly is to contain molecular weight less than 204, and promptly carbon number is less than 15 monoterpenes component, wherein total content is 30.43%, and the content of atractylone is 15.46%.Second is heated up in a steamer sectional monoterpenes chemical compound and all removes, and mainly contains molecular weight more than or equal to 204 sesquiterpene, and the derivant of the ketone of sesquiterpene, aldehyde, lactone, and wherein the content of atractylone reaches 52.13%, and it is remarkable to take off the terpene effect.
The extraction of embodiment 2 Rhizoma Atractylodis Macrocephalae volatile oils
Present embodiment is investigated the extraction process of Rhizoma Atractylodis Macrocephalae volatile oil.200g Rhizoma Atractylodis Macrocephalae medical material is packed in the extractor inner bag into capping.Open CO
2Steel cylinder, CO
2Gas is after cold machine 3 is cooled to liquid, by entering extractor 6 after high-pressure metering pump 4 pressurizations.After extracting volatile oil under the extraction conditions of 25MPa, 308K, Open valve V1, valve-off V2, supercritical CO
2Carrying volatile oil and entering into separator 10, at 5MPa, 323K resolves down.CO
2Flow-control is at 5L/min, through spinner flowmeter 12 emptyings.The volatile oil that collection extracts, the content of monoterpene and atractylone in the employing gas Chromatographic Determination component, the result is as shown in table 2.
Table 2 supercritical extraction Rhizoma Atractylodis Macrocephalae volatile oil
This routine result shows supercritical CO
2The extraction Rhizoma Atractylodis Macrocephalae volatile oil, main component is to contain monoterpenes compositions such as myrcene, ocimene, limonene, australene, the derivant of the sesquiterpene that sesquiterpenoids components such as δ-selinene, elemene, cedrene, Flos Caryophylli alkene, atractylol, atractylone, atractylodes lactone A, atractylodes lactone B, 3-β-acetoxyl group atractylone, 3-beta-hydroxy atractylone etc. exist with forms such as alcohol, ketone, lactones.Wherein the monoterpene total content is 8.66%, and the content of atractylone is 36.65%, and still needing is further purified.
Embodiment 3 extracting pressure are to Rhizoma Atractylodis Macrocephalae volatile oil extraction influence
This example is investigated the influence of extracting pressure to Rhizoma Atractylodis Macrocephalae volatile oil.200g Rhizoma Atractylodis Macrocephalae medical material is packed in the extractor inner bag into capping.Press the method and parameter of embodiment 2, under the temperature of 308K, the control supercritical CO
2Pressure is 15～30MPa, extract volatile oil after, adopt the content of monoterpene and atractylone in the gas Chromatographic Determination fraction, the result is as shown in table 3.
Table 3 extracting pressure is to Rhizoma Atractylodis Macrocephalae volatile oil extraction influence
Present embodiment is the result show, under lower pressure, the volatile oil extraction yield is lower, and main component is the lower monoterpene composition of molecular weight, and atractylone content is very low.Along with the rising of pressure, to the dissolubility increase of volatile oil component, the component that the atractylone equimolecular quantity is bigger is extracted out gradually, and extraction yield increases, and the content of atractylone increases, and the monoterpenes relative amount descends.When pressure was increased to 20MPa, extraction yield reached 1.98%, and the content of atractylone increases to 22.45%.When extracting pressure further increases, the volatile oil component substantially extracts, and extraction yield no longer increases, and the content of monoterpene and atractylone remains unchanged substantially.Therefore, preferred extracting pressure is 20～30MPa, and this moment, volatile oil was extracted fully.
Embodiment 4 extraction temperature are to the influence of Rhizoma Atractylodis Macrocephalae volatile oil extraction
This example is investigated the influence of extracting pressure to Rhizoma Atractylodis Macrocephalae volatile oil.200g Rhizoma Atractylodis Macrocephalae medical material is packed in the extractor inner bag into capping.Press the method and parameter of embodiment 2, under the temperature of 308K～348K, the control supercritical CO
2Pressure is 25MPa, extract volatile oil after, adopt the content of monoterpene and atractylone in the gas Chromatographic Determination fraction, the result is as shown in table 4.
Present embodiment is the result show, the extraction of Rhizoma Atractylodis Macrocephalae volatile oil and constituent content and temperature correlation.Temperature raises, supercritical CO
2Density descend, the solvability of Rhizoma Atractylodis Macrocephalae volatile oil is descended, the extraction yield of volatile oil descends.Simultaneously, the decline of density, the component littler than molecular weight for the influence of the big components dissolved degree of molecular weight is bigger, and the dissolubility suppression ratio monoterpenes composition of atractylone descends manyly, show as that the content of atractylone reduces gradually in the extract, and the phenomenon that the content of monoterpenes composition increases on the contrary.Along with the increase of temperature, atractylone content downward trend is more obvious.Therefore, preferred extraction temperature is at 308K～328K, and prepared volatile oil monoterpene composition is less than 20%.
Table 4 extraction temperature is to Rhizoma Atractylodis Macrocephalae volatile oil extraction influence
Embodiment 5 cut points are taken off the terpene influence to Rhizoma Atractylodis Macrocephalae volatile oil
This example is investigated cut point is taken off terpene to Rhizoma Atractylodis Macrocephalae volatile oil influence.200g Rhizoma Atractylodis Macrocephalae medical material is packed in the extractor inner bag into capping.Press the method and parameter of embodiment 1, fractional distillation pressure is 25MPa, and thermograde is 308K～358K.Collect 1h fraction and 2h fraction respectively, the content of monoterpene and atractylone in the employing gas Chromatographic Determination fraction, the result is as shown in table 5.
Present embodiment is the result show: keep higher column top temperature can make the sesquiterpene that extracts separate out falling, improve reflux ratio, increased selectivity.But because at high temperature, atractylone can be degraded, and increases column top temperature again and can make fractional distillation speed slow excessively, consumes supercritical CO
2Amount increase, take off the terpene effect and atractylone content does not have obvious raising.Therefore, comprehensively take off the terpene effect with from economic considerations, column top temperature fixes on 343K and is advisable.Temperature is decided to be 313K at the bottom of the post, and is close with extraction temperature, capable of reducing energy consumption.The temperature control hop count is also influential to separating effect in the post, and the temperature control hop count is many more, and the backflow number of times is many more.Evenly the thermograde that increases can produce metastable internal reflux, helps improving separation efficiency.Therefore, cut point is preferably 313K～343K, is divided into four sections temperature controls, and thermograde is 10K.
Table 5 cut point is to the influence of sesquiterpene complex preparation
Embodiment 6 fractional distillation pressure take off the terpene influence to Rhizoma Atractylodis Macrocephalae volatile oil
This example is investigated fractional distillation pressure takes off terpene to Rhizoma Atractylodis Macrocephalae volatile oil influence.200g Rhizoma Atractylodis Macrocephalae medical material is packed in the extractor inner bag into capping.Press the method and parameter of embodiment 1, fractional distillation pressure is 25～30MPa, and cut point is 313K～323K～333K～343K.Collect 1h fraction and 2h fraction respectively, the content of monoterpene and atractylone in the employing gas Chromatographic Determination fraction, the result is as shown in table 6.
Consider the convenience of operation, the method for having taked extraction and fractional distillation pressure to be consistent.Under lower pressure, fractional distillation speed is slower, and light composition for example monoterpene composition is distributed in two fraction sections simultaneously, and separating degree is lower.Along with the increase of pressure, Rhizoma Atractylodis Macrocephalae volatile oil is at supercritical CO
2In dissolubility increase, but light composition and heavy ingredient are at supercritical CO
2In the difference of dissolubility reduce, reduced separating effect.After pressure was elevated to 28MPa, fractional distillation was not good to the separating effect of heavy ingredient sesquiterpene.Compositing characteristic according to Rhizoma Atractylodis Macrocephalae volatile oil weight component, use for reference the way that the supercritical chromatographic program boosts, take small amplitude staged to regulate pressure carries out selective extraction to component method, this is equivalent to carry out the fractional distillation of many wheels, guarantee the separating degree of monoterpene light composition and sesquiterpene heavy ingredient simultaneously, can reduce supercritical CO simultaneously
2Consumption, shorten the fractional distillation time.Therefore the fractional distillation pressure preferable procedure mode of boosting boosts to 30MPa from 25MPa in the boost mode of 1MPa of every 20min, and keeps 20min.Rhizoma Atractylodis Macrocephalae oil is after fractionation separates, and the monoterpene composition removes fully, and the content of atractylone reaches more than 50%, satisfies the content requirement of Chinese Pharmacopoeia about five class Chinese medicine intermediate.
Table 6 fractional distillation pressure is to the influence of sesquiterpene complex preparation
Terpene is taken off in embodiment 7 caloic transmission to Rhizoma Atractylodis Macrocephalae volatile oil influence
This example is investigated terpene is taken off in the caloic transmission to Rhizoma Atractylodis Macrocephalae volatile oil influence.200g Rhizoma Atractylodis Macrocephalae medical material is packed in the extractor inner bag into capping.Press the method and parameter of embodiment 1, CO
2Flow speed control is 2～10L/min, fractional distillation pressure be programmed pressure: 25MPa → 30MPa (20min) (1MPa/20min), thermograde is 313K～323K～333K～343K.Collect 1h fraction and 2h fraction respectively, the content of monoterpene and atractylone in the employing gas Chromatographic Determination fraction, the result is as shown in table 7.
Heat in the dephlegmator and the transmission of quality exchange be direct influence Rhizoma Atractylodis Macrocephalae volatile oil take off the terpene effect.When flow velocity is 10L/min, though accelerated Rhizoma Atractylodis Macrocephalae volatile oil diffusion rate in fluid, caused the insufficient of caloic transmission, cause back-mixing, reduce separating effect.Make Rhizoma Atractylodis Macrocephalae volatile oil at supercritical CO as far as possible
2In near saturation, this flow velocity with regard to requiring to keep less and stable is to prolong fraction in the post internal reflux time.Therefore, preferred CO
2Flow velocity is 2～5L/min, can make CO
2With volatile oil two poised state that is close, increased reflux ratio, improved the caloic transmission efficiency, help separating of monoterpene and sesquiterpenoid.
The influence of terpene is taken off in the transmission of table 7 caloic to Rhizoma Atractylodis Macrocephalae volatile oil
Embodiment 1～7 shows, supercritical CO
2Extraction coupling fractionating technology provides a Rhizoma Atractylodis Macrocephalae monoterpene to remove a new way for preparing with sesquiterpene, the extraction that has realized Rhizoma Atractylodis Macrocephalae volatile oil becomes separating/enriching to finish simultaneously with sesquiterpene, effectively overcome traditional method extraction and separate Rhizoma Atractylodis Macrocephalae volatile oil flow process complexity, need to use a large amount of organic solvents, sesquiterpene in separation process, to hold degradation-labile defect, the content of atractylone reaches the prescription of state-promulgated pharmacopoeia about the new Chinese medicine intermediate greater than 50% in the prepared sesquiterpene complex.
Claims (2)
1. method for preparing Rhizoma Atractylodis Macrocephalae sesquiterpene complex may further comprise the steps:
1) dry rhizome of the feverfew Rhizoma Atractylodis Macrocephalae (Atractylodes macrocephala koidz) is put into the supercritical extraction device, extract under the temperature of setting, pressure, extract is with supercritical CO
2Fluid enters in the dephlegmator;
2) under certain fractional distillation pressure, on dephlegmator, apply a thermograde from low to high, the control supercritical CO
2Fluid carries out the segmentation fractional distillation to volatile oil under certain flow rate;
3) volatile oil is separated into monoterpene component and two fraction sections of sesquiterpene complex after fractional distillation, enters separator successively after decompression, collects sesquiterpene complex fraction section, CO
2Emptying after the rotameter metering;
Wherein the described extractor pressure of step 1) is 20～30MPa; The extractor temperature is 308～328K;
Step 2 wherein) described dephlegmator pressure is 25～30MPa, takes the mode of programmed pressure, boosts to 30MPa from 25MPa, and every 20min rising 1MPa, 30MPa keep 20min down; Cut point is 313～343K, is divided into four sections temperature controls, and thermograde is 10K;
Step 2 wherein) described supercritical CO
2Flow velocity is 2～5L/min;
Wherein the described separator pressure of step 3) is 5MPa, and separator temperature is 323K.
2. method according to claim 1 is characterized in that, the Rhizoma Atractylodis Macrocephalae sesquiterpene complex of gained is a molecular weight greater than 204 the sesquiterpene and the mixture of sesquiterpene derivative, and wherein the mass percent of atractylone is not less than 50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102972103A CN101978984B (en) | 2010-09-29 | 2010-09-29 | Method for preparing large-head atractylodes rhizome and sesquiterpene compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102972103A CN101978984B (en) | 2010-09-29 | 2010-09-29 | Method for preparing large-head atractylodes rhizome and sesquiterpene compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101978984A CN101978984A (en) | 2011-02-23 |
| CN101978984B true CN101978984B (en) | 2013-07-24 |
Family
ID=43599539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102972103A Expired - Fee Related CN101978984B (en) | 2010-09-29 | 2010-09-29 | Method for preparing large-head atractylodes rhizome and sesquiterpene compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101978984B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104398552B (en) * | 2014-09-30 | 2017-12-22 | 浙江中医药大学 | A kind of Rhizoma Atractylodis Macrocephalae extract and its application with regulating blood lipid action |
| CN106699711B (en) * | 2016-11-23 | 2018-07-27 | 甘肃中医药大学 | A kind of technique that macroporous absorbent resin isolates and purifies atractyloide I and atractyloide II in Radix Codonopsis |
| EP3678994A4 (en) * | 2017-09-05 | 2021-06-02 | Sensient Natural Extraction Inc. | Purification methods using sorbents and pressurized low-polarity water extraction |
-
2010
- 2010-09-29 CN CN2010102972103A patent/CN101978984B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 张忠义等.超临界CO2萃取-分子蒸馏对白术挥发油的提取分离和GC-MS分析.《分析测试学报》.2003,第22卷(第4期), |
| 超临界CO2萃取-分子蒸馏对白术挥发油的提取分离和GC-MS分析;张忠义等;《分析测试学报》;20030731;第22卷(第4期);61页第1行－26行 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101978984A (en) | 2011-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Giray et al. | Comparing the effect of sub-critical water extraction with conventional extraction methods on the chemical composition of Lavandula stoechas | |
| Peterson et al. | Extraction of essential oil from geranium (Pelargonium graveolens) with supercritical carbon dioxide | |
| EP2844243B1 (en) | Method for preparing a cannabis plant isolate comprising delta-9-tetrahydrocannabinol | |
| CN102504957A (en) | Method for preparing essential oils | |
| JP2023078465A (en) | Cannabis extracts and preparation and use methods thereof | |
| CN101928642B (en) | Method for extracting and separating spice and medicinal components from whole plants of Dendranthema indicum | |
| CN105802738A (en) | Extraction method of Flos chrysanthemi indici volatile oil | |
| Raal et al. | Composition of the essential oil of Levisticum officinale WDJ Koch from some European countries | |
| CN102351819A (en) | Extraction, purification and preparation method of high-purity salvianolic acid B | |
| Noori et al. | Subcritical Water Extraction of Essential Oils from Matricaria Chamomilla L. | |
| CN102965197A (en) | Method for extracting and separating ginger essential oil and ginger oil resin enriched in gingerol | |
| CN101978984B (en) | Method for preparing large-head atractylodes rhizome and sesquiterpene compound | |
| CN103540405A (en) | Method for preparing aromatic plant essential oil by using subcritical CO2 fluid extraction technology | |
| CN105018235A (en) | Method for rapid extracting of rose essential oil from fresh rose flower | |
| Kakasy et al. | Comparative study of traditional essential oil and supercritical fluid extracts of Moldavian dragonhead (Dracocephalum moldavica L.) | |
| CN110373267A (en) | It is a kind of for the additive of extraction essential oil and the extracting method of plants essential oil | |
| Kirimer et al. | Composition of the essential oil of Micromeria congesta | |
| CN105294722B (en) | A kind of preparation method of high-purity glabrene monomer | |
| CN109810789A (en) | A kind of extracting method of ginkgo essential oil | |
| CN109222213A (en) | The green Extraction and enrichment and isolation and purification method of neophytadiene in a kind of tobacco material | |
| CN108042758A (en) | A kind of method that volatile oil in curcuma zedoary medicinal material is separated based on postcritical preparative | |
| CN101255087B (en) | Method for extracting and purifying natural flavor valencene and nootkatone from juglans regia | |
| CN106433985A (en) | Fresh ginger essential oil and preparation method thereof | |
| Poiana et al. | Supercritical carbon dioxide separation of bergamot essential oil by a countercurrent process | |
| CN101606954B (en) | Method for extracting and purifying flavonoid substance from selaginella tamariscina |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130724 Termination date: 20130929 |