CN101575279B - Method for supercritical fluid extraction of juglone in walnut seed green skin waste residue - Google Patents
Method for supercritical fluid extraction of juglone in walnut seed green skin waste residue Download PDFInfo
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- CN101575279B CN101575279B CN200910148072A CN200910148072A CN101575279B CN 101575279 B CN101575279 B CN 101575279B CN 200910148072 A CN200910148072 A CN 200910148072A CN 200910148072 A CN200910148072 A CN 200910148072A CN 101575279 B CN101575279 B CN 101575279B
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- extraction
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- regianin
- juglone
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- 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
Abstract
The invention discloses a method for supercritical fluid extraction of juglone in walnut seed green skin waste residue. In the invention, supercritical CO2 fluid in the supercritical fluid extraction method is adopted for extracting, walnut seed external skin (green skin) waste residue which is high in juglone content and easily available is preferably selected as the raw material for extraction. The best conditions are as follows: flow rate of the supercritical CO2 fluid is 1-3L/min, the extraction pressure is 10-18MPa, the extraction temperature is below 65 DEG C and the extraction time is within 20min. In the invention, one-time extraction yield of the juglone reaches 87%, the product purity is 92%, the productive rate is 0.21%. The method of the invention features not only high extraction yield but also innocuity, no taste, incombustibility, no erosion, low price and easy recovering of the extraction liquid, thus meeting the requirements of environmental protection and industrialization. The extracted juglone is wide in application, the active ingredients play a role in resisting bacterium and cancer and calming nervus centralis, thus enjoying very wide application prospect inmedicine, agricultural chemical, dye and pH indicator and other fields.
Description
Technical field
The present invention relates to a kind of process for extracting of regianin, more particularly say, relate to a kind of supercritical extraction method of active skull cap components regianin.
Background technology
Regianin is the activeconstituents that from the prematurity outer peel of juglandaceae plant-English walnut and congener black walnut thereof (being rascal), extracts, and has antibiotic, anticancer and the nervus centralis sedative effect.The regianin of from the mixed solution of benzene and sherwood oil, separating out is orange-yellow needle crystal, and the regianin of from chloroform, separating out is the crystallization of reddish yellow prism-shaped, and it has special foul smell flavor, and fusing point is 155 ℃, can distil; And can volatilize with water vapour.Regianin is insoluble to cold water, is slightly soluble in hot water, dissolves in ethanol, ether, and can be miscible with chloroform, benzene.When it is dissolved in alkaline solution, be red-purple, be blood red when being dissolved in the vitriol oil.In the prior art, the process for extracting of regianin mainly contains three kinds: and conventional extraction method, soxhlet extraction and ultrasonic-assisted extraction method (specifically can be referring to Sun Molong. Juglans mandshurica total flavones and regianin assay. chemistry of forest product and industry, 2006,26 (2): 93).Wherein, conventional extraction method adopts organic solvents such as chloroform, benzene to carry out lixiviate, and vat liquor concentrates again, separates out crystal then.It is refining to carry out recrystallization etc. in case of necessity again.The extraction time 2.0h of (referring to Sun Molong, application number is the one Chinese patent application of 200610150876.X) this method, extraction effect is better, is one of domestic method of extracting at present regianin.And soxhlet extraction is used for the extraction in the testing laboratory more, and its extraction effect is relatively poor, 3h consuming time.Ultrasonic extraction 1.5h consuming time, extraction yield are slightly high, are superior to preceding two kinds of methods.Yet,, can not guarantee the validity of extract because extraction time length will cause regianin to destroy.Because these three kinds of process for extracting have all used a large amount of organic solvents, organic solvent reclaims difficulty and causes environmental pollution easily, does not meet environmental requirement, has greatly limited the use of these methods again.Therefore, research is efficient, the method for the extraction regianin of energy-saving and environmental protection has bigger Practical significance, will make huge contribution for society.
At present, utilize supercutical fluid to extract and just obtaining extensive concern, still,, utilize the method for supercritical fluid extraction regianin, especially utilize SC-CO in the green peel of walnut waste residue through retrieval with natural product such as purifying medicine, food
2The method of (supercritical carbon dioxide fluid) extraction regianin does not see that also report is arranged.
Summary of the invention
The method that the purpose of this invention is to provide the regianin in a kind of method of extracting regianin, particularly supercritical extraction green peel of walnut waste residue, this method is a raw material with walnut fruit crust waste residue, through supercritical technology, utilizes supercritical CO
2Fluid extracts regianin from the rascal histocyte of rascal waste residue.This method is not only quick, extraction yield is high, and extracting solution nontoxic, tasteless, do not fire, burn into low price and be easy to reclaim not, satisfied environmental protection and industrialization demands.
In order to realize the foregoing invention purpose, the present invention has adopted following technical scheme:
A kind of method of extracting regianin is wherein utilized supercritical CO through supercritical extraction
2Fluid extracts.Preferably higher and draw materials easily that walnut shell (rascal) waste residue is that raw material extracts with regianin content.
Particularly, the method for extraction regianin of the present invention may further comprise the steps:
1, preparation supercritical CO
2Fluid;
2, under the temperature and pressure of setting, make the supercritical CO of preparation
2Fluid flows through column extractor, in the column extractor there is through broken and filtering green peel of walnut powder, supercritical CO prepackage
2Fluid contacts about 30 minutes with powder after (static extracting duration of contact) begin to receive product to receiving fully; Supercritical CO wherein
2Flow rate of fluid is 1～3L/min, preferred 1.5L/min; Extracting pressure 10～18Mpa, extraction temperature is below 65 ℃; The extraction time (promptly finishing to receiving with micrometering valve) from opening dropping valve within 20min, preferred 15min (dynamic extraction time).Above-mentioned numerical range can arbitrary combination, does not have inevitable corresponding relation.
3, extract is along with supercritical CO
2Fluid carries out throttling expansion through the fine adjustment valve, subsequently extract and supercritical CO
2The CO that fluid is transformed into
2Gas separates in receiving bottle, and is received by receiving bottle, and CO
2Through discharging after the under meter metered volume; The extraction experiments apparatus sketch is as shown in Figure 1.
4, after extract and the chloroform solvent oscillation treatment,, concentrate and obtain regianin through the decompression rotary evaporation.
Further, the step of preparation supercutical fluid is included in through inlet valve and gets into before the column extractor, the CO that will come out from steel cylinder
2After cold temperature groove cooling, get into HPP, and boost to 10MPa-18MPa.
Wherein, extracting pressure is regulated through the HPP that column extractor connects, and its sharpness of regulation is ± 1%;
Wherein, column extractor heats through the heated constant temperature casing, and temperature is regulated through temperature regulator and shown that control accuracy is ± 0.1 ℃.
Remarkable advantage of the present invention is, 1. higher and draw materials easily that walnut fruit crust (rascal) waste residue is a raw material with regianin content, nontoxic, tasteless, do not fire, not burn into low price, the CO that is easy to reclaim
2For supercutical fluid (Tc=31.3 ℃, Pc=7.38MPa), utilize supercritical extraction, to treatment the extracting of cancer drug, the method for another kind of extraction medicine is provided.2. this method is quick, and carries out at a lower temperature, can effectively avoid the decomposes of regianin, has guaranteed the validity of extract.3. extraction yield is high, is superior to all methods of report at present.4. be widely used, but medicine, also agricultural chemicals.At medicine, agricultural chemicals, dyestuff, perfume base, there is boundless application prospect aspects such as pH indicator.
Description of drawings
Fig. 1 is the extraction experiments apparatus sketch of method that is used for the supercritical extraction green peel of walnut waste residue regianin of embodiment of the present invention.
Wherein, 1 CO
2Steel cylinder; The 2-cooling tank; The 3-HPP; The 4-pressure controller; The 5-inlet valve; The 6-column extractor; The 7-thermostat container; The 8-dropping valve; The 9-micrometering valve; The 10-receiving bottle; The 11-spinner-type flowmeter; 12-column extractor temperature regulator; 13-spin manifold temperature unit; 14-micrometering valve temperature regulator.
Fig. 2 is the IR spectrogram of regianin standard specimen, product;
Fig. 3 is the GC figure of regianin mark article;
Fig. 4 is regianin product G C figure;
Fig. 5 is regianin mark article MS figure;
Fig. 6 is regianin product MS figure.
Embodiment
Below in conjunction with concrete accompanying drawing and embodiment the present invention is further described.
The key instrument that the present invention uses comprises: SFT-100 supercritical extraction small testing device (U.S.); FE80 Universalpulverizer (neat housework scientific instrument factory); 220A dual wavelength scanning spectrophotometer (Japan); The AEL-160 electronic balance; PE-52A rotatory evaporator (Shanghai Yarong Biochemical Instrument Plant); SHB-III circulation ability of swimming is used vacuum pump (Zhengzhou Greatwall Scientific Industrial & Trading Co., Ltd.) more; AVATAR360 type Fourier transformation infrared spectrometer (U.S.); GCMS-QP2011S type gas chromatograph-mass spectrometer (day island proper Tianjin).
The main medicine that the present invention uses: anhydrous methanol, regianin standard substance (97%), magnesium acetate, NaOH, HCl available from U.S. Sigma company.
Raw material: green peel of walnut (Zunhua, Hebei, the place of production)
10 kilograms of rascal are used crusher in crushing, filter.The powder of the getting broken shape column extractor of packing into carries out according to the supercritical extraction operation steps.Adjustment CO
2Flow velocity 1.5L/min, extracting pressure 15MPa, 50 ℃ of extractions of temperature, extraction time 15min.Fully contact with raw material, guarantee that about 30min after duration of contact, begins to receive product.Extract is with CO
2Carry out throttling expansion through the fine adjustment valve, extract and CO
2Gas separates the back and is received CO by receiving bottle in receiving bottle
2Through discharging after the under meter metered volume.Recycle.
After extract and the solvent oscillation treatment, through the decompression rotary evaporation concentrate the product regianin, carry out each index determining.Wherein,, obtain regianin mark article and sample collection of illustrative plates (seeing accompanying drawing 1～5), and analyse and compare, confirm that product is a regianin through AVATAR360 type Fourier transformation infrared spectrometer and GCMS-QP2011S type gas chromatograph-mass spectrometer.
Calculating the regianin extraction yield is 87%, and purity is 92%, and productive rate is 0.21%.Effective constituent regianin atlas analysis:
Regianin standard specimen and product ir spectra are at 3065cm among Fig. 2
-1, 2922cm
-1, 1645cm
-1, 1598cm
-1, 1453cm
-1, 1363cm
-1, 1291cm
-1, 750cm
-1There is identical crest the position.
2922cm among the IR figure of regianin product
-1, 2851cm
-1Be-CH
3Flexible, the symmetrical stretching vibration of unsymmetrically, peak intensity shows and contains the impurity of being with methyl in the bullion than the intensity increase of mark article.Other is local higher with the regianin standard specimen infrared spectrogram check analysis goodness of fit, proves that this compound should be regianin.
GC figure Fig. 3 of regianin mark article, the last one peak all also appears in GC figure Fig. 4 of product when RT is 8.4min, be the regianin peak.Among GC Fig. 4 of product, be that the less peak of peak intensity appears in 4.9min, 5.4min, 7.2min, 8.7min, 12.7min, 25.1min, 26.1min, be and the similar impurity peaks of regianin in RT.
Detection ion abundance among mark article mass spectrum Fig. 5 is respectively 4%, 6%, 8.5%, 32%, 33%, 54%, 16%, 100%; Detection ion abundance among product mass spectrum Fig. 6 is respectively 5%, 7%, 9%, 34%, 36%, 57%, 15%, 100%, and the ion abundance in the product differs than the same ion relative abundance with standard substance and is 3% to the maximum.
In sum, can confirm that product is a regianin.
Embodiment 2
10 kilograms of rascal are used crusher in crushing, filter.The powder of the getting broken shape column extractor of packing into carries out according to the supercritical extraction operation steps.Adjustment CO
2Flow velocity 1.0L/min, extracting pressure 18MPa, 65 ℃ of extractions of temperature, extraction time 10min.。Fully contact with raw material, guarantee that about 30min after duration of contact, begins to receive product.Extract is with CO
2Carry out throttling expansion through the fine adjustment valve, extract and CO
2Gas separates the back and is received CO by receiving bottle in receiving bottle
2Through discharging after the under meter metered volume.
After extract and the solvent oscillation treatment, through the decompression rotary evaporation concentrate the product regianin, carry out each index determining.Obtaining the regianin extraction yield is 85%, and purity is 92%, and productive rate is 0.20%.
10 kilograms of rascal are used crusher in crushing, filter.The powder of the getting broken shape column extractor of packing into carries out according to the supercritical extraction operation steps.Adjustment CO
2Flow velocity 3.0L/min, extracting pressure 10MPa, 30 ℃ of extractions of temperature, extraction time 20min.Fully contact with raw material, guarantee that about 30min after duration of contact, begins to receive product.Extract is with CO
2Carry out throttling expansion through the fine adjustment valve, extract and CO
2Gas separates the back and is received CO by receiving bottle in receiving bottle
2Through discharging after the under meter metered volume.
After extract and the solvent oscillation treatment, through the decompression rotary evaporation concentrate the product regianin, carry out each index determining.Obtaining the regianin extraction yield is 80%, and purity is 89%, and productive rate is 0.19%.
Although the preceding text specific embodiments of the invention has given to describe in detail and explanation; But should indicatedly be; We can carry out various equivalences to above-mentioned embodiment according to conception of the present invention and change and modification; When the function that it produced does not exceed spiritual that specification sheets and accompanying drawing contain yet, all should be within protection scope of the present invention.
Claims (6)
1. a method of extracting regianin is characterized in that, through supercritical extraction, utilizes supercritical CO
2Fluid extracts, and is higher and draw materials easily that the walnut husk waste residue is a raw material with regianin content, extracts, and may further comprise the steps:
1) preparation supercritical CO
2Fluid;
2) under the pressure of setting, temperature and time, make the supercritical CO of preparation
2Fluid flows through column extractor, in the column extractor there is through broken and filtering green peel of walnut powder, supercritical CO prepackage
2Fluid with begin to receive product after powder contacts 30min; Supercritical CO wherein
2Flow rate of fluid is 1～3L/min; Extracting pressure 10～18Mpa; Extraction temperature is below 65 ℃; Static extracting time 30min, dynamic extraction time 15min;
3) extract is along with supercritical CO
2Fluid carries out throttling expansion through the fine adjustment valve, subsequently extract and supercritical CO
2The CO that fluid is transformed into
2Gas separates in receiving bottle, and is received by receiving bottle, and CO
2Through discharging after the under meter metered volume;
4) after extract and the chloroform solvent oscillation treatment,, concentrate and obtain regianin through the decompression rotary evaporation.
2. the method for claim 1, wherein controlling extracting pressure is 15Mpa.
3. the method for claim 1, wherein supercritical CO
2Flow rate of fluid is 1.5L/min.
4. the method for claim 1, wherein extraction temperature is 50 ℃.
5. the step that the method for claim 1, wherein prepares supercutical fluid is included in through inlet valve and gets into before the column extractor, the CO that will come out from steel cylinder
2After cold temperature groove cooling, get into HPP, and boost to 10～18Mpa.
6. the method for claim 1, wherein extracting pressure is regulated through the HPP that column extractor connects, and its sharpness of regulation is ± 1%; Column extractor heats through the heated constant temperature casing, and temperature is regulated through temperature regulator and shown that control accuracy is ± 0.1 ℃.
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Cited By (1)
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| CN104529737A (en) * | 2014-12-25 | 2015-04-22 | 北京化工大学常州先进材料研究院 | Method for rectifying vitamin K1 by supercritical carbon dioxide continuous extraction |
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| CN101906030B (en) * | 2010-08-23 | 2013-12-04 | 河北理工大学 | Method for extracting juglone from walnut green husk residue by microwave reflux |
| CN103319321B (en) * | 2013-06-09 | 2014-12-17 | 吕梁学院 | Extraction method of juglone and derivative in walnut green tangerine peel |
| CN103807158B (en) * | 2014-02-25 | 2016-01-13 | 大连理工大学 | Tiny flow quantity continuous adjustment system under high pressure |
| CN104478878B (en) * | 2014-11-08 | 2017-05-31 | 吕梁学院 | A kind of method that separation from green peel of walnut prepares alkaloid |
| CN108969555B (en) * | 2017-09-25 | 2021-08-10 | 安徽九鑫药业有限公司 | A Chinese medicinal composition comprising herba Epimedii with kidney invigorating, blood and essence replenishing, and immunity improving effects, and its preparation method |
| CN111454587B (en) * | 2020-04-24 | 2021-07-13 | 杭州彩润科技有限公司 | Comprehensive processing and utilizing method for dyeing of pericarpium juglandis |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104529737A (en) * | 2014-12-25 | 2015-04-22 | 北京化工大学常州先进材料研究院 | Method for rectifying vitamin K1 by supercritical carbon dioxide continuous extraction |
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