CN108084293A - A kind of method of highly selective extraction north Chinese mugwort polysaccharide - Google Patents

A kind of method of highly selective extraction north Chinese mugwort polysaccharide Download PDF

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CN108084293A
CN108084293A CN201810139414.0A CN201810139414A CN108084293A CN 108084293 A CN108084293 A CN 108084293A CN 201810139414 A CN201810139414 A CN 201810139414A CN 108084293 A CN108084293 A CN 108084293A
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extraction
chinese mugwort
polysaccharide
north chinese
highly selective
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CN108084293B (en
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蒋志惠
张元臣
张光杰
张守泉
祁鲲
朱新亮
张坤朋
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HENAN YALINJIE EXTRACTION TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd.
Tangyin Pharmaceutical Industry Development Service Center
Anyang Institute of Technology
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Henan Subcritical Extraction Technology Research Institute Co Ltd
Tangyin County Medical Industry Management Office
Anyang Institute of Technology
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0003General processes for their isolation or fractionation, e.g. purification or extraction from biomass
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/54Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Sustainable Development (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Medicines Containing Plant Substances (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The present invention discloses a kind of method of highly selective extraction north Chinese mugwort polysaccharide, step 1)North Chinese mugwort leaf raw material is dried, is then ground into Argy Wormwood Leaf, step 2 again)Argy Wormwood Leaf is placed in closed extractor, it vacuumizes and reaches 100 kPa, distilled water is injected as extractant, and extraction is added in being extracted after ionic liquid entrainer [C4mim] Cl, extraction temperature is controlled by automatic controller, origin of heat is to be placed in the far infrared generating means, handle for extracting pot bottom, step 3)Liquid flux is pumped into evaporator, constant temperature decompression carrying out precipitation treatment is carried out to the liquid flux in evaporator, crude extract, step 4 are obtained after liquid flux precipitation)Dissolved with 95% ethanol solution, being placed in 4 DEG C of refrigerators makes polysaccharide precipitate completely, using filter, be freeze-dried to north Chinese mugwort polysaccharide, be it is a kind of it is simple for process, input is low, efficient, can industrialization production high-quality north Chinese mugwort polysaccharide extracting process.

Description

A kind of method of highly selective extraction north Chinese mugwort polysaccharide
Technical field
The present invention relates to natural products to extract field, and in particular to a kind of property simple for process, selection is high, recovery rate is high, It will not be to north Chinese mugwort extraction method of polysaccharides that active polysaccharide damages.
Background technology
North Chinese mugwort(Artemisia vulgarisL.)For a kind for composite family artemisia herbaceos perennial Chinese mugwort, the Ming Dynasty Li Shizhen (1518-1593 A.D.)《Compendium of Materia Medica》It carries:“(Chinese mugwort)Book on Chinese herbal medicine does not write local products, but Yun Sheng fields.With Tangyin Fu Dao during Song(Note:I.e. present Tangyin County Fu Dao towns)The north Chinese mugwort for modern age only Tangyin person meaning that person is preferred ... ".North Chinese mugwort is collectively referred to as with Hai Ai, Chinese mugwort, Qi Ai on Chinese history " four big names Chinese mugwort ".North Chinese mugwort herb is medicinal, has wet blood, by cold-dampness, hemostasis, Wen Jing, tocolysis and other effects.North Chinese mugwort yield is high, battalion Form point abundant, crude protein, crude fat, nitrogen-free extracts content are higher;Rich in polysaccharide, essential oil, flavones, mineral in north Chinese mugwort leaf The multiple efficacies ingredient such as matter, trace element, tannic acid and vitamin A, B1, B2, C.It is a kind of natural plant of great Development volue Goods and materials source.
The present immunological regulation of multilist of the effect of north Chinese mugwort polysaccharide, antitumor, antiviral, anticancer, anti-oxidant, anti-aging, beauty Liver and kidney disease symptom, hypoglycemic, antibacterial etc. are alleviated in beauty treatment, treatment.Polysaccharide is soluble easily in water, so extraction polysaccharide is most basic often Method is water extraction and alcohol precipitation method, and the effect of this method extraction polysaccharide is good, at low cost, but impurity is more in extract, especially Protein, subsequent purification process is complicated, it is serious to take longer polysaccharide loss.It is thick that Shen Xia et al. uses response phase method to optimize folium artemisiae argyi Polysaccharide extracting process, it is determined that water carries argyi leaf polysaccharide optimum process condition:99 DEG C of extraction temperature, 2.3 h of extraction time, ratio of water to material 20(Shen Xia, Zhang Yanhong, Yuan Huihui wait Responds Surface Methodologies to optimize in research [J] of folium artemisiae argyi Thick many candies extraction process Patent medicine, 2010,32 (1):48-51.)." mugwort polysaccharides extract and purification process(Application number:201110075571.8)" announce A kind of method using ethanol solution percolation extraction polysaccharide mugwort polysaccharides, subsequently through physiological saline solution, repeatedly removing protein, Finished product is obtained after desalination, technique is cumbersome.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art and provide it is a kind of it is simple for process, input is low, effect Rate is high, can industrialization production high-quality north Chinese mugwort polysaccharide extracting process.
The technical proposal of the invention is realized in this way:
A kind of method of highly selective extraction north Chinese mugwort polysaccharide, it is characterised in that:Comprise the following steps:
Step 1)Pretreatment:Before being extracted, north Chinese mugwort leaf raw material is dried, is then ground into granularity again as 40~60 mesh Argy Wormwood Leaf;
Step 2)Extraction:Pretreated Argy Wormwood Leaf is placed in closed extractor, is vacuumized until vacuum degree in extractor Reach -100 kPa, distilled water is injected into extractor as extractant, folium artemisiae argyi sample is totally submerged, and adds in extraction and uses Ionic liquid entrainer [C4Mim] it is extracted after Cl, the amount of entrainer is the 0.1~1% of extractant volume;
Extraction temperature is controlled by automatic controller, and origin of heat is to be placed in the far infrared generating means, handle for extracting pot bottom, extractor Bottom offers glass vision panel, and far infrared is made to penetrate extractor, 500~1000 W of power, far infrared wave-length coverage 25~200 μm;
Step 3)Precipitation:After extraction, liquid flux is pumped into evaporator, in the material residue and evaporator in extractor Liquid flux carries out constant temperature decompression carrying out precipitation treatment respectively, and crude extract is obtained after liquid flux precipitation;
Step 4)Alcohol precipitation:95% ethanol solution of said extracted object is dissolved, being placed in 4 DEG C of refrigerators makes polysaccharide precipitate completely, then passes through Filtering is freeze-dried to get to north Chinese mugwort polysaccharide.
The step one)Described in drying after folium artemisiae argyi raw material water content be less than 8%.
The step two)Described in the mass volume ratio of pretreated Argy Wormwood Leaf and water be 1:5~15 g/ml, Extraction time be 5~10 minutes, temperature be 105~115 DEG C, pressure be 0.1~0.2 Mpa, cycling extraction 1~3 time.
The step two)Described in extraction can use [C with entrainer4C11OHim]CF3SO3[C4mim]CF3SO3In One kind replace, the amount of entrainer is the 0.1~1% of extractant volume.
The step three)Described in decompression precipitation temperature be 50~65 DEG C.
The step three)Described in slave material residue and liquid flux in the vapor that evaporates, after condensation liquefaction Solvent storage tank is flowed back to, is recycled.
The step four)Described in the mass volume ratio of extract and 95% ethanol solution be 1:3~4,4 DEG C of refrigerators are quiet The time is put as 2~4 h.
The vapor evaporated in the material residue and liquid flux flows back to the knot of solvent storage tank after condensation liquefaction Structure is:By pipeline and the inlet communication of compressor, the outlet of compressor passes through pipeline and condenser for extractor, evaporator Inlet communication, the outlet of condenser are connected with solvent storage tank top.
The positive effect of the present invention is:(1)Water under by the use of subcritical state is as extractant, in closed, anaerobic, low In the extractor of pressure, according to the similar principle to mix of organic matter, the polysaccharide component in material is made to be transferred to the extractant of liquid In, then it is more to be finally obtained by extractant and separation of polysaccharides, then through dedoping step pure north Chinese mugwort by the process of reduction vaporization Sugar.Polysaccharide dissolution rate is high, and dissolution rate is fast.(2)Its energy of photon in far infrared region is less than visible and ultraviolet region Photon, therefore the vibration of polysaccharide molecule can only be excited in the form of stretching, bend, shake and distort, these vibrations and molecule rub Wiping can generate heat, raise the temperature of system, so that polysaccharide dissolves out with high selectivity.The three-dimensional mode of heating of far infrared, And the enhancing to interact caused by molecular vibration between sample and solvent, all so that extraction efficiency greatly improves, significantly contract Short extraction time.In addition, far infrared radiation and polarity and nonpolar solvent are all compatible, and harmless.(3) Ionic liquid is interacted by hydrophily, hydrogen bond and steric effect are used as predominant intermolecular forces, optionally in sample Polysaccharide component is combined, and so as to promote solvability of the extraction system for polysaccharide, realizes that system extracts for the selectivity of polysaccharide It takes.
Therefore, the present invention has the following advantages in the case where far infrared is strengthened with ionic liquid auxiliary:Asepsis environment-protecting, it is non- Hot-working prevents oxidation, does not destroy Product Activity, and extraction selectivity is high, and product purity is high, and production capacity is big, can industrialize big rule Mould produces, energy saving, operating cost is low etc., has very wide application prospect.
Description of the drawings
Fig. 1 is the extraction equipment schematic diagram of the application.
Fig. 2 is the glucose curve of embodiment 1.
Specific embodiment
Reference numeral:1- solvents holding vessel, 2- extractors, 3- evaporators, 4- receiving flasks, 5- metering pumps, 6- compressors, 7- Condenser, 8- boilers, 9- heat-exchanger pumps, 101- pressure gauges one, 102- pressure gauges two, 103- pressure gauges three, 111- thermometers one, 112- thermometers two, 113- thermometers three, 13- vacuum pumps, 14- far infrared generating means, handles, 15- controllers
A kind of method of highly selective extraction north Chinese mugwort polysaccharide, comprises the following steps:
Step 1)Pretreatment:North Chinese mugwort leaf is subjected to heated-air drying, the water content of folium artemisiae argyi raw material is made then to be ground into again less than 8% Granularity is 40~60 mesh powders, obtains pretreated north Chinese mugwort leaf sample;
Step 2)Extraction:Argy Wormwood Leaf after crushing is placed in closed extractor, is added by the 0.1~1% of extractant volume Enter ionic liquid [C4mim]Cl、[C4C11OHim]CF3SO3、[C4mim]CF3SO3In it is a kind of as entrainer, vacuumize until Vacuum degree reaches -100 kPa in extractor, and distilled water is injected into extractor as extractant, folium artemisiae argyi sample is soaked completely Not yet, extraction conditions is that the mass volume ratio of pretreated Argy Wormwood Leaf and water is 1:5~15 g/ml, extraction time are 5~10 Minute, temperature is 105~115 DEG C, and pressure is 0.1~0.2 Mpa, and cycling extraction 1~3 time, wherein extraction temperature by controlling automatically Device control processed, origin of heat are to be placed in the far infrared generating means, handle for extracting pot bottom, 500~1000 W of power, far infrared wavelength 25~200 μm of scope;
Step 3)Precipitation:After extraction, liquid flux is pumped into evaporator, folium artemisiae argyi material residue and liquid flux are carried out respectively Constant temperature depressurizes carrying out precipitation treatment, and precipitation temperature is 50~65 DEG C, and liquid flux precipitation obtains extract later.Material residue and liquid are molten The vapor evaporated in agent flows back to solvent storage tank after condensation liquefaction, recycles.
Step 4)Alcohol precipitation:Said extracted object and 95% ethanol solution are pressed into mass volume ratio 1:3~4 are dissolved, and are placed in 4 DEG C refrigerator stands 2~4 h, using filter, is freeze-dried to get to north Chinese mugwort polysaccharide.
Embodiment 1, the making of glucose standard curve and the detection method of north Chinese mugwort polysaccharide
The detection of polysaccharide is carried out using phend-sulphuric acid, draws glucose standard curve first:It is dried extremely under the conditions of taking 105 DEG C The dextrose standard sample configuration concentration of constant weight is the mother liquor of 0.1 mg/mL, and row order of going forward side by side ladder dilution, ultimate density, which is respectively configured, is 0.01st, the standard solution of 0.02,0.03,0.04 and 0.05 mg/mL;The standard solution of 2 mL various concentrations is respectively taken, is sequentially added The phenol solution of 1 mL 5% and the 5 mL concentrated sulfuric acids, 10 min of boiling water bath after mixing, take out and are cooled to room temperature, made with distilled water Blank measures light absorption value at 490 nm, records data;Using glucose standard concentration as abscissa, light absorption value OD490 is vertical Coordinate makes standard curve(Fig. 2), and be fitted and obtain regression equation:
Y=13.205x+0.236
Related coefficient:R 2 = 0.98977
The range of linearity:0.01-0.05 mg/mL.
The detection of north Chinese mugwort polysaccharide:0.001 g polyoses extracts is taken to be prepared into the aqueous solution that concentration is 50.0 μ g/mL, are taken 1.0 mL are placed in 15 mL tool plug test tubes, sequentially add the phenol solution and the 5 mL concentrated sulfuric acids of 1 mL 5%, boiling water bath after mixing 10 min, take out and are cooled to room temperature, and make blank with distilled water, and light absorption value is measured at 490 nm, record data, substitute into and return Equation is the concentration that can obtain polysaccharide.
Embodiment 2, traditional water extraction and alcohol precipitation method extraction polysaccharide extraction
With document report(Shen Xia, Zhang Yanhong, Yuan Huihui wait Responds Surface Methodologies optimization folium artemisiae argyi Thick many candies extraction process Study [J] Chinese patent drugs, 2010,32 (1):48-51.)The folium artemisiae argyi Thick many candies extraction optimum condition that response phase method optimizes Carry out the extraction of north Chinese mugwort polysaccharide:99 DEG C of extraction temperature, 2.3 h of extraction time, ratio of water to material 20.Extracting solution is carried out after extraction Centrifugal treating, 5000 rpm of rotating speed, 15 min of time;Supernatant after centrifugation is concentrated under reduced pressure, and 4 times of volumes of addition 95% ethanol solution is placed in 4 DEG C of 4 h of refrigerator, polysaccharide is made to precipitate completely, using filter, is freeze-dried to get to north Chinese mugwort polysaccharide.
It is calculated with 1 method therefor of embodiment, the purity of gained polysaccharide is 518.61 mg/g.
Embodiment 3, method therefor of the present invention extract north Chinese mugwort polysaccharide
North Chinese mugwort leaf of the water content less than 8% is smashed it through into 40 mesh sieves, 100 g is taken to be placed in extractor, are vacuumized until extractor Interior vacuum degree reaches -100 kPa, and distilled water is injected into extractor as extractant, folium artemisiae argyi sample is totally submerged, folium artemisiae argyi Mass volume ratio with distilled water is 1:8 g/ml, extraction entrainer are [C4Mim] 8 g of Cl ionic liquids, extraction temperature by The far infrared generating means, handle Collaborative Control of automatic controller and extraction pot bottom is at 110 DEG C, 1000 W of far infrared power, wavelength model 25~200 μm are enclosed, extracting pressure is 0.15 Mpa, and extraction time is 6 minutes, cycling extraction 2 times;After extraction, by liquid Solvent is pumped into evaporator, carries out constant temperature decompression carrying out precipitation treatment respectively to folium artemisiae argyi material residue and liquid flux, and precipitation temperature is 65 DEG C;It will Extract and 95% ethanol solution after precipitation press mass volume ratio 1:3 are dissolved, and are placed in 4 DEG C of refrigerators and are stood 2 h, using Filter is freeze-dried to get to north Chinese mugwort polysaccharide.
It is calculated with 1 method therefor of embodiment, the purity of gained polysaccharide is 761.48mg/g.The knot of comparative example 2 Fruit is it can be found that the present embodiment carries out under undercritical conditions, and combines Far-infrared spoke and shine and ionic liquid entrainment, extraction effect Rate is obviously improved, and extraction time is shortened to 6 minutes and cycled 2 times by 2.3 original h.Extraction process is to north Chinese mugwort polysaccharide simultaneously Selectivity significantly increases, and polyoses content is promoted by 284.61 mg/g to 761.48 mg/g in extract.
4 method therefor of the present invention of embodiment extracts north Chinese mugwort polysaccharide
North Chinese mugwort leaf of the water content less than 8% is smashed it through into 40 mesh sieves, 100 g is taken to be placed in extractor, are vacuumized until extractor Interior vacuum degree reaches -100 kPa, and distilled water is injected into extractor as extractant, folium artemisiae argyi sample is totally submerged, folium artemisiae argyi Mass volume ratio with distilled water is 1:10 g/ml, extraction entrainer are [C4C11OHim]CF3SO310 g of ionic liquid, extraction Take temperature by the far infrared generating means, handle Collaborative Control of automatic controller and extraction pot bottom at 105 DEG C, far infrared power 800 W, 25~200 μm of wave-length coverage, extracting pressure are 0.10 Mpa, and extraction time is 8 minutes, cycling extraction 2 times;Extraction terminates Afterwards, liquid flux is pumped into evaporator, carries out constant temperature decompression carrying out precipitation treatment, precipitation temperature respectively to folium artemisiae argyi material residue and liquid flux For 65 DEG C;Extract after precipitation and 95% ethanol solution are pressed into mass volume ratio 1:4 are dissolved, and are placed in 4 DEG C of refrigerators and are stood 3 H using filter, is freeze-dried to get to north Chinese mugwort polysaccharide.
It is calculated with 1 method therefor of embodiment, the purity of gained polysaccharide is 865.26 mg/g.Comparative example two As a result it can be found that the present embodiment carries out under undercritical conditions, and combine Far-infrared spoke and shine and ionic liquid entrainment, extraction Efficiency is obviously improved, and extraction time is shortened to 8 minutes and cycled 2 times by 2.3 original h.Extraction process is to north Chinese mugwort polysaccharide simultaneously Selectivity significantly increase, polyoses content is promoted by 284.61 mg/g to 865.26 mg/g in extract.
Above-described embodiment the result shows that, of the invention compared with traditional water extraction and alcohol precipitation method, simple for process, the material residue after extraction It will not be denatured, not influence to be processed further utilizing;Molecular vibration, ionic liquid and the target product that far infrared excites Intermolecular interaction makes the polysaccharide in sample dissolve out with high selectivity, improves the content of polysaccharide in extract;It is in addition, remote The enhancing to interact caused by infrared three-dimensional mode of heating, molecular vibration between sample and solvent so that extraction efficiency is big It is big to improve, significantly shorten extraction time.
Although the present invention has been described by way of example and in terms of the preferred embodiments, it is not limited to the present invention, and the present invention is similary suitable For other sample classes.Any person skilled in the art without departing from the spirit and scope of the present invention, can do various change Dynamic and modification, therefore protection scope of the present invention should be subject to what claims were defined.

Claims (8)

  1. A kind of 1. method of highly selective extraction north Chinese mugwort polysaccharide, it is characterised in that:Comprise the following steps:
    Step 1)Pretreatment:Before being extracted, north Chinese mugwort leaf raw material is dried, is then ground into granularity again as 40~60 mesh Argy Wormwood Leaf;
    Step 2)Extraction:Pretreated Argy Wormwood Leaf is placed in closed extractor, is vacuumized until vacuum degree in extractor Reach -100 kPa, distilled water is injected into extractor as extractant, folium artemisiae argyi sample is totally submerged, and adds in extraction and uses Ionic liquid entrainer [C4Mim] it is extracted after Cl, the amount of entrainer is the 0.1~1% of extractant volume;
    Extraction temperature is controlled by automatic controller, and origin of heat is to be placed in the far infrared generating means, handle for extracting pot bottom, extractor Bottom offers glass vision panel, and far infrared is made to penetrate extractor, 500~1000 W of power, far infrared wave-length coverage 25~200 μm;
    Step 3)Precipitation:After extraction, liquid flux is pumped into evaporator, in the material residue and evaporator in extractor Liquid flux carries out constant temperature decompression carrying out precipitation treatment respectively, and crude extract is obtained after liquid flux precipitation;
    Step 4)Alcohol precipitation:95% ethanol solution of said extracted object is dissolved, being placed in 4 DEG C of refrigerators makes polysaccharide precipitate completely, then passes through Filtering is freeze-dried to get to north Chinese mugwort polysaccharide.
  2. 2. the method for highly selective extraction north Chinese mugwort polysaccharide according to claim 1, it is characterised in that:The step one) Described in drying after folium artemisiae argyi raw material water content be less than 8%.
  3. 3. the method for highly selective extraction north Chinese mugwort polysaccharide according to claim 1, it is characterised in that:The step two) Described in the mass volume ratio of pretreated Argy Wormwood Leaf and water be 1:5~15 g/ml, extraction time are 5~10 minutes, temperature It spends for 105~115 DEG C, pressure is 0.1~0.2 Mpa, cycling extraction 1~3 time.
  4. 4. the method for highly selective extraction north Chinese mugwort polysaccharide according to claim 1, it is characterised in that:The step two) Described in extraction can use [C with entrainer4C11OHim]CF3SO3[C4mim]CF3SO3In one kind replace, entrainer It measures as the 0.1~1% of extractant volume.
  5. 5. the method for highly selective extraction north Chinese mugwort polysaccharide according to claim 1, it is characterised in that:The step three) Described in decompression precipitation temperature be 50~65 DEG C.
  6. 6. according to the method for the highly selective extraction north Chinese mugwort polysaccharide of claim 1-5 any one of them, it is characterised in that:Described Step 3)Described in slave material residue and liquid flux in the vapor that evaporates, solvent storage tank is flowed back to after condensation liquefaction, It recycles.
  7. 7. according to the method for the highly selective extraction north Chinese mugwort polysaccharide of claim 1-5 any one of them, it is characterised in that:Described Step 4)Described in the mass volume ratio of extract and 95% ethanol solution be 1:3~4,4 DEG C of refrigerator time of repose are 2~4 h.
  8. 8. the method for highly selective extraction north Chinese mugwort polysaccharide according to claim 6, it is characterised in that:The material residue and liquid The vapor evaporated in body solvent, the structure that solvent storage tank is flowed back to after condensation liquefaction are:Extractor, evaporator are logical The inlet communication of pipeline and compressor is crossed, the outlet of compressor passes through pipeline and the inlet communication of condenser, the outlet of condenser It is connected with solvent storage tank top.
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CN111481582A (en) * 2020-04-13 2020-08-04 珠海中科先进技术研究院有限公司 Method for extracting wormwood polyphenol from EDTA (ethylene diamine tetraacetic acid) alcamines ionic liquid

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