CN106674247A - Method for extracting cantharidin by using supercritical carbon dioxide - Google Patents
Method for extracting cantharidin by using supercritical carbon dioxide Download PDFInfo
- Publication number
- CN106674247A CN106674247A CN201611110775.XA CN201611110775A CN106674247A CN 106674247 A CN106674247 A CN 106674247A CN 201611110775 A CN201611110775 A CN 201611110775A CN 106674247 A CN106674247 A CN 106674247A
- Authority
- CN
- China
- Prior art keywords
- extraction
- cantharidin
- carbon dioxide
- supercritical carbon
- cosolvent
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
- C07D493/18—Bridged systems
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention relates to a method for extracting cantharidin by using supercritical carbon dioxide. The method comprises the following steps: performing raw material pretreatment, crushing, soaking, feeding a soaked material into a supercritical carbon dioxide extraction kettle, adjusting the extraction temperature and the extraction pressure, adding a cosolvent for extraction, and adjusting the velocity of the cosolvent and the extraction time; collecting an extract at the outlet of the kettle, performing vacuum concentration on the extract so as to remove a part of a solvent, performing cooling devitrification on a concentrated solution so as to obtain a crude product of cantharidin, heating to dissolve the crude product by using petroleum ether, filtering so as to remove undissolved substances, and performing cooling devitrification on filtrate, so as to obtain the cantharidin. As the cantharidin is extracted by using the supercritical carbon dioxide, the method is good in extraction property, high in extraction rate, rapid in extraction time, simple in process procedure, convenient to operate, small in environment pollution and is classified as a novel method for efficient extraction, separation, preparation and concentration.
Description
Technical field：
The present invention relates to a kind of method of supercritical carbon dioxide extraction cantharidin, belongs to tcm development technical field, should
For the extraction of cantharidin in Meloidae insecticide Mylabris phalarata or yellow black mylabris cichorii.
Background technology：
Mylabris are Arthropoda Insecta Meloidae (Meloidae) insecticide Mylabris phalarata Mylabris
The black mylabris cichorii Mylabris cichorii L.'s of phalerata Pallas or yellow is dried polypide, with detumescence removing blood stasis, eliminating stagnation
The effects such as note of the ancient Chinese, counteracting toxic substances phagedenoma of disappearing.Principle active component in Mylabris is cantharidin, is the serine (PP1) and Soviet Union's ammonia of specificity
Sour (PP2A) protein phosphatase inhibitor, plays important regulating and controlling effect, with anti-in the activity such as cancer cell multiplication and differentiation
Various drug effects such as tumor, antiviral, leukocyte increasing, immunostimulant.
As cantharidin is utilized more and more widely, people are studied it progressively deeply, current cantharidin extracting method
It is most that using ethanol, chloroform, toluene etc., directly merceration is extracted or concentrated hydrochloric acid is acidified after polypide and is carried with acetone, methylene chloride reflux
Take, above method complex procedures, extraction ratio are low, cycle length, pollution big, harmful to human, pollution environment.And supercritical carbon dioxide
Abstraction technique has Extracting temperature low, and extraction efficiency is high, cycle is short, and pollution is few, low cost and other advantages.
The content of the invention：
The present invention seeks to be directed to current cantharidin extracting method technical deficiency, there is provided a kind of supercritical carbon dioxide is carried
The method for taking cantharidin, it comprises the steps：
(1) pretreatment of raw material：Choose from Mylabris medical material and pick impurity, part of going mouldy, remaining tap water is cleaned, natural
Dry；
(2) crush：The Mylabris medical material dried in above-mentioned (1) is crushed, sieved；
(3) soak：Above-mentioned (2) gained medical material precision weighing is put in volumetric flask and adds entrainer immersion；Medical material and folder
Mass volume ratio with agent is 1:5~10.
(4) supercritical carbon dioxide extraction：By in the sample input supercritical carbon dioxide extraction kettle in above-mentioned (3), adjust
Section extraction temperature is 30~40 DEG C, and extracting pressure is 10~20MPa, and adds the entrainer described in above-mentioned (3) as cosolvent
Extracted, cosolvent flow velocity is 2~10g/min, 2~3h of extraction time；Extract is collected kettle outlet is collected；
(5) concentration, crystallize, purification：Above-mentioned (4) extract concentrating under reduced pressure is boiled off into partial solvent, concentrated solution cooling crystallization
Cantharidin crude product is obtained, crude product petroleum ether heating for dissolving is filtered, and removes insoluble matter, and filtrate cooling crystallization obtains Mylabris
Element；
Entrainer or cosolvent used by described step (3), (4) is the acetone soln that volume ratio is 10~70%.
Described step (2) is crushed, sieve mesh used time of sieving is for 20~30 mesh.
In described step (5), concentrating under reduced pressure pressure is 4~8MPa, filtrate cooling crystallization temperature is 40~50 DEG C.
The method of supercritical carbon dioxide extraction cantharidin of the present invention, is obtained in that compared with prior art following
Good effect：
(1) supercritical carbon dioxide extraction cantharidin extracting power of the present invention is strong, and extraction ratio is high, uses supercritical carbon dioxide
Effective Component of Chinese Medicine is extracted, under optimum process condition, the composition of required extraction almost can completely be extracted, so as to greatly improve
The utilization rate of product yield and resource.
(2) operation temperature of supercritical carbon dioxide extraction cantharidin extraction of the present invention is low, can more fully preserve Chinese medicine
Effective ingredient is not destroyed, and time biochemistry does not occur.
(3) supercritical carbon dioxide extraction cantharidin extraction time of the present invention is fast, with short production cycle, supercritical CO2Extract
At the beginning, separation is just proceeded by for circulation, and general extraction just has composition separation to separate out for 10 minutes, 2~4 hours or so just can be complete
Extract.
(4) supercritical carbon dioxide extraction cantharidin operating parameter of the present invention is easily controlled, therefore can guarantee that effective ingredient
And the stability of product quality.
(5) there is antioxidation, sterilizing to make for supercritical carbon dioxide extraction cantharidin of the present invention, wherein supercritical carbon dioxide
With advantageously ensuring that and improve the quality of product.
(6) supercritical carbon dioxide extraction cantharidin of the present invention technological process is simple, easy to operate, saves labour force and big
Amount organic solvent, reduces three-waste pollution, is the new method of a kind of efficient extracting and developing, preparation and concentration.
Specific embodiment：
Supercritical carbon dioxide extraction cantharidin under the optimal factor level of embodiment 1
Test method：Mylabris medical material is weighed, is chosen from Mylabris medical material and is picked impurity, part of going mouldy, it is remaining to use tap water
Clean, dry naturally；The Mylabris medical material for drying is crushed, sieved, sieve mesh time is 30 mesh；Precision weighs Mylabris medicinal powder
100g is put in volumetric flask, is 1 by the mass volume ratio of sample and entrainer:6 ratios add entrainer to soak 3h, and entrainer is
Volume ratio is 50% acetone soln, and soaked sample is put in the extraction kettle in supercritical device, before being extracted, first will
Carbon dioxide refrigeration liquefies, and arranges extracting pressure 20MPa, and 30 DEG C of temperature, regulation of carbon dioxide enters the inlet valve for collecting kettle
Aperture, will collect the Stress control of kettle in 10MPa, while temperature control is at 30 DEG C, the flow velocity for arranging cosolvent is 5g/min, and two
Carbonoxide flow velocity is 20g/min.Cosolvent is added in extraction kettle by high-pressure pump, and cosolvent is that the acetone that volume ratio is 50% is molten
Liquid, pressure and temperature to be extracted is reached after preset value, starts timing, after extraction 2h, stops extraction, closes dioxide bottle,
Opening manual exhaust valve carries out pressure release, and kettle outlet is collected extract is collected, and above-mentioned extract decompression (pressure is 5MPa) is dense
Contracting boils off partial solvent, and but crystallize obtains cantharidin crude product to concentrated solution cold (temperature is 40 DEG C), crude product petroleum ether heating for dissolving,
Filter, remove insoluble matter, filtrate cooling crystallization obtains cantharidin.Analytical calculation show that cantharidin extracts content up to 2.8%.
Supercritical carbon dioxide extraction cantharidin under the general factor level of embodiment 2
Test method：Mylabris medical material is weighed, is chosen from Mylabris medical material and is picked impurity, part of going mouldy, it is remaining to use tap water
Clean, dry naturally；The Mylabris medical material for drying is crushed, sieved, sieve mesh time is 20 mesh；Precision weighs Mylabris medicinal powder
100g is put in volumetric flask, is 1 by the mass volume ratio of sample and entrainer:10 ratios add entrainer immersion 2h, entrainer
It is acetone soln that volume ratio is 30%, soaked sample is put in the extraction kettle in supercritical device, before being extracted, first
Carbon dioxide refrigeration is liquefied, extracting pressure 15MPa is set, 30 DEG C of temperature, regulation of carbon dioxide enters the inlet valve for collecting kettle
Door aperture, will collect the Stress control of kettle in 20MPa, while temperature control is at 30 DEG C, the flow velocity for arranging cosolvent is 2g/min,
Carbon dioxide flow rate is 20g/min.Cosolvent is added in extraction kettle by high-pressure pump, and cosolvent is the acetone that volume ratio is 30%
Solution, pressure and temperature to be extracted is reached after preset value, starts timing, after extraction 3h, stops extraction, closes carbon dioxide gass
Bottle, opening manual exhaust valve carries out pressure release, and kettle outlet is collected extract is collected, and above-mentioned extract is reduced pressure into (pressure is 8MPa)
Concentration boils off partial solvent, and concentrated solution cooling (temperature is 50 DEG C) crystallize obtains cantharidin crude product, and crude product petroleum ether adds thermosol
Solution, filters, and removes insoluble matter, and filtrate cooling crystallization obtains cantharidin.Analytical calculation show that cantharidin extracts content and is
1.46%.
Supercritical carbon dioxide extraction cantharidin under the poor factor level of embodiment 3
Test method：Mylabris medical material is weighed, is chosen from Mylabris medical material and is picked impurity, part of going mouldy, it is remaining to use tap water
Clean, dry naturally, the Mylabris medical material for drying is crushed, sieved, sieve mesh time is 40 mesh；Precision weighs Mylabris medicinal powder
100g is put in volumetric flask, is 1 by the mass volume ratio of sample and entrainer:3 ratios add entrainer to soak 3h, and entrainer is
Volume ratio is 30% acetone soln, and soaked sample is put in the extraction kettle in supercritical device, before being extracted, first will
Carbon dioxide refrigeration liquefies, and arranges extracting pressure 20MPa, and 30 DEG C of temperature, regulation of carbon dioxide enters the inlet valve for collecting kettle
Aperture, will collect the Stress control of kettle in 10MPa, while temperature control is at 30 DEG C, the flow velocity for arranging cosolvent is 5g/min, and two
Carbonoxide flow velocity is 20g/min.Cosolvent is added in extraction kettle by high-pressure pump, and cosolvent is that the acetone that volume ratio is 50% is molten
Liquid, pressure and temperature to be extracted is reached after preset value, starts timing, after extraction 2h, stops extraction, closes dioxide bottle,
Opening manual exhaust valve carries out pressure release, and kettle outlet is collected extract is collected, and above-mentioned extract decompression (pressure is 5MPa) is dense
Contracting boils off partial solvent, and but crystallize obtains cantharidin crude product to concentrated solution cold (temperature is 40 DEG C), crude product petroleum ether heating for dissolving,
Filter, remove insoluble matter, filtrate cooling crystallization obtains cantharidin.Analytical calculation show that cantharidin extracts content and is
0.914%.
The traditional extraction process of embodiment 4 extracts cantharidin
Test method：Mylabris medical material is weighed, is chosen from Mylabris medical material and is picked impurity, part of going mouldy, it is remaining to use tap water
Clean, dry naturally, the Mylabris medical material for drying is crushed, sieved, sieve mesh time is 30 mesh；Precision weighs Mylabris medicinal powder
100g is put in volumetric flask, and 50% acetone soln, the Mylabris medicinal powder are added toward volumetric flask：Acetone soln presses quality
Than for 1:6,5-10 hours are shaken at normal temperatures and pressures, sucking filtration obtains filtrate, and residue acetone is washed 3 times, each 200ml, sucking filtration,
Merge above-mentioned filtrate several times, the filtrate after merging is carried out into distillation and concentration at 60 DEG C, distill to no liquid flowing out, will steam
Good concentrated solution is cooled to room temperature crystallize and obtains cantharidin crude product, and crude product uses petroleum ether heating for dissolving, filters, and removes insoluble matter,
Filtrate cooling crystallization, that is, obtain cantharidin.It is 0.864% that analytical calculation show that cantharidin extracts content.
Claims (3)
1. a kind of method of supercritical carbon dioxide extraction cantharidin, it is characterised in that comprise the steps：
(1) pretreatment of raw material：Choose from Mylabris medical material and pick impurity, part of going mouldy, it is remaining with tap water clean, dry in the air naturally
It is dry；
(2) crush：The Mylabris medical material dried in above-mentioned (1) is crushed, sieved；
(3) soak：Above-mentioned (2) gained medical material precision weighing is put in volumetric flask and adds entrainer immersion；Medical material and entrainer
Mass volume ratio be 1:5~10.
(4) supercritical carbon dioxide extraction：By in the sample input supercritical carbon dioxide extraction kettle in above-mentioned (3), extraction is adjusted
Temperature is taken for 30~40 DEG C, extracting pressure is 10~20MPa, and adds the entrainer described in above-mentioned (3) to carry out as cosolvent
Extraction, cosolvent flow velocity is 2~10g/min, 2~3h of extraction time；Extract is collected kettle outlet is collected；
(5) concentration, crystallize, purification：Above-mentioned (4) extract concentrating under reduced pressure is boiled off into partial solvent, concentrated solution cooling crystallization is obtained
Cantharidin crude product, crude product petroleum ether heating for dissolving is filtered, and removes insoluble matter, and filtrate cooling crystallization obtains cantharidin；
Entrainer or cosolvent used by described step (3), (4) is the acetone soln that volume ratio is 10~70%.
2. the method for supercritical carbon dioxide extraction cantharidin according to claim 1, it is characterised in that described step
(5) in, concentrating under reduced pressure pressure is 4~8MPa, filtrate cooling crystallization temperature is 40~50 DEG C.
3. the method for supercritical carbon dioxide extraction cantharidin according to claim 1 and 2, it is characterised in that described
Step (2) is crushed, sieve mesh used time of sieving is for 20~30 mesh.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611110775.XA CN106674247A (en) | 2016-12-06 | 2016-12-06 | Method for extracting cantharidin by using supercritical carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611110775.XA CN106674247A (en) | 2016-12-06 | 2016-12-06 | Method for extracting cantharidin by using supercritical carbon dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106674247A true CN106674247A (en) | 2017-05-17 |
Family
ID=58867671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611110775.XA Pending CN106674247A (en) | 2016-12-06 | 2016-12-06 | Method for extracting cantharidin by using supercritical carbon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106674247A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966508A (en) * | 2006-08-18 | 2007-05-23 | 芜湖天远科技开发有限责任公司 | Method for extracting cantharidin |
| CN101108853A (en) * | 2007-07-27 | 2008-01-23 | 贵州大学 | Separation purification process of cantharidin |
| CN101798309A (en) * | 2009-12-04 | 2010-08-11 | 南京泽朗医药科技有限公司 | Method for preparing cantharidin from cantharides |
| CN102146086A (en) * | 2011-04-12 | 2011-08-10 | 贵州金桥药业有限公司 | Preparation method of sodium cantharidate |
| CN102268006A (en) * | 2011-06-15 | 2011-12-07 | 北京联合大学生物化学工程学院 | Method for extracting cantharidin from compound enzyme |
-
2016
- 2016-12-06 CN CN201611110775.XA patent/CN106674247A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966508A (en) * | 2006-08-18 | 2007-05-23 | 芜湖天远科技开发有限责任公司 | Method for extracting cantharidin |
| CN101108853A (en) * | 2007-07-27 | 2008-01-23 | 贵州大学 | Separation purification process of cantharidin |
| CN101798309A (en) * | 2009-12-04 | 2010-08-11 | 南京泽朗医药科技有限公司 | Method for preparing cantharidin from cantharides |
| CN102146086A (en) * | 2011-04-12 | 2011-08-10 | 贵州金桥药业有限公司 | Preparation method of sodium cantharidate |
| CN102268006A (en) * | 2011-06-15 | 2011-12-07 | 北京联合大学生物化学工程学院 | Method for extracting cantharidin from compound enzyme |
Non-Patent Citations (3)
| Title |
|---|
| HUNG-CHI NIAN ET AL.: ""Pressurized CO2 Extraction of Cantharidin from Mylabris for Anticancer Bioactive Component"", 《SEPARATION SCIENCE AND TECHNOLOGY》 * |
| 李俊 等: ""斑蝥中斑蝥素提取工艺研究"", 《苏州大学学报(自然科学版)》 * |
| 王君为 等: ""斑蝥水提液中总斑蝥素提取工艺的优化"", 《广东药学院学报》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104120037A (en) | Extracting method for jasmine flower essential oil | |
| CN106993789B (en) | Method for extracting high-quality propolis by using subcritical multi-component mixed solvent | |
| CN105602719B (en) | A kind of supercritical extraction method of tea oil | |
| CN101463027A (en) | Method for extracting and separating flavone and anthocyanidin from elder fruit | |
| CN104177455A (en) | Method for extracting amygdalin from bitter almond | |
| CN107098942B (en) | Method for subcritical water extraction of kaempferitrin in radish leaves | |
| CN104844584B (en) | A kind of method that Puerarin is extracted in Pueraria lobota slag | |
| CN102138960A (en) | Novel extraction process of dalbergiae oil through super (sub) critical carbon dioxide | |
| CN109651526A (en) | A kind of method of supercritical carbon dioxide extracting low Froude | |
| CN109568360A (en) | A kind of preparation method of Radix Angelicae Pubescentis granule | |
| CN104193711A (en) | New method for extracting apigenin from celery | |
| CN104327092A (en) | Method for extracting artemisinin from artemisia annua L | |
| CN106674247A (en) | Method for extracting cantharidin by using supercritical carbon dioxide | |
| CN100516060C (en) | preparation of flavone compound with guava leaf | |
| CN1332010C (en) | Preparation and purification method for plant linoleic acid | |
| CN110386861A (en) | The novel technological method of cannabidiol is extracted in industrial hemp | |
| WO2016110216A1 (en) | Method for extracting stilbene compounds | |
| CN102649784A (en) | Method for extracting piperlonguminine from long pepper | |
| CN109568402A (en) | A kind of preparation method of white peony root dispensing granule | |
| CN108794551A (en) | A method of preparing high-purity gardenoside from gardenia yellow pigment waste liquor | |
| CN108579123A (en) | The method for extracting liposoluble constituent with solvent recovery integrated apparatus using fat-soluble ingredient cycle extraction | |
| CN103110678A (en) | Method for preparing saponin | |
| CN109568359A (en) | A kind of preparation method of angelica dahurica root dispensing granule | |
| CN107281273A (en) | A kind of method of supercritical carbon dioxide extracting fruit of glossy privet liposoluble constituent | |
| CN106749487A (en) | A kind of method that separating ursolic acid is extracted from seabuckthorn fruit peel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170517 |
|
| RJ01 | Rejection of invention patent application after publication |