CN107445924A - A kind of method of subcritical abstraction pyrethrins - Google Patents
A kind of method of subcritical abstraction pyrethrins Download PDFInfo
- Publication number
- CN107445924A CN107445924A CN201710637580.9A CN201710637580A CN107445924A CN 107445924 A CN107445924 A CN 107445924A CN 201710637580 A CN201710637580 A CN 201710637580A CN 107445924 A CN107445924 A CN 107445924A
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- pyrethrins
- extraction
- subcritical abstraction
- extract
- hfc
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
- C07D307/45—Oxygen atoms acylated by a cyclopropane containing carboxylic acyl radical, e.g. chrysanthemumates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
Abstract
The invention provides a kind of method of subcritical abstraction pyrethrins, including by Dalmatian chrysanthemum raw material subcritical abstraction kettle is put into by crushing pack；1,1,1,2 HFC-134a is added in extraction kettle and makees extractant, in the 1.0MPa of pressure 0.6, temperature is 40 60 DEG C and extracted 30 minutes, extractant evaporation recovery, as extraction finished product after extract purification.The present invention is using extracting pyrethrin under subcritical and pressurized conditions, and higher than conventional method recovery rate, content is high, and post processing is simple, and whole process temperature effectively can prevent pyrethrins from volatilizing in high temperature environments below 60 DEG C.
Description
Technical field
The present invention relates to pyrethrins extractive technique field, and in particular to a kind of method of subcritical abstraction pyrethrins.
Background technology
Dalmatian chrysanthemum is the pesticide plant of current intensive cultivating unique in the world, and Dalmatian chrysanthemum is also a kind of for treating skin
Sick " mange ", the herbal medicine of children's " anthelmintic ".Insecticide-the pyrethrins extracted from Dalmatian chrysanthemum exists because of its non-harmful feature
Supply falls short of demand for international market, and Dalmatian chrysanthemum is the certification first choice Biocidal medicament of organic food, pollution-free food.Dalmatian chrysanthemum plant height 50
Centimetre, May blooms, and one plant of full-bloom stage can be wounded 200 or so.There is very much ornamental value, can be potted plant for optimizing the environment.Interior 4
The effect of repellent mosquitos and flies can be played by square metre putting a basin, and effect is fairly obvious.1st, Dalmatian chrysanthemum fruit-bearing forest garden set is planted：One mu of fruit-bearing forest set cultivation removes
200 plants of worm chrysanthemum, every 3-4 square metres are planted one plant, can effectively be suppressed insect and be entered orchard, deduction and exemption use the harm of chemical pesticide.
Also Dalmatian chrysanthemum cane can be cut into broken embedment underground in autumn end can kill the insect that survives the winter.2nd, Dalmatian chrysanthemum plant transplants：Ox, sheep, pig,
In chicken, plant, average 4 square metres of one plant of Dalmatian chrysanthemums can mosquitos and flies in repellent field.Dalmatian chrysanthemum dry product is crushed and is sprinkled into colony house,
The parasites such as poultry ectosome not pediculosis, flea, bedbug can be made, summer can control fly maggot life to overflow, prevent transmission.3rd, deinsectization
Chrysanthemum is used for house greening and interior decoration, the existing higher economic value of Dalmatian chrysanthemum to be had ornamental value, uses it as indoor drive again
Except mosquito, fly view and admire potted landscape industry development, its economic benefit is also very considerable, every mu can income members up to ten thousand.The root of Dalmatian chrysanthemum, stem,
Leaf, flower etc. all contain poisonous insect element material, are the raw materials for extracting pyrethrins, are the good raw materials for preparing various insecticides, remove
Worm chrysanthemum is the deadly enemy of the insects such as aphid, mosquitos and flies, dark greyish green, cotton boll.The mosquito-repellent incense made of pyrethrum leaves, can with mosquitocidal drive fly, to bedbug,
Louse and flea have special efficacy.Dalmatian chrysanthemum is free from environmental pollution, does not destroy the ecological balance, no resistance to the action of a drug, people and animals' poultry lactation is moved
The advantages that thing nonhazardous, therefore artificial cultivation Dalmatian chrysanthemum is greatly developed, there are bright prospects.
It is domestic at present using being all n-hexane sub-critical extraction, because n-hexane is inflammable and explosive, to employee's equipment requirement and
Environmental requirement is higher, easily anti-event of making trouble.And supercritical carbon dioxide extracting because equipment design and manufacture cost and operating cost compared with
Height, because pressure is excessive, treating capacity is small, and carbon dioxide is nonpolar molecule, low to pyrethrins extraction yield, is not suitable for work
Industry metaplasia is produced.And a kind of novel extraction technology that subcritical fluid extraction technology, which is developed recently, gets up, according to the similar original that mixes
Reason, molecule diffusion is carried out by extract and extractant in a reservoir, then by being evaporated under reduced pressure extractant and purpose product point
From finally giving a kind of technology of purpose product.
The content of the invention
In view of this, the invention provides a kind of method of subcritical abstraction pyrethrins, can be incited somebody to action by subcritical abstraction
Pyrethrins extracts totally and without other solvent contaminations substantially in raw material, reduces last handling process.
The invention provides a kind of method of subcritical abstraction pyrethrins, step includes：
S1, raw material subcritical abstraction:Raw material is added into tetrafluoro as in extraction container, vacuumizing in backward extraction container
Ethane liquid, 40-60 DEG C of temperature, static pressure extraction 20-40min under pressure 0.8-1Mpa；40-60 DEG C of temperature, pressure 0.6-
0.8Mpa, dynamic extraction 15-25min；Then gaseous state HFC-134a is extracted at 55-65 DEG C and carries out heating decompression separation, collected
Pyrethrins extract；
S2, pyrethrins purification；Extractant is added into pyrethrins extract, takes oil reservoir to be concentrated to give most after layering
Whole pyrethrins extract.
The beneficial effects of the invention are as follows：Loss of effective components mistake be present for the existing method for preparing pyrethrins in the present invention
Greatly, extraction yield is low, post-processes the shortcomings of complicated, there is provided a kind of efficient, the side of the easy subcritical abstraction pyrethrins of environmental protection
Method, this method can extract pyrethrins in raw material substantially clean and without other solvent contaminations, reduce last handling process, whole
Individual process temperature effectively can prevent pyrethrins from volatilizing in high temperature environments below 60 DEG C, and the pyrethrins of final products contains
Amount>38%, moisture content ＜ 5%, pyrethrins yield ＞ 80%.Meanwhile this method is adapted to mass produce pyrethrins, is big
Push wide pyrethrins purposes and development provides advantage.
Embodiment
The invention provides a kind of method of subcritical abstraction pyrethrins, step includes：
S1, raw material subcritical abstraction:Raw material is added into tetrafluoro as in extraction container, vacuumizing in backward extraction container
Ethane liquid, 40-60 DEG C of temperature, static pressure extraction 20-40min under pressure 0.8-1Mpa；40-60 DEG C of temperature, pressure 0.6-
0.8Mpa, dynamic extraction 15-25min；Then gaseous state HFC-134a is extracted at 55-60 DEG C and carries out heating decompression separation, collected
Pyrethrins extract；
S2, pyrethrins purification；Extractant is added into pyrethrins extract, takes oil reservoir to be concentrated to give most after layering
Whole pyrethrins extract.
Pyrethrins in raw material can substantially be extracted clean and simply, adopted without other solvent contaminations, post processing by this method
Extractant is made with HFA 134a and carries out subcritical abstraction, avoids using inflammable and explosive n-hexane, process safety and is removed
Worm chrysanthemum ester takes rate high, and content is high, and processing step is easy to operate and realize, streamlining, is very suitable for mass producing Dalmatian chrysanthemum
Ester.
Preferably, in step S1, the dynamic extraction is to make HFC-134a liquid in extraction process in extraction container and divide
From being circulated in container.
Preferably, in step S1, the extraction gaseous state HFC-134a is in extract gaseous state HFC-134a to extraction system
Tend under conditions of vacuum.The heating decompression separation step is carried out in separation container, and gaseous state tetrafluoro second is extracted by air compressor machine
Alkane in separation container until be in close to vacuum state, recovery HFC-134a gas.By step S1 processing, obtained extraction
Pyrethrins content in liquid>30%, moisture content ＜ 10%, pyrethrins yield ＞ 80%.
Preferably, it is described to vacuumize to make pressure in below 150Pa in step S1.
Preferably, in step S1, the raw material is the Dalmatian chrysanthemum for being crushed to 60-100 mesh.
Preferably, in step S2, the extractant is petroleum ether, and the petroleum ether dosage is pyrethrins extract volume
Twice.The extractant is not limited to petroleum ether, can also use the insoluble solvent of other pyrethrins.
Preferably, in step S2, the concentration is the vacuum concentration carried out under pressure 0.09-0.095MPa.By this
Pyrethrins content in the final extract obtained after true concentration>38%, moisture content ＜ 5%.
For the ease of understanding the present invention, present invention work more comprehensively, is meticulously described below in conjunction with embodiment, but this hair
Bright protection domain is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1
A kind of method of subcritical abstraction pyrethrins is present embodiments provided, step includes：
(1) raw material are handled for the first time, the raw material Dalmatian chrysanthemum for taking 100Kg pyrethrins content to be 2.7%, raw material are carried out
It is crushed to 60-100 mesh.
(2) second of processing of raw material, below 150Pa is down to by being vacuumized in the raw material input extraction kettle after crushing, is arranged
Air to the greatest extent in kettle；Then out of storage tank toward squeezing into HFC-134a liquid untill raw material is flooded in extraction kettle, static pressure extraction
30min, temperature 50 C, pressure 0.8Mpa；Open No. 1 air compressor and carry out dynamic extraction, extract HFC-134a liquid
Extraction 20min, temperature 50 C, pressure 0.6MPa are circulated in kettle and separating still；By HFC-134a in extraction kettle and extract
It is put into separating still, heating decompression separation is then carried out in separating still, temperature is 60 DEG C, starts No. 2 air compressor machines and extracts gaseous state
HFC-134a in separating still until be in close to vacuum state, recovery HFC-134a gas, collection pyrethrins (extract)
7.2KG.Wherein pyrethrins content 31.2%, moisture content 9%, pyrethrins yield 83.2%.
(3) purification of pyrethrins：The petroleum ether of 2 times of amounts of volume will be added in pyrethrins extract, taken after being layered
Oil reservoir is concentrated in vacuo, and is that 0.09MPa vacuums obtain final extract 5.73Kg, wherein pyrethrins content in pressure
38.5%, moisture content 4.5%.
It is described above, pyrethrins yield=(gained pyrethrins quality × content)/(pyrethrins quality in raw material ×
Content) × %, similarly hereinafter.
Embodiment 2
Present embodiments provide it is a kind of provide a kind of method of subcritical abstraction pyrethrins, step includes：
(1) raw material are handled for the first time, the raw material Dalmatian chrysanthemum for taking 100Kg pyrethrins content to be 2.7%, raw material are carried out
It is crushed to 60-100 mesh.
(2) second of processing of raw material, below 150Pa is down to by being vacuumized in the raw material input extraction kettle after crushing, is arranged
Air to the greatest extent in kettle；Then out of storage tank toward squeezing into HFC-134a liquid untill raw material is flooded in extraction kettle, static pressure extraction
30min, 40 DEG C of temperature, pressure 1Mpa；Open No. 1 air compressor and carry out dynamic extraction, make HFC-134a liquid in extraction kettle
And extraction 20min, 40 DEG C of temperature, pressure 0.8MPa are circulated in separating still；HFC-134a in extraction kettle and extract are put
Enter in separating still, heating decompression separation is then carried out in separating still, temperature is 60 DEG C, starts No. 2 air compressor machines and extracts gaseous state four
Fluoroethane in separating still until be in close to vacuum state, recovery HFC-134a gas, collection pyrethrins (extract)
6.8KG.Wherein pyrethrins content 32.8%, moisture content 8.8%, pyrethrins yield 82.6%.
(3) purification of pyrethrins：2 times of amount petroleum ethers will be added in pyrethrins extract, take oil reservoir to enter after being layered
Row is concentrated in vacuo, and is that 0.095MPa vacuums obtain final extract 5.75Kg, wherein pyrethrins content 38.2% in pressure, is contained
Water rate 4.8%.
It is described above, pyrethrins yield=(gained pyrethrins quality × content)/(pyrethrins quality in raw material ×
Content) × %, similarly hereinafter.
Embodiment 3
Present embodiments provide it is a kind of provide a kind of method of subcritical abstraction pyrethrins, step includes：
(1) raw material are handled for the first time, the raw material Dalmatian chrysanthemum for taking 100Kg pyrethrins content to be 2.7%, raw material are carried out
It is crushed to 60-100 mesh.
(2) second of processing of raw material, below 150Pa is down to by being vacuumized in the raw material input extraction kettle after crushing, is arranged
Air to the greatest extent in kettle；Then out of storage tank toward squeezing into HFC-134a liquid untill raw material is flooded in extraction kettle, static pressure extraction
30min, 55 DEG C of temperature, pressure 0.9Mpa；Open No. 1 air compressor and carry out dynamic extraction, extract HFC-134a liquid
Extraction 20min, 55 DEG C of temperature, pressure 0.7MPa are circulated in kettle and separating still；By HFC-134a in extraction kettle and extract
It is put into separating still, heating decompression separation is then carried out in separating still, temperature is 60 DEG C, starts No. 2 air compressor machines and extracts gaseous state
HFC-134a in separating still until be in close to vacuum state, recovery HFC-134a gas, collection pyrethrins (extract)
6.9KG.Wherein pyrethrins content 31.5%, moisture content 8.4%, pyrethrins yield 80.5%.
(3) purification of pyrethrins：2 times of amount petroleum ethers will be added in pyrethrins extract, take oil reservoir to enter after being layered
Row is concentrated in vacuo, and is that 0.09MPa vacuums obtain final extract 5.52Kg, wherein pyrethrins content 38.8% in pressure, is contained
Water rate 4.1%.
It is described above, pyrethrins yield=(gained pyrethrins quality × content)/(pyrethrins quality in raw material ×
Content) × %, similarly hereinafter.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (7)
- A kind of 1. method of subcritical abstraction pyrethrins, it is characterised in that step includes：S1, raw material subcritical abstraction:Raw material is added into HFC-134a as in extraction container, vacuumizing in backward extraction container Liquid, 40-60 DEG C of temperature, static pressure extraction 20-40min under pressure 0.8-1Mpa；40-60 DEG C of temperature, pressure 0.6-0.8Mpa, move State extracts 15-25min；Then gaseous state HFC-134a is extracted at 55-60 DEG C and carries out heating decompression separation, collect pyrethrins extraction Take liquid；S2, pyrethrins purification；Extractant is added into pyrethrins extract, takes oil reservoir be concentrated to give and finally remove after layering Worm chrysanthemum ester extract.
- 2. the method for subcritical abstraction pyrethrins as claimed in claim 1, it is characterised in that：In step S1, the dynamic Extract to make HFC-134a liquid be circulated in extraction container and separation container in extraction process.
- 3. the method for subcritical abstraction pyrethrins as claimed in claim 1, it is characterised in that：In step S1, the extraction Gaseous state HFC-134a tends under conditions of vacuum to extract gaseous state HFC-134a and being in extraction system.
- 4. the method for subcritical abstraction pyrethrins as claimed in claim 1, it is characterised in that：It is described to take out very in step S1 Sky is to make pressure in below 150Pa.
- 5. the method for subcritical abstraction pyrethrins as claimed in claim 1, it is characterised in that：In step S1, the raw material To be crushed to the Dalmatian chrysanthemum of 60-100 mesh.
- 6. the method for subcritical abstraction pyrethrins as claimed in claim 1, it is characterised in that：In step S2, the extraction Agent is petroleum ether, and the petroleum ether dosage is twice of pyrethrins extract volume.
- 7. the method for subcritical abstraction pyrethrins as claimed in claim 1, it is characterised in that：In step S2, the concentration For the vacuum concentration carried out under pressure 0.09-0.095MPa.
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| CN201710637580.9A CN107445924B (en) | 2017-07-31 | 2017-07-31 | Subcritical pyrethrin extraction method |
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| CN201710637580.9A CN107445924B (en) | 2017-07-31 | 2017-07-31 | Subcritical pyrethrin extraction method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108614055A (en) * | 2017-12-30 | 2018-10-02 | 青岛袁策生物科技有限公司 | A kind of high performance liquid chromatography pretreating device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147208A (en) * | 1994-03-31 | 1997-04-09 | 帝国化学工业公司 | Solvent extraction process |
| CN1424303A (en) * | 2002-11-21 | 2003-06-18 | 中国科学院昆明植物研究所 | Refinery pyrethrin preparation |
| CN102204574A (en) * | 2010-03-31 | 2011-10-05 | 魏立文 | Subcritical mixed fluid extraction method for natural pyrethrin |
| CN102698466A (en) * | 2012-06-13 | 2012-10-03 | 晨光生物科技集团股份有限公司 | Method for removing pesticide residues in natural extract |
-
2017
- 2017-07-31 CN CN201710637580.9A patent/CN107445924B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147208A (en) * | 1994-03-31 | 1997-04-09 | 帝国化学工业公司 | Solvent extraction process |
| CN1424303A (en) * | 2002-11-21 | 2003-06-18 | 中国科学院昆明植物研究所 | Refinery pyrethrin preparation |
| CN102204574A (en) * | 2010-03-31 | 2011-10-05 | 魏立文 | Subcritical mixed fluid extraction method for natural pyrethrin |
| CN102698466A (en) * | 2012-06-13 | 2012-10-03 | 晨光生物科技集团股份有限公司 | Method for removing pesticide residues in natural extract |
Non-Patent Citations (1)
| Title |
|---|
| 杨倩 等: "亚临界流体萃取技术在茶叶降低菊酯类农残方面的应用", 《中国茶叶加工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108614055A (en) * | 2017-12-30 | 2018-10-02 | 青岛袁策生物科技有限公司 | A kind of high performance liquid chromatography pretreating device |
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