CN107445924B - Subcritical pyrethrin extraction method - Google Patents
Subcritical pyrethrin extraction method Download PDFInfo
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- CN107445924B CN107445924B CN201710637580.9A CN201710637580A CN107445924B CN 107445924 B CN107445924 B CN 107445924B CN 201710637580 A CN201710637580 A CN 201710637580A CN 107445924 B CN107445924 B CN 107445924B
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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
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- 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
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- 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
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Abstract
The invention provides a method for subcritical extraction of pyrethrin, which comprises the steps of crushing and bagging pyrethrin raw materials in a subcritical extraction kettle; adding 1, 1, 1, 2-tetrafluoroethane as an extractant into an extraction kettle, extracting for 30 minutes at the pressure of 0.6-1.0MPa and the temperature of 40-60 ℃, evaporating and recovering the extractant, and purifying the extract to obtain the final product. The invention adopts subcritical and pressurized conditions to extract the pyrethrin, has higher extraction rate, higher content and simple post-treatment compared with the conventional method, and can effectively prevent the pyrethrin from volatilizing in a high-temperature environment when the temperature in the whole process is below 60 ℃.
Description
Technical Field
The invention relates to the technical field of pyrethrin extraction, in particular to a subcritical pyrethrin extraction method.
Background
Pyrethrum is the only insect killing plant cultivated intensively in the world at present, and is a herbal medicine for treating dermatosis scabies and children's insecticide. Pyrethrin, an insecticide extracted from pyrethrum, is a preferred biological insecticide for the certification of organic food and green food because of its non-pollution characteristic. The pyrethrum has the plant height of 50 cm, flowers in 5 months, and can be hung with about 200 flowers in the full-bloom period. Has ornamental value, is used for optimizing the environment and can be potted. One pot is placed at 4 square meters indoors, so that the mosquito and fly repelling effect can be achieved, and the effect is very obvious. 1. Interplanting of pyrethrum in a orchard: 200 pyrethrum plants are planted in each acre of fruit forest, and one pyrethrum plant is planted in each 3-4 square meters, so that pests can be effectively inhibited from entering an orchard, and the harm of using chemical pesticides is reduced. The stem of pyrethrum can be cut into pieces at the end of autumn and buried underground to kill the overwintering pests. 2. Planting pyrethrum in a pyrethrum farm: in cattle, sheep, pigs, chickens and breeding farms, avermectin pyrethrum is grown in an average of 4 square meters, and can repel mosquitoes and flies in the farms. The dry pyrethrum product is crushed and spread into animal raising house to prevent the pests, such as lice, flea, bedbug, etc. from growing outside the animal raising house and to control the fly maggot to overflow in summer to prevent disease spreading. 3. The pyrethrum is used for the afforestation of the house and interior decoration, the pyrethrum has higher economic value and ornamental value, use it as dispelling mosquito, fly ornamental potted landscape industrial development indoor, its economic benefits are considerable too, can profit ten thousand yuan per mu. The roots, stems, leaves, flowers and the like of the pyrethrum contain toxigenin substances, are raw materials for extracting pyrethrin, are good raw materials for preparing various insecticides, and the pyrethrum is a dead or killed insect of pests such as aphids, mosquitoes and flies, cabbage, cotton bolls and the like. The mosquito-repellent incense made of pyrethrum leaf can kill mosquito and fly, and has special effect for bed bug, louse and flea. The pyrethrum has the advantages of no environmental pollution, no damage to ecological balance, no drug resistance, no toxicity to human, livestock, poultry and mammals and the like, so that the artificial cultivation of the pyrethrum is vigorously developed, and the method has wide prospects.
At present, subcritical n-hexane extraction is adopted in China, and the n-hexane is flammable and explosive, so that the requirements on staff and equipment and the environment are high, and accidents are easy to occur. The supercritical carbon dioxide extraction has higher equipment design and manufacturing cost and operating cost, and the supercritical carbon dioxide extraction is not suitable for industrial production because the pressure is overlarge, the treatment capacity is small, and the carbon dioxide is a nonpolar molecule and has low extraction rate on the pyrethrin. The subcritical fluid extraction technology is a novel extraction technology developed in recent years, and is a technology for finally obtaining a target product by performing molecular diffusion on an extract and an extractant in a container according to the principle of similarity and intermiscibility and then separating the extractant and the target product through reduced pressure evaporation.
Disclosure of Invention
In view of the above, the present invention provides a method for subcritical extraction of pyrethrin, which can substantially completely extract pyrethrin from raw materials through subcritical extraction without other solvent pollution, thereby reducing post-treatment process.
The invention provides a method for subcritical extraction of pyrethrin, which comprises the following steps:
s1, subcritical extraction of raw materials, namely putting the raw materials into an extraction container, vacuumizing, and adding tetrafluoroethane liquid into the extraction container for static pressure extraction for 20-40min at the temperature of 40-60 ℃ and under the pressure of 0.8-1 Mpa; dynamic extracting at 40-60 deg.C and 0.6-0.8Mpa for 15-25 min; then extracting gaseous tetrafluoroethane at 55-65 ℃ for temperature rise and pressure reduction separation, and collecting pyrethrin extract;
s2, purifying pyrethrin; adding an extracting agent into the pyrethrin extract, layering, taking an oil layer, and concentrating to obtain the final pyrethrin extract.
The invention has the beneficial effects that: the invention provides a high-efficiency, environment-friendly and simple subcritical pyrethrin extraction method aiming at the defects of excessive loss of effective components, low extraction rate, complex post-treatment and the like of the existing method for preparing pyrethrin, the method can basically extract the pyrethrin from the raw materials completely without other solvent pollution, the post-treatment process is reduced, the temperature in the whole process is below 60 ℃, the pyrethrin can be effectively prevented from volatilizing in a high-temperature environment, the content of the pyrethrin in the final product is more than 38%, the water content is less than 5%, and the yield of the pyrethrin is more than 80%. Meanwhile, the method is suitable for large-scale production of the pyrethrin, and provides favorable conditions for popularizing the application and development of the pyrethrin.
Detailed Description
The invention provides a method for subcritical extraction of pyrethrin, which comprises the following steps:
s1, subcritical extraction of raw materials, namely putting the raw materials into an extraction container, vacuumizing, and adding tetrafluoroethane liquid into the extraction container for static pressure extraction for 20-40min at the temperature of 40-60 ℃ and under the pressure of 0.8-1 Mpa; dynamic extracting at 40-60 deg.C and 0.6-0.8Mpa for 15-25 min; then extracting gaseous tetrafluoroethane at 55-60 ℃ for temperature rise and pressure reduction separation, and collecting pyrethrin extract;
s2, purifying pyrethrin; adding an extracting agent into the pyrethrin extract, layering, taking an oil layer, and concentrating to obtain the final pyrethrin extract.
The method can be used for basically completely extracting the pyrethrin from the raw materials without other solvent pollution, has simple post-treatment, adopts 1, 1, 1, 2-tetrafluoroethane as an extracting agent for subcritical extraction, avoids using flammable and explosive normal hexane, has safe process, high pyrethrin extraction rate and content, easy operation and realization of process steps and simple flow, and is very suitable for large-scale production of the pyrethrin.
Preferably, in step S1, the dynamic extraction is to circulate the tetrafluoroethane liquid in the extraction vessel and the separation vessel during the extraction process.
Preferably, in step S1, the extracting gaseous tetrafluoroethane is extracting gaseous tetrafluoroethane until the extraction system is in a condition tending to vacuum. The temperature-rising and pressure-reducing separation step is carried out in a separation container, and the gaseous tetrafluoroethane is pumped by an air compressor until the separation container is in a near vacuum state, so that the tetrafluoroethane gas is recovered. The extract obtained by the processing of step S1 has a pyrethrin content of > 30%, a water content of < 10%, and a pyrethrin yield of > 80%.
Preferably, in step S1, the evacuation is performed so that the pressure is 150Pa or less.
Preferably, in step S1, the raw material is pyrethrum crushed to 60-100 mesh.
Preferably, in step S2, the extracting agent is petroleum ether, and the amount of petroleum ether is twice the volume of the pyrethrin extract. The extractant is not limited to petroleum ether, and other pyrethrin insoluble solvents can be used.
Preferably, in step S2, the concentration is vacuum concentration performed under a pressure of 0.09 to 0.095 MPa. The final extract obtained by the true concentration has pyrethrin content of more than 38% and water content of less than 5%.
In order to facilitate understanding of the present invention, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following specific examples.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1
The embodiment provides a method for subcritical extraction of pyrethrin, which comprises the following steps:
(1) the raw material is treated for the first time, 100Kg of pyrethrum with pyrethrin content of 2.7% is taken and crushed to 60-100 meshes.
(2) Performing secondary treatment on the raw materials, putting the crushed raw materials into an extraction kettle, vacuumizing to reduce the pressure to below 150Pa, and exhausting air in the kettle; then, pumping tetrafluoroethane liquid into the extraction kettle from the storage tank until the raw materials are submerged, and extracting for 30min under static pressure at the temperature of 50 ℃ and the pressure of 0.8 Mpa; opening an air compressor No. 1 for dynamic extraction, and circularly flowing and extracting tetrafluoroethane liquid in an extraction kettle and a separation kettle for 20min at the temperature of 50 ℃ and the pressure of 0.6 MPa; putting tetrafluoroethane and extract liquor in an extraction kettle into a separation kettle, then heating and decompressing and separating in the separation kettle at the temperature of 60 ℃, starting a No. 2 air compressor to extract gaseous tetrafluoroethane until the separation kettle is in a near vacuum state, recovering tetrafluoroethane gas, and collecting 7.2KG of pyrethrin (extract liquor). Wherein the content of the pyrethrin is 31.2 percent, the water content is 9 percent, and the yield of the pyrethrin is 83.2 percent.
(3) And (3) purifying pyrethrin: adding petroleum ether with 2 times of volume into the pyrethrin extract, layering, vacuum concentrating the oil layer, and obtaining 5.73Kg of final extract under the pressure of 0.09MPa and the vacuum degree, wherein the content of the pyrethrin is 38.5%, and the water content is 4.5%.
As described above, the yield of pyrethrin (mass × content of obtained pyrethrin)/(mass × content of pyrethrin in raw material) ×% is the same as below.
Example 2
This example provides a method for subcritical extraction of pyrethrin, comprising the steps of:
(1) the raw material is treated for the first time, 100Kg of pyrethrum with pyrethrin content of 2.7% is taken and crushed to 60-100 meshes.
(2) Performing secondary treatment on the raw materials, putting the crushed raw materials into an extraction kettle, vacuumizing to reduce the pressure to below 150Pa, and exhausting air in the kettle; then, pumping tetrafluoroethane liquid into the extraction kettle from the storage tank until the raw materials are submerged, and carrying out static pressure extraction for 30min at the temperature of 40 ℃ and the pressure of 1 Mpa; opening an air compressor No. 1 for dynamic extraction, and circularly flowing and extracting tetrafluoroethane liquid in an extraction kettle and a separation kettle for 20min at the temperature of 40 ℃ and the pressure of 0.8 MPa; putting tetrafluoroethane and extract liquor in an extraction kettle into a separation kettle, then heating and decompressing and separating in the separation kettle at the temperature of 60 ℃, starting a No. 2 air compressor to extract gaseous tetrafluoroethane until the separation kettle is in a near vacuum state, recovering tetrafluoroethane gas, and collecting 6.8KG pyrethrin (extract liquor). Wherein the content of the pyrethrin is 32.8 percent, the water content is 8.8 percent, and the yield of the pyrethrin is 82.6 percent.
(3) And (3) purifying pyrethrin: adding 2 times of petroleum ether into the pyrethrin extract, layering, vacuum concentrating the oil layer, and obtaining 5.75Kg of final extract under the pressure of 0.095MPa and the vacuum degree, wherein the content of the pyrethrin is 38.2 percent, and the water content is 4.8 percent.
As described above, the yield of pyrethrin (mass × content of obtained pyrethrin)/(mass × content of pyrethrin in raw material) ×% is the same as below.
Example 3
This example provides a method for subcritical extraction of pyrethrin, comprising the steps of:
(1) the raw material is treated for the first time, 100Kg of pyrethrum with pyrethrin content of 2.7% is taken and crushed to 60-100 meshes.
(2) Performing secondary treatment on the raw materials, putting the crushed raw materials into an extraction kettle, vacuumizing to reduce the pressure to below 150Pa, and exhausting air in the kettle; then, pumping tetrafluoroethane liquid into the extraction kettle from the storage tank until the raw materials are submerged, and carrying out static pressure extraction for 30min at the temperature of 55 ℃ and the pressure of 0.9 MPa; opening an air compressor No. 1 for dynamic extraction, and circularly flowing and extracting tetrafluoroethane liquid in an extraction kettle and a separation kettle for 20min at the temperature of 55 ℃ and the pressure of 0.7 MPa; putting tetrafluoroethane and extract liquor in an extraction kettle into a separation kettle, then heating and decompressing and separating in the separation kettle at the temperature of 60 ℃, starting a No. 2 air compressor to extract gaseous tetrafluoroethane until the separation kettle is in a near vacuum state, recovering tetrafluoroethane gas, and collecting 6.9KG pyrethrin (extract liquor). Wherein the content of the pyrethrin is 31.5 percent, the water content is 8.4 percent, and the yield of the pyrethrin is 80.5 percent.
(3) And (3) purifying pyrethrin: adding 2 times of petroleum ether into the pyrethrin extract, layering, vacuum concentrating the oil layer, and obtaining 5.52Kg of final extract under the pressure of 0.09MPa and the vacuum degree, wherein the content of the pyrethrin is 38.8 percent, and the water content is 4.1 percent.
As described above, the yield of pyrethrin (mass × content of obtained pyrethrin)/(mass × content of pyrethrin in raw material) ×% is the same as below.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (4)
1. A method for subcritical extraction of pyrethrin, comprising the steps of:
s1, performing subcritical extraction on the raw material, namely putting the raw material into an extraction container, vacuumizing, adding tetrafluoroethane liquid into the extraction container, and performing static pressure extraction for 20-40min at the temperature of 40-60 ℃ and under the pressure of 0.8-1 MPa; performing dynamic extraction at 40-60 deg.C and 0.6-0.8MPa for 15-25 min; then extracting gaseous tetrafluoroethane at 55-60 ℃ for temperature rise and pressure reduction separation, and collecting pyrethrin extract;
s2, purifying pyrethrin; adding an extracting agent into the pyrethrin extract, layering, taking an oil layer, and concentrating to obtain a final pyrethrin extract;
in step S1, the dynamic extraction is to make the tetrafluoroethane liquid circularly flow in the extraction container and the separation container in the extraction process;
in step S1, the extracting gaseous tetrafluoroethane is extracting gaseous tetrafluoroethane until the extraction system is in a condition of tending to vacuum;
the extractant is petroleum ether, and the using amount of the petroleum ether is two times of the volume of the pyrethrin extract liquid.
2. The method of subcritical extraction of pyrethrin of claim 1, wherein: in step S1, the evacuation is performed so that the pressure is 150Pa or less.
3. The method of subcritical extraction of pyrethrin of claim 1, wherein: in step S1, the raw material is pyrethrum crushed to 60-100 mesh.
4. The method of subcritical extraction of pyrethrin of claim 1, wherein: in step S2, the concentration is vacuum concentration at a pressure of 0.09 to 0.095 MPa.
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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 |
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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 |
|---|
| 亚临界流体萃取技术在茶叶降低菊酯类农残方面的应用;杨倩 等;《中国茶叶加工》;20151231(第3期);第31-36页 * |
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