CN1833748A - Method of removing pesticide residual in natural extracts by adsorbing resin process - Google Patents
Method of removing pesticide residual in natural extracts by adsorbing resin process Download PDFInfo
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- CN1833748A CN1833748A CN 200610013224 CN200610013224A CN1833748A CN 1833748 A CN1833748 A CN 1833748A CN 200610013224 CN200610013224 CN 200610013224 CN 200610013224 A CN200610013224 A CN 200610013224A CN 1833748 A CN1833748 A CN 1833748A
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Abstract
A process for removing the residual agricultural chemical from the extract of natural product by screening-type adsorptive resin method includes such steps as preparing the screen-type adsorptive resin through dissolving PVC in water, heating, adding oil phase prepared from styrene and divinylbenzene, slow heating, reaction, filtering, washing to obtain white gel balls of polystyrene, swelling in organic solvent, adding bichloroary/hydrocarbon, Friedel-Craft reaction, filtering out resin and washing, loading the resin in column, making the solution of said extract in alcohol-water to flow through the column, and drying.
Description
[technical field]: the removal method that the present invention relates to residues of pesticides in the natural extracts such as Chinese herbal medicine.Utilize screening type adsorption resin that the residues of pesticides in the natural extracts such as Chinese herbal medicine are removed.
[background technology]: traditional Chinese medicine is the magnificent crystallization of Chinese nation's excellent culture, and the domestic and international market of plant extracts is all developed rapidly in recent years, but the share that China's Chinese medical extract occupies is considerably less, and the status of this and China Chinese medicine big country is extremely unbecoming.It is the two big obstacles that Chinese medicine ranks among the world that residues of harmful substances amounts such as the uncertain and agricultural chemicals of Chinese medicine active ingredient, heavy metal exceed standard.
Research about agricultural chemicals residue problem in the Chinese medical extract at present focuses mostly in detection, really can be used for industrial production on a large scale and remove residues of pesticides, the separation method research of the extract that the preparation pesticide concentration is qualified is shortcoming very, though solvent extraction is arranged, the research report of methods such as supercritical extract, but Chinese medicine complicated component, the remains of pesticide kind is various and often combine closely with biological cell, people are difficult in when utilizing organic solvent to remove residues of pesticides, do not lose the active ingredient of Chinese medicine and do not cause the secondary pollution of organic solvent, the supercritical extraction equipment investment is very expensive in addition, is difficult to satisfy requirement of large-scale production.The most serious with organo-chlorine pesticide harm in remains of pesticide, this can be at the occurring in nature extended residual because its chemical property is stable, degradation half life is long, the biological concentration coefficient is big.
Advantages such as adsorption resin method, environmental friendliness simple because of its technology, production cost be low have in recent years caused that in natural product extraction people pay close attention to greatly.But common macroporous absorbent resin is because the restriction of its preparation method, make that this kind resin aperture is big, the pore-size distribution broad, the less pesticide molecule of larger-size active ingredient of natural product and size all can enter in the resin hole and be adsorbed, and loss of active ingredients is very serious.
[summary of the invention]: purpose of the present invention overcomes the deficiencies in the prior art exactly, and a kind of method of utilizing screening type adsorption resin to remove residues of pesticides in the natural extracts is provided.
A kind of adsorption resin method is removed the method for the residues of pesticides in the natural extracts, it is characterized in that:
(1) natural extracts that will contain remains of pesticide is dissolved in 20%～40% ethanol/water, and being mixed with concentration is 2g/L～6g/L upper prop liquid;
(2) screening type adsorption resin is packed into volume is in the adsorption column of 10-30ml, by resin column, pesticide molecule wherein is attracted on the resin with upper prop liquid, and the natural extracts molecule is not by resin adsorption, flow out from resin column, the two can reach fully separates;
(3) will flow out the natural extracts that the liquid concentrate drying can not contained residues of pesticides.
Above-mentioned natural extracts is a Chinese herbal medicine.
The present invention utilizes screening type adsorption resin, and the medium and small molecule organic agricultural chemicals of natural extracts such as removal Chinese herbal medicine are residual, only through adsorbing a step, can make the clearance of remains of pesticide surpass 99%, and the rate of recovery of active ingredient are more than 95% in the extract.Because this method is removed residues of pesticides and is based on the different screening separation mechanism of molecular dimension, therefore, irrelevant with concrete molecular structure as long as the suitable pesticide molecule of molecular dimension all can be by resin adsorption, should have universality for removal this method of residues of pesticides.
The preparation method of above-mentioned screening type adsorption resin, finish by following steps:
---a: at normal temperatures, polyvinyl alcohol is dissolved in the water, is made into 0.5%～5% the aqueous solution;
---b: the solution of a in the step is heated to 30～50 ℃, adds the oil phase of forming with 99.5%～99.9% styrene and 0.1%～0.5% divinylbenzene, wherein water: oil phase volume ratio 2: 1～4: 1;
---c: the solution of b in the step is warming up to 70～90 ℃, and programming rate is 2 ℃/min, reacts 2～4 hours, is warming up to 95～100 ℃ again, reacts 5 hours;
---d: after filtration, after the carrying out washing treatment, prepare the gel type polystyrene Archon with the reaction solution in c step;
---e: the polystyrene Archon that d was made in the step after the abundant swelling, adds dichloro-aromatic hydrocarbons as alkylating reagent in dichloroethanes, carry out the Fu Shi alkylated reaction, 80 ℃ are incubated 10～12 hours, stop reaction, leach resin, clean, obtain screening type adsorption resin.
Advantage of the present invention and effect: 1, the present invention utilizes screening type adsorption resin, the medium and small molecule organic agricultural chemicals of natural extracts such as removal Chinese herbal medicine are residual, only, can make the clearance of remains of pesticide surpass 99%, and the rate of recovery of active ingredient is more than 95% in the extract through adsorbing a step.2, since the structural design of this resinoid just based on the regulation and control of pore size, irrelevant as long as the suitable pesticide molecule of molecular dimension all can be by resin adsorption, so this resinoid has universality for the removal of residues of pesticides with concrete molecular structure.3, this method technology is simple, is suitable for large-scale industrial production.
[specific embodiment]:
Embodiment 1
Above-mentioned polymeric adsorbent is in the application of the residues of pesticides from arasaponin extract
The arasaponin extract that will contain pentachloronitrobenzene (PCNB), BHC, DDT is the upper prop liquid that 40% ethanol-water solution is formulated as concentration 6g/L with volumn concentration.Get above-mentioned solution 600ml with the flow velocity of 0.5mL/min by 30mL wet resin post, collect and flow out liquid, measure the content that flows out PCNB, BHC, DDT and notoginsenoside in the liquid.Flow out liquid behind concentrate drying, calculate the clearance of three kinds of agricultural chemicals and the rate of recovery of notoginsenoside.After testing, the PCNB clearance is 99.6%, and the clearance of BHC is 99.5%, and the clearance of DDT is 99.1%, and the rate of recovery of arasaponin is 98.9%.
Embodiment 2
The ginsenoside extract that will contain PCNB, BHC, DDT is the upper prop liquid that 40% alcohol-water is formulated as concentration 5g/L with volumn concentration.Get above-mentioned solution 400mL with the flow velocity of 0.5mL/min by 20mL wet resin post, collect and flow out liquid.After absorption is finished, measure the content that flows out PCNB, BHC, DDT and ginsenoside in the liquid, flow out the liquid concentrate drying and calculate the clearance of three kinds of agricultural chemicals and the rate of recovery of ginsenoside.After testing, the clearance of PCNB is 99.3%, and the BHC clearance is 99.5%, and the clearance of DDT is 99.2%, and the rate of recovery of general ginsenoside is 98.5%.
Embodiment 3
The kudzu root flavone extract that will contain PCNB, BHC and DDT is the upper prop liquid that 20% alcohol-water is formulated as concentration 3g/L with volumn concentration.Get above-mentioned solution 250mL with the flow velocity of 0.5mL/min by 10mL wet resin post, collect and flow out liquid.After absorption is finished, measure the content that flows out PCNB, BHC, DDT and kudzu root flavone in the liquid, flow out the liquid concentrate drying and calculate the clearance of three kinds of agricultural chemicals and the rate of recovery of kudzu root flavone.After testing, PCNB and BHC clearance are 99.1%, and the clearance of DDT is 99.0%, and the rate of recovery of kudzu root flavone is 95.2%.
Claims (3)
1, a kind of method of utilizing screening type adsorption resin to remove residues of pesticides in the natural extracts is characterized in that:
(1) natural extracts that will contain remains of pesticide is dissolved in 20%～40% the ethanol/water, and being mixed with concentration is 2g/L～6g/L upper prop liquid;
(2) screening type adsorption resin is packed into internal diameter is in the adsorption column of 10-30ml, by resin column, pesticide molecule wherein is attracted on the resin with upper prop liquid, and the natural extracts molecule is not by resin adsorption, flow out from resin column, the two can reach fully separates;
(3) will flow out the natural extracts that the liquid concentrate drying can not contained residues of pesticides.
2, the application of screening type adsorption resin according to claim 1 residues of pesticides in removing natural extracts is characterized in that described natural extracts is a Chinese herbal medicine.
3, the preparation method of the described screening type adsorption resin of claim 1 is characterized in that it comprises the steps:
---a: at normal temperatures, polyvinyl alcohol is dissolved in the water, is made into 0.5%～5% the aqueous solution;
---b: the solution of a in the step is heated to 30～50 ℃, adds the oil phase of forming with 99.5%～99.9% styrene and 0.1%～0.5% divinylbenzene, wherein water: oil phase volume ratio 2: 1～4: 1;
---c: the solution of b in the step is warming up to 70～90 ℃, and programming rate is 2 ℃/min, reacts 2～4 hours, is warming up to 95～100 ℃ again, reacts 5 hours;
---d: after filtration, after the carrying out washing treatment, prepare the gel type polystyrene Archon with the reaction solution in c step;
---e: the polystyrene Archon that d was made in the step after the abundant swelling, adds dichloro-aromatic hydrocarbons as alkylating reagent in dichloroethanes, carry out the Fu Shi alkylated reaction, 80 ℃ are incubated 10～12 hours, stop reaction, leach resin, clean, obtain screening type adsorption resin.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100132241A CN100345610C (en) | 2006-02-28 | 2006-02-28 | Method of removing pesticide residual in natural extracts by adsorbing resin process |
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| CNB2006100132241A CN100345610C (en) | 2006-02-28 | 2006-02-28 | Method of removing pesticide residual in natural extracts by adsorbing resin process |
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| CN1833748A true CN1833748A (en) | 2006-09-20 |
| CN100345610C CN100345610C (en) | 2007-10-31 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101731493A (en) * | 2008-11-14 | 2010-06-16 | 周京石 | Production process for removing pesticide residue from extract of Ginkgo biloba |
| CN101838357A (en) * | 2010-05-17 | 2010-09-22 | 北京欧凯纳斯科技有限公司 | Application of macromolecular resin in removing pesticide residue |
| CN102091438A (en) * | 2010-12-29 | 2011-06-15 | 浙江绍兴东灵保健食品有限公司 | Method for removing pesticide residue in plant extract |
| CN101598707B (en) * | 2009-05-19 | 2012-05-02 | 烟台杰科检测服务有限公司 | Method for detecting various pesticide residue in oil-containing food |
| CN101849595B (en) * | 2010-02-03 | 2012-08-22 | 福建农林大学 | Method for reducing pesticide residue in instant tea by resin adsorption method |
| CN103304836A (en) * | 2013-06-28 | 2013-09-18 | 天津欧瑞生物科技有限公司 | Preparation of imprinting type sieving adsorbent resin and method for removing pesticide residue in traditional Chinese medicine extract by using imprinting type sieved adsorbing resin |
| CN107335401A (en) * | 2016-12-01 | 2017-11-10 | 上海绿强新材料有限公司 | A kind of method that traditional Chinese medical science herbal paste Pesticide Residues are removed using inorganic adsorbent |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1327850A (en) * | 2001-06-19 | 2001-12-26 | 灵素(北京)药业有限公司 | American ginseng extract (CNT-2000) without residual agricultural chemical and its usage |
| CN1131112C (en) * | 2001-11-05 | 2003-12-17 | 南京大学环境学院 | Process for synthesizing weakly alkaline anionic exchange resin with double functions and superhigh cross-linking |
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2006
- 2006-02-28 CN CNB2006100132241A patent/CN100345610C/en active Active
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101731493A (en) * | 2008-11-14 | 2010-06-16 | 周京石 | Production process for removing pesticide residue from extract of Ginkgo biloba |
| CN101598707B (en) * | 2009-05-19 | 2012-05-02 | 烟台杰科检测服务有限公司 | Method for detecting various pesticide residue in oil-containing food |
| CN101849595B (en) * | 2010-02-03 | 2012-08-22 | 福建农林大学 | Method for reducing pesticide residue in instant tea by resin adsorption method |
| CN101838357A (en) * | 2010-05-17 | 2010-09-22 | 北京欧凯纳斯科技有限公司 | Application of macromolecular resin in removing pesticide residue |
| CN101838357B (en) * | 2010-05-17 | 2012-02-22 | 北京欧凯纳斯科技有限公司 | Application of macromolecular resin in removing pesticide residue |
| CN102091438A (en) * | 2010-12-29 | 2011-06-15 | 浙江绍兴东灵保健食品有限公司 | Method for removing pesticide residue in plant extract |
| CN102091438B (en) * | 2010-12-29 | 2012-12-05 | 浙江绍兴东灵保健食品有限公司 | Method for removing pesticide residue in plant extract |
| CN103304836A (en) * | 2013-06-28 | 2013-09-18 | 天津欧瑞生物科技有限公司 | Preparation of imprinting type sieving adsorbent resin and method for removing pesticide residue in traditional Chinese medicine extract by using imprinting type sieved adsorbing resin |
| CN107335401A (en) * | 2016-12-01 | 2017-11-10 | 上海绿强新材料有限公司 | A kind of method that traditional Chinese medical science herbal paste Pesticide Residues are removed using inorganic adsorbent |
| CN107335401B (en) * | 2016-12-01 | 2020-07-14 | 上海绿强新材料有限公司 | Method for removing pesticide residues in traditional Chinese medicine ointment formula by using inorganic adsorbent |
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| CN100345610C (en) | 2007-10-31 |
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Owner name: ZHEJIANG HUISONG PHARMACEUTICALS CO., LTD. Free format text: FORMER OWNER: NANKAI UNIVERSITY Effective date: 20120203 |
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Effective date of registration: 20120203 Address after: 310018, No. 39, No. 25, Hangzhou economic and Technological Development Zone Patentee after: Zhejiang Huisong Pharmaceuticals Co., Ltd. Address before: 300071 Tianjin City, Nankai District Wei Jin Road No. 94, Nankai University Patentee before: Nankai University |