CN109078610B - Preparation method of silane modified attapulgite and application of silane modified attapulgite in removal of Chinese herbal medicine pesticide residues - Google Patents
Preparation method of silane modified attapulgite and application of silane modified attapulgite in removal of Chinese herbal medicine pesticide residues Download PDFInfo
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- 229960000892 attapulgite Drugs 0.000 title claims abstract description 109
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 109
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000000447 pesticide residue Substances 0.000 title claims abstract description 40
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 40
- 241000411851 herbal medicine Species 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000575 pesticide Substances 0.000 claims abstract description 39
- 239000000284 extract Substances 0.000 claims abstract description 30
- 239000004927 clay Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 12
- 238000005303 weighing Methods 0.000 claims abstract description 10
- 239000006228 supernatant Substances 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims abstract description 5
- 230000020477 pH reduction Effects 0.000 claims abstract description 3
- 238000000746 purification Methods 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
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- 238000000227 grinding Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000002728 pyrethroid Substances 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 239000005944 Chlorpyrifos Substances 0.000 claims description 6
- 239000005821 Propamocarb Substances 0.000 claims description 6
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical group CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 claims description 6
- LKPLKUMXSAEKID-UHFFFAOYSA-N pentachloronitrobenzene Chemical group [O-][N+](=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl LKPLKUMXSAEKID-UHFFFAOYSA-N 0.000 claims description 6
- 241000208340 Araliaceae Species 0.000 claims description 5
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 claims description 5
- 235000003140 Panax quinquefolius Nutrition 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 235000008434 ginseng Nutrition 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 4
- 239000009636 Huang Qi Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- CXBMCYHAMVGWJQ-CABCVRRESA-N (1,3-dioxo-4,5,6,7-tetrahydroisoindol-2-yl)methyl (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical group CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCN1C(=O)C(CCCC2)=C2C1=O CXBMCYHAMVGWJQ-CABCVRRESA-N 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- QBSJMKIUCUGGNG-UHFFFAOYSA-N isoprocarb Chemical group CNC(=O)OC1=CC=CC=C1C(C)C QBSJMKIUCUGGNG-UHFFFAOYSA-N 0.000 claims description 3
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003987 organophosphate pesticide Substances 0.000 claims description 3
- WZZLDXDUQPOXNW-UHFFFAOYSA-N propamocarb Chemical compound CCCOC(=O)NCCCN(C)C WZZLDXDUQPOXNW-UHFFFAOYSA-N 0.000 claims description 3
- 229960005199 tetramethrin Drugs 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- VXSIXFKKSNGRRO-MXOVTSAMSA-N [(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate;[(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-3-[(e)-3-methoxy-2-methyl-3-oxoprop-1-enyl Chemical class CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1.CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VXSIXFKKSNGRRO-MXOVTSAMSA-N 0.000 claims description 2
- 239000000152 carbamate pesticide Substances 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940070846 pyrethrins Drugs 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 13
- 239000007822 coupling agent Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 241000202726 Bupleurum Species 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910020175 SiOH Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 235000020710 ginseng extract Nutrition 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052604 silicate mineral Inorganic materials 0.000 description 2
- 238000000194 supercritical-fluid extraction Methods 0.000 description 2
- 241001061264 Astragalus Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 235000006533 astragalus Nutrition 0.000 description 1
- 235000019206 astragalus extract Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 description 1
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- 235000013376 functional food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 239000003993 organochlorine pesticide Substances 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a preparation method of silane modified attapulgite and application thereof in removing pesticide residues in Chinese herbal medicines, wherein the preparation method of the silane modified attapulgite comprises the steps of attapulgite purification, attapulgite acidification and attapulgite silane modification; the application of the silane modified attapulgite in the removal of Chinese herbal medicine pesticide residues comprises the following steps: weighing Chinese medicinal material extract and silane modified attapulgite, placing in mixed pesticide water solution, shaking and adsorbing at constant temperature of 15-25 deg.C for 1-2 hr at 11000 r.min‑1Centrifuging at rotating speed for 5-10min, analyzing pesticide content in the supernatant by GC-MS/MS, and analyzing pesticide content in the Chinese medicinal material extract raw materials by GC-MS/MS. The invention has simple process, convenient operation and no potential safety hazard, and pesticide residues in the Chinese medicinal material extract are removed to meet the maximum pesticide residue limit standard of China, European Union, America and other countries and regions. And the attapulgite clay has rich storage capacity and low price in China.
Description
Technical Field
The invention belongs to the technical field of natural mineral utilization, relates to a preparation method and application of modified attapulgite, and particularly relates to a preparation method of silane modified attapulgite and application of the silane modified attapulgite in removal of Chinese herbal medicine pesticide residues.
Background
With the coming of the big health age, the traditional Chinese medicine in China plays an irreplaceable role and is widely used for developing medicines and functional foods.
In the planting process of the traditional Chinese medicinal materials, in order to prevent the loss caused by plant diseases and insect pests, pesticide farmers inevitably use pesticides to reduce risks, so that the overproof pesticide residues seriously lag the pace of innovation and development of the traditional Chinese medicinal materials in China. At present, the residual pesticides in the traditional Chinese medicinal materials mainly comprise 3 types of organochlorines, organophosphorus and pyrethroids. The organochlorine pesticide has stable property and long half-life period, is difficult to degrade in soil, and can still be detected by most traditional Chinese medicinal materials. The organophosphorus pesticide has many varieties and high pesticide effect, and is a highly toxic product. Pyrethroid pesticides are synthetic bionic insecticides, most of the current researches are focused on foods such as tea leaves, and the researches on Chinese herbal medicines are less. The methods for removing pesticide residues of Chinese herbal medicines reported in the literature at present mainly comprise a water washing method, a preparation method, a photocatalysis method, a subcritical and supercritical extraction method and the like, and the methods have advantages and disadvantages, so that the method for removing the pesticide residues of the Chinese herbal medicines which can be universally applied is not common.
The attapulgite clay is silicate mineral salt with a layer-chain structure, is rich in storage capacity and wide in application, and has good adsorption performance due to the huge specific surface area. Organosilane, one of the most widely used coupling agents, is capable of polymerizing functional groups linked to the substrate, thereby modifying the surface of the hydroxyl-terminated substrate, which can form chemical bonds or interactions with the attapulgite, thereby enhancing the interaction between the attapulgite and other materials. At present, the attapulgite prepared by silane modification reported in documents is mostly used for wastewater treatment or metal ion adsorption, the method for removing pesticide residues in traditional Chinese medicine extracts is rare, and the method for preparing the attapulgite by silane modification is also complex and is not easy to operate.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of silane modified attapulgite and application thereof in removing Chinese herbal medicine pesticide residues.
The invention is realized by the following technical scheme:
a preparation method of silane modified attapulgite comprises the following steps:
and (3) purifying the attapulgite: mixing attapulgite with water, stirring at normal temperature of 15-25 ℃ for 2-3 days, standing for 3-4 days, taking the middle layer after precipitation, supplementing water to the original volume, repeating the steps for 2-3 times, finally taking the middle layer, placing the middle layer in an oven at the temperature of 100-120 ℃, drying, weighing and grinding to obtain purified attapulgite;
acidifying the attapulgite clay: mixing the purified attapulgite with a hydrochloric acid solution, stirring for 2-3 days at the normal temperature of 15-25 ℃, standing for 3-4 days, washing the lower-layer clay solid with distilled water for 3-5 times, performing suction filtration, drying, grinding, and sieving with a 150-mesh and 200-mesh sieve to obtain acidified attapulgite;
modifying attapulgite clay: mixing the acidified attapulgite with a medium solution, adding a silane coupling agent and triethylamine, stirring, heating and refluxing for 1-2 days, after the reaction is finished, performing suction filtration, washing a filter cake with ethanol for 3-5 times, drying in an oven at the temperature of 100 ℃ and 120 ℃, weighing, and grinding to obtain the silane modified attapulgite.
The invention further improves the scheme as follows:
the weight ratio of the attapulgite to water in the attapulgite purification step is 1: 20-50.
The weight ratio of the purified attapulgite to the hydrochloric acid solution in the acidification step of the attapulgite is 1:20-30, and the concentration of the hydrochloric acid solution is 1 mol-1。
In the attapulgite modification step, the weight-volume ratio of the acidified attapulgite to the medium solution is 1:8-12, the addition amount of the silane coupling agent is 5-10wt% of the mass of the acidified attapulgite, and the addition amount of the triethylamine is 1% of the volume of the medium solution.
The silane coupling agent is KH-792, KH-550 or KH-1161.
The medium solution is ethanol-water, methanol-water, acetone or toluene.
A further improvement of the present invention is
The application of the prepared silane modified attapulgite in the removal of Chinese herbal medicine pesticide residues comprises the following steps:
two kinds of traditional Chinese medicine extract samples, namely a sample containing pesticide residues and a sample without pesticide residues, are selected through GC/MS/MS analysis. The former are difficult to obtain; therefore, an international traffic method is adopted, and a standard pesticide solution is added into a sample without pesticide residues to construct a model system so as to verify the removal capacity of the removal material.
Weighing a sample without pesticide residue extract and silane modified attapulgite, placing the sample and the silane modified attapulgite in a mixed pesticide aqueous solution, oscillating and adsorbing at a constant temperature of 15-25 ℃ for 1-2h, and performing adsorption at 11000 r.min-1Centrifuging at rotating speed for 5-10min, and analyzing pesticide content in the supernatant by GC-MS/MS. After the silane modified attapulgite clay is removed, the pesticide residue in the traditional Chinese medicine extract meets the maximum pesticide residue limit standard.
The invention has the further improvement scheme that:
the weight volume ratio of the traditional Chinese medicine extract to the mixed pesticide aqueous solution is 1:1-3, and the addition amount of the silane modified attapulgite is 1-2wt% of the mass amount of the traditional Chinese medicine extract.
The Chinese medicinal material extract is Ginseng radix extract, radix astragali extract or bupleuri radix extract.
The mixed pesticide aqueous solution is a mixed solution of 4 different types of pesticides including organic chlorine, organic phosphorus, pyrethrins and carbamate.
The concentration of 4 different types of pesticides including organochlorine, organophosphorus, pyrethroid and carbamate in the mixed pesticide aqueous solution is 2-5mg-1
The organic chlorine pesticide is quintozene; the organophosphorus pesticide is chlorpyrifos; the pyrethroid pesticide is tetramethrin; the carbamate pesticide is isoprocarb or propamocarb.
The invention has the beneficial effects that:
the preparation method of the silane modified attapulgite provided by the invention has the advantages of simple process, convenience in operation, no potential safety hazard, readily available attapulgite raw materials and low price. The modified system is green solvent such as ethanol, water, methanol and the like, and is green and environment-friendly. Acid treatment of attapulgite can dissolve out carbonate precipitate to promote interlayer Ca2+、Na+、K+、Mg2+Plasma is released, the pore channel is dredged, the specific surface area is increased, the polarity-SiOH on the surface is fully exposed, silane groups are introduced on the surface of the attapulgite material after the silane coupling agent is combined with the surface-SiOH, the hydrophilicity and the hydrophobicity of the surface can be adjusted, different silane coupling agents are selected to design different silanized attapulgite materials according to different adsorption objects, and the adsorption performance can be adjusted conveniently. FT-IR and XRD pattern analysis of silane modified attapulgite clay shows that silane coupling agent is hydrolyzed to generate silicon hydroxyl which reacts with active hydroxyl on the surface of attapulgite clay to form chemical bonds, and functional groups are successfully grafted on the surface of attapulgite clay to improve the hydrophilicity and hydrophobicity of the attapulgite clay; based on the fat-soluble characteristic of most pesticides, a proper silane coupling agent modified attapulgite material is selected, so that the attapulgite material is easier to adsorb fat-soluble pesticide residues.
The attapulgite clay is silicate mineral salt with a layer-chain structure, so the attapulgite clay has abundant storage capacity and wide application, and has good adsorption performance due to the huge specific surface area. Organosilane, one of the most widely used coupling agents, is capable of polymerizing functional groups linked to the substrate, thereby altering the surface of the hydroxyl-terminated substrate, and forming chemical bonds or interactions with the attapulgite clay, thereby enhancing the interaction between the attapulgite clay and other substances. Therefore, when the silane modified attapulgite is applied to removing pesticide residues in Chinese herbal medicine extracts, the problems of long sample pretreatment time, non-universal applicability, potential safety hazard and the like existing when the pesticide residues in the Chinese herbal medicine extracts are removed by a water washing method, a preparation method, a photocatalysis method, a subcritical and supercritical extraction method and the like can be solved.
Drawings
FIG. 1 is a GC-MS/MS comparison chart before and after removal of pesticide residues in the ginseng extract of example 1;
wherein, 1 is propamocarb, 2 is isoprocarb, 3 is quintozene, 4 is chlorpyrifos and 5 is tetramethrin.
FIG. 2 is a FT-IR comparison of purified attapulgite, acidified attapulgite and silane modified attapulgite prepared in examples 1 to 3;
FIG. 3 is a comparison XRD of purified attapulgite, acidified attapulgite and silane modified attapulgite prepared in examples 1 to 3.
The specific implementation mode is as follows:
the invention takes the removal of pesticide residues in the extracts of ginseng, astragalus and bupleurum as an example, and examines the removal capability of silane modified attapulgite on pesticide residues.
Example 1:
placing attapulgite and water in a proportion of 1:20 in a beaker, stirring at normal temperature for 2 days, standing for 2 days, precipitating, placing the middle layer in another beaker, adding water to the original volume, and repeating the steps for 2-3 times. Finally, the middle layer is dried in an oven at 105 ℃, weighed and ground. Mixing the purified attapulgite with 1 mol.L-1The hydrochloric acid is acidified according to the proportion of 1:20, stirred for 2 days at normal temperature, kept stand for 2 days, washed with distilled water for a plurality of times to obtain lower-layer clay solid, filtered, dried, ground, sieved by a 150-mesh sieve, and the attapulgite is acidified. Putting 10g of acidified attapulgite and 100mL of toluene into a 250mL three-neck flask, adding 0.7g of KH-792 and 1mL of triethylamine, magnetically stirring, heating and refluxing for 24h, repeatedly washing the attapulgite with ethanol after the reaction is finished until the coupling agent is completely eluted, drying for 24h at 105 ℃, and grinding for later use.
Precisely weighing 50g of Ginseng radix extract in conical flask, and adding into the conical flask with concentration of 2.0 mg.L-1Pentachloronitrobenzene, 2.0 mg.L-1Isoprocarb, 2.0 mg.L-1Tetramethrin, 2.0 mg.L-1Propamocarb, 2.0 mg.L-1100mL of mixed pesticide aqueous solution of chlorpyrifos and 5g of silane modified attapulgite which are precisely weighed are added into a conical flask, and the mixture is vibrated and adsorbed for 2 hours at constant temperature and 11000 r.min-1Centrifuging at rotating speed for 5min, and analyzing pesticide content in the supernatant by GC-MS/MS, and analyzing pesticide content in Ginseng radix extract material by GC-MS/MS. The removal rate of 5 pesticides is higher than 77%, the removal rate of organic chlorine is even as high as 90%, and the pesticide residue in the ginseng extract after removal meets the maximum pesticide residue limit standard of China, European Union, America and other countries and regions.
Example 2:
placing attapulgite and water in a proportion of 1:40 in a beaker, stirring at normal temperature for 2 days, standing for 2 days, precipitating, placing the middle layer in another beaker, adding water to the original volume, and repeating the steps for 2-3 times. Finally placing the middle layer inOven drying at 105 deg.C, weighing, and grinding. Mixing the purified attapulgite with 1 mol.L-1The hydrochloric acid is acidified according to the proportion of 1:25, stirred for 2 days at normal temperature, kept stand for 2 days, washed with distilled water for a plurality of times to obtain lower-layer clay solid, filtered, dried, ground, sieved by a 150-mesh sieve, and the attapulgite is acidified. Putting 10g of acidified attapulgite and 80mL of methanol-water into a 250mL three-neck flask, adding 0.5g of KH-550 and 0.8mL of triethylamine, magnetically stirring, heating and refluxing for 24h, repeatedly washing the attapulgite with ethanol after the reaction is finished until the coupling agent is completely eluted, drying for 24h at 105 ℃, and grinding for later use.
Precisely weighing 50g of bupleuri radix extract in a conical flask, and adding 3.0 mg.L-1Pentachloronitrobenzene, 3.0 mg.L-1Isoprocarb, 3.0 mg.L-1Tetramethrin, 3.0 mg.L-1Propamocarb, 3.0 mg.L-150mL of mixed pesticide aqueous solution of chlorpyrifos and 10g of silane modified attapulgite which are precisely weighed are added into a conical flask, and the mixture is vibrated and adsorbed for 2 hours at constant temperature and 11000 r.min-1Centrifuging at rotating speed for 5min, analyzing pesticide content in the supernatant by GC-MS/MS, and analyzing pesticide content in bupleuri radix extract raw material by GC-MS/MS. The removal rate of 5 pesticides is higher than 80%, and the removal rate of organic chlorine is higher than 96%. The pesticide residue in the removed bupleurum extract meets the maximum pesticide residue limit standard of China, European Union, America and other countries and regions.
Example 3:
placing attapulgite and water in a proportion of 1:50 in a beaker, stirring at normal temperature for 2 days, standing for 2 days, precipitating, placing the middle layer in another beaker, adding water to the original volume, and repeating the steps for 2-3 times. Finally, the middle layer is dried in an oven at 105 ℃, weighed and ground. Mixing the purified attapulgite with 1 mol.L-1The hydrochloric acid is acidified according to the proportion of 1:30, stirred for 2 days at normal temperature, kept stand for 2 days, washed with distilled water for a plurality of times to obtain lower-layer clay solid, filtered, dried, ground, sieved by a 150-mesh sieve, and the attapulgite is acidified. Placing 10g of acidified attapulgite and 120mL of ethanol-water in a 250mL three-neck flask, adding 1g of KH-1161 and 1.2mL of triethylamine, magnetically stirring, heating and refluxing for 24h, repeatedly washing the attapulgite with ethanol after the reaction is finished until the coupling agent is completely eluted, drying at 105 ℃ for 24h, and grindingAnd then standby.
Weighing 50g radix astragali extract in a conical flask, and adding 5.0 mg.L-1Pentachloronitrobenzene, 5.0 mg.L-1Isoprocarb, 5.0 mg.L-1Tetramethrin, 5.0 mg.L-1Propamocarb, 5.0 mg.L-1150mL of mixed pesticide aqueous solution of chlorpyrifos, weighing 10g of silane modified attapulgite, adding into a conical flask, vibrating and adsorbing for 2h at constant temperature, and performing 11000 r.min-1Centrifuging at rotating speed for 5min, and analyzing pesticide content in the supernatant by GC-MS/MS, and analyzing pesticide content in radix astragali extract material by GC-MS/MS. The removal rate of 5 pesticides is higher than 73%, and the removal rate of organic chlorine is as high as 93%. The pesticide residue in the removed astragalus extract meets the maximum pesticide residue limit standard of China, European Union, United states and other countries and regions.
Claims (8)
1. The application of the silane modified attapulgite in removing pesticide residues in Chinese herbal medicines is characterized by comprising the following steps:
weighing Chinese herbal medicine extract sample without pesticide residue and silane modified attapulgite, placing in mixed pesticide water solution, shaking and adsorbing at constant temperature of 15-25 deg.C for 1-2 hr, and performing adsorption at 11000 r.min-1Centrifuging at rotating speed for 5-10min, and analyzing pesticide content in the supernatant by GC-MS/MS;
the mixed pesticide aqueous solution is a mixed solution of 4 different types of pesticides including organic chlorine, organic phosphorus, pyrethrins and carbamate; wherein the concentration of 4 different types of pesticides including organochlorine, organophosphorus, pyrethroid and carbamate in the mixed pesticide aqueous solution is 2-5 mg.L-1；
The silane modified attapulgite clay comprises the following preparation steps:
and (3) purifying the attapulgite: mixing attapulgite with water, stirring at normal temperature of 15-25 deg.C for 2-3 days, standing for 3-4 days, precipitating, collecting the middle layer, adding water to original volume, repeating the above steps for 2-3 times, and drying and grinding the middle layer in an oven at 120 deg.C and 100 deg.C;
acidifying the attapulgite clay: mixing the purified attapulgite with a hydrochloric acid solution, stirring at the normal temperature of 15-25 ℃ for 2-3 days, standing for 3-4 days, washing the lower-layer solid with water for 3-5 times, performing suction filtration, drying, grinding, and sieving with a 150-mesh sieve of 200 meshes;
modifying attapulgite clay: mixing the acidified attapulgite with a medium solution, adding a silane coupling agent and triethylamine, stirring, heating and refluxing for 1-2 days, after the reaction is finished, performing suction filtration, washing a filter cake with ethanol for 3-5 times, drying in an oven at the temperature of 100 ℃ and 120 ℃, and grinding to obtain the silane modified attapulgite.
2. The use of the silane modified attapulgite clay in the removal of Chinese herbal medicine pesticide residues as claimed in claim 1, wherein: the weight ratio of the attapulgite to water in the attapulgite purification step is 1: 20-50.
3. The use of the silane modified attapulgite clay in the removal of Chinese herbal medicine pesticide residues as claimed in claim 1, wherein: in the acidification step of the attapulgite, the weight ratio of the purified attapulgite to the hydrochloric acid solution is 1:20-30, and the concentration of the hydrochloric acid solution is 1 mol-1。
4. The use of the silane modified attapulgite clay in the removal of Chinese herbal medicine pesticide residues as claimed in claim 1, wherein: in the attapulgite modification step, the weight-volume ratio of the acidified attapulgite to the medium solution is 1:8-12, the addition amount of the silane coupling agent is 5-10wt% of the mass of the acidified attapulgite, and the addition amount of the triethylamine is 1% of the volume of the medium solution.
5. The use of the silane-modified attapulgite clay in the removal of Chinese herbal medicine pesticide residues as claimed in claim 1 or 4, wherein: the silane coupling agent is KH-792, KH-550 or KH-1161; the medium solution is ethanol-water, methanol-water, acetone or toluene.
6. The use of the silane modified attapulgite clay in the removal of Chinese herbal medicine pesticide residues as claimed in claim 1, wherein: the weight volume ratio of the traditional Chinese medicine extract to the mixed pesticide aqueous solution is 1:1-3, and the addition amount of the silane modified attapulgite is 1-2wt% of the mass amount of the traditional Chinese medicine extract.
7. The use of the silane-modified attapulgite clay in the removal of Chinese herbal medicine pesticide residues as claimed in claim 1 or 6, wherein: the Chinese medicinal material extract is Ginseng radix extract, radix astragali extract or bupleuri radix extract.
8. The use of the silane modified attapulgite clay in the removal of Chinese herbal medicine pesticide residues as claimed in claim 1, wherein: the organic chlorine pesticide is quintozene; the organophosphorus pesticide is chlorpyrifos; the pyrethroid pesticide is tetramethrin; the carbamate pesticide is isoprocarb or/and propamocarb.
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| US6020282A (en) * | 1997-09-08 | 2000-02-01 | Oil-Dri Corporation Of America | Substantially inert clay product and process for manufacture |
| CN102247807A (en) * | 2011-05-17 | 2011-11-23 | 江苏麦阁吸附剂有限公司 | Preparation method and usage of modified attapulgite adsorption material |
| CN104226263A (en) * | 2014-09-29 | 2014-12-24 | 陕西科技大学 | Method I for preparing amino-modified attapulgite adsorbent and method II for removing hexavalent chromium from water |
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| CN106560235A (en) * | 2016-11-24 | 2017-04-12 | 淮阴师范学院 | Preparation method and application of organic isocyanate-and-isorhodanate modified attapulgite |
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| US6020282A (en) * | 1997-09-08 | 2000-02-01 | Oil-Dri Corporation Of America | Substantially inert clay product and process for manufacture |
| CN102247807A (en) * | 2011-05-17 | 2011-11-23 | 江苏麦阁吸附剂有限公司 | Preparation method and usage of modified attapulgite adsorption material |
| CN104226263A (en) * | 2014-09-29 | 2014-12-24 | 陕西科技大学 | Method I for preparing amino-modified attapulgite adsorbent and method II for removing hexavalent chromium from water |
| CN104787833A (en) * | 2015-04-10 | 2015-07-22 | 环境保护部南京环境科学研究所 | Method for disposing organochlorine pesticide POPs of lixivium in dangerous and polluted sites by utilizing modified attapulgite clay. |
| CN106560235A (en) * | 2016-11-24 | 2017-04-12 | 淮阴师范学院 | Preparation method and application of organic isocyanate-and-isorhodanate modified attapulgite |
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