CN109078610A - A kind of preparation method of silane-modified recessed soil and its application in the residual removing of medium-height grass medicinal herb grower - Google Patents
A kind of preparation method of silane-modified recessed soil and its application in the residual removing of medium-height grass medicinal herb grower Download PDFInfo
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- recessed soil
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- 239000002689 soil Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 244000025254 Cannabis sativa Species 0.000 title claims abstract description 13
- 239000000575 pesticide Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000284 extract Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 230000020477 pH reduction Effects 0.000 claims abstract description 10
- 239000006228 supernatant Substances 0.000 claims abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 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 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 241000202726 Bupleurum Species 0.000 claims description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 6
- 239000005821 Propamocarb Substances 0.000 claims description 6
- 229960000892 attapulgite Drugs 0.000 claims description 6
- 235000020710 ginseng extract Nutrition 0.000 claims description 6
- 229910052625 palygorskite Inorganic materials 0.000 claims description 6
- LKPLKUMXSAEKID-UHFFFAOYSA-N pentachloronitrobenzene Chemical compound [O-][N+](=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl LKPLKUMXSAEKID-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical class 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 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000003020 moisturizing effect Effects 0.000 claims description 5
- 235000021317 phosphate Nutrition 0.000 claims description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229940107666 astragalus root Drugs 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 241000411851 herbal medicine Species 0.000 claims description 3
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 3
- WZZLDXDUQPOXNW-UHFFFAOYSA-N propamocarb Chemical compound CCCOC(=O)NCCCN(C)C WZZLDXDUQPOXNW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- VQXSOUPNOZTNAI-UHFFFAOYSA-N Pyrethrin I Natural products CC(=CC1CC1C(=O)OC2CC(=O)C(=C2C)CC=C/C=C)C VQXSOUPNOZTNAI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 238000005304 joining Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000003986 organophosphate insecticide Substances 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
- VJFUPGQZSXIULQ-XIGJTORUSA-N pyrethrin II Chemical compound 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 VJFUPGQZSXIULQ-XIGJTORUSA-N 0.000 claims description 2
- 235000007516 Chrysanthemum Nutrition 0.000 claims 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 239000000447 pesticide residue Substances 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 239000003814 drug Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 239000004927 clay Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910020175 SiOH Inorganic materials 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 210000004899 c-terminal region Anatomy 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002728 pyrethroid Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 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 compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCN1C(=O)C(CCCC2)=C2C1=O CXBMCYHAMVGWJQ-CABCVRRESA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 241001061264 Astragalus Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000009636 Huang Qi Substances 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 235000006533 astragalus Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013376 functional food Nutrition 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 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
- 239000003993 organochlorine pesticide Substances 0.000 description 1
- 239000003987 organophosphate pesticide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 210000004233 talus Anatomy 0.000 description 1
- 229960005199 tetramethrin Drugs 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses a kind of preparation method of silane-modified recessed soil and its application in the residual removing of medium-height grass medicinal herb grower, the preparation method of silane-modified recessed soil includes the silane-modified of the purifying of recessed soil, the acidification of recessed soil and recessed soil；Silane-modified recessed applying step of the soil in the residual removing of medium-height grass medicinal herb grower include: weigh Chinese medicinal material extract, silane-modified recessed soil is placed in blended aqueous solution, 15 DEG C of -25 DEG C of isothermal vibrations adsorb 1-2h, in 11000 r min‑15-10min is centrifuged under revolving speed, the pesticide concentration in supernatant is analyzed using GC-MS/MS, and the pesticide concentration in Chinese medicinal material extract raw material equally uses GC-MS/MS to analyze.Present invention process is simple, easy to operate, no security risk, and pesticide residue meets the standard of the maximum Pesticide Residues of countries and regions such as China, European Union and the U.S. after removing in Chinese medicinal material extract.And recessed soil is abundant in China's amount of storage, it is cheap.
Description
Technical field
The invention belongs to technical field of natural mineral utilization, are related to a kind of preparation method and application of modified attapulgite, specifically
The preparation method for being related to the silane-modified recessed soil of one kind and its application in the residual removing of medium-height grass medicinal herb grower.
Background technique
With the arriving in " big health epoch ", the traditional Chinese medicine in China plays irreplaceable effect, is widely used in
Drug, development of functional food.
Chinese medicine is in planting process, and to prevent loss caused by pest and disease damage, medicinal herb grower is inevitably dropped using pesticide
Low-risk, therefore excessive pesticide residues have seriously lagged the paces of China's Chinese medicine innovation and development.Agriculture is remained in Chinese medicine at present
Medicine is mainly organochlorine class, organic phosphates, pyrethroid this 3 class.Organic chlorine agriculture chemicals are because its property is stablized, half-life period
It is long, it is difficult to degrade in the soil, most Chinese medicines remain to detect organo-chlorine pesticide.Organophosphorus pesticide is wide in variety, drug effect is high, more
For hypertoxic product.Pyrethroid pesticide is the bionical insecticide of synthesis, and current research focuses mostly in the food such as tealeaves,
Research in Chinese herbal medicine is less.The current remaining method of removing pesticide made of Chinese medicinal herbs reported in the literature mainly have WATER-WASHING METHOD, concocted method,
Photocatalytic method, Subcritical and supercritical leaching method etc., these methods respectively have advantage and disadvantage, and really the blanket medium-height grass medicinal herb grower of energy is residual
The method report of removing is not common.
Attapulgite clay is the silicic acid mineral salt of a kind of layer of chain structure, and amount of storage is abundant, widely used, huge
Specific surface area allows it to possess preferable absorption property.Organosilan is a kind of most popular coupling agent, it can be by functional group
Link aggregation is on substrate, to change the surface of C-terminal substrate, it can form chemical bond or phase between recessed soil
Interreaction force, to enhance the interaction between recessed soil and other substances.Current silane-modified preparation reported in the literature it is recessed
Soil is chiefly used in wastewater treatment or adsorption of metal ions, remaining more rare for removing pesticide in Chinese medicinal material extract, and silicon
The modified method for preparing recessed soil of alkane is not also complicated easy to operate.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation method of silane-modified recessed soil and its in Chinese herbal medicine
Application in the residual removing of agriculture.
The present invention is achieved by the following technical solutions:
A kind of preparation method of silane-modified recessed soil, comprising the following steps:
The purification step of recessed soil: recessed soil being mixed with water, -25 DEG C of stirrings 2-3 days of 15 DEG C of room temperature, standing 3-4 days, is taken after precipitating
Between one layer, moisturizing to original volume repeats above step 2-3 time, finally takes in intermediate one baking oven for being placed on 100-120 DEG C and dries
It is dry, it weighs, grinding must both purify recessed soil；
The acidification step of recessed soil: will purify recessed soil and mix with hydrochloric acid solution, -25 DEG C of stirrings 2-3 days of 15 DEG C of room temperature, stand 3-4 days,
Lower layer's clay solid is washed with distilled water 3-5 times, is filtered, dry, and grinding crosses 150-200 mesh, must both be acidified recessed soil；
The modification procedure of recessed soil: will be acidified recessed soil and mix with medium solution, and silane coupling agent, triethylamine is added, and stirring is heated back
Stream 1-2 days filters after reaction, and filter cake is dried in 100-120 DEG C of baking oven with ethanol washing 3-5 time, and weighing is ground,
Both silane-modified recessed soil.
Further improvement of the present invention scheme are as follows:
The weight ratio of recessed soil described in the purification step of recessed soil and water is 1:20-50.
The recessed soil of purifying described in the acidification step of recessed soil and the weight ratio of hydrochloric acid solution be 1:20-30, the hydrochloric acid is molten
Liquid concentration is 1 mol L-1。
The recessed soil of acidification described in the modification procedure of recessed soil and the w/v of medium solution are 1:8-12, and the silane is even
The additional amount for joining agent is the 5-10wt% for being acidified recessed soil property amount, and the triethylamine additional amount is the 1% of medium solution volume.
The silane coupling agent is KH-792, KH-550 or KH-1161.
The medium solution is alcohol-water, methanol-water, water, acetone or toluene.
Further improvement negative side case of the invention is
Application of the silane-modified recessed soil of one kind obtained in the residual removing of medium-height grass medicinal herb grower, includes the following steps:
Two class Chinese medical extract samples are selected through GC/MS/MS analysis, i.e., containing the residual sample of agriculture and without the residual sample of agriculture.The former is difficult to
It obtains；For this purpose, using current international practice method, standard pesticide solution is added to construct model system with without the residual sample of agriculture, so as to
In the removing ability of verifying removing material.
It weighs and is placed in blended aqueous solution without the residual extract sample of agriculture, silane-modified recessed soil, 15 DEG C of -25 DEG C of constant temperature
Concussion absorption 1-2h, in 11000 r min-15-10min is centrifuged under revolving speed, the pesticide concentration in supernatant uses GC-MS/MS
Analysis.After silane-modified recessed soil removing, pesticide residue meets maximum Pesticide Residue standard in Chinese medicinal material extract.
Further improvement project of the invention are as follows:
The w/v of the Chinese medicinal material extract and blended aqueous solution is 1:1-3, the additional amount of silane-modified recessed soil
It is the 1-2wt% of Chinese medicinal material extract quality.
The Chinese medicinal material extract is ginseng extract, Astragalus Root P.E or bupleurum extract.
The blended aqueous solution is organochlorine class, 4 kinds of organic phosphates, pyrethroids class and carbamate different type agricultures
The mixed solution of medicine.
The organochlorine class, organic phosphates, pyrethroids class and 4 kinds of different type pesticides of carbamate are water-soluble in blended
Concentration in liquid is 2-5mg L-1
The organic chlorine agriculture chemicals are pentachloronitrobenzene；The organophosphorus insecticide is chlopyrifos；The pyrethrin pesticide is amine
Pyrethroids；The carbamate chemicals for agriculture is Mobucin or and Propamocarb.
The invention has the benefit that
The preparation method of silane-modified recessed soil provided by the invention, simple process is easy to operate, no security risk, recessed soil raw material
It is easy to get and cheap.Modified system is the green solvents such as ethyl alcohol, water, methanol, environmentally protective.Acid handles recessed soil, can will wherein
Carbonate deposition dissolution, and then promote the Ca of interlayer2+、Na+、K+、Mg2+Plasma release, duct are dredged, its specific surface is increased
Product, the polarity-SiOH on surface is sufficiently exposed, and after silane coupling agent is combined with surface-SiOH, introduces silicon on attapulgite material surface
Groups, and the hydrophilic and hydrophobic on adjustable surface are conducive to select different silane coupling agent designs different according to different absorption objects
Silanization attapulgite material, convenient for adjust its absorption property.To it is silane-modified it is recessed soil carry out FT-IR, XRD atlas analysis it is found that
Silane coupling agent hydrolysis generates silicone hydroxyl and the activity hydroxy on recessed native surface acts on, and forms chemical bond, functional group is successfully grafted on
Recessed soil surface, improves its hydrophilic and hydrophobic；Be mostly fat-soluble characteristic based on pesticide, select suitable silane coupling agent be modified it is recessed
Soil material makes it be easier to adsorb fat-soluble pesticide residue.
Since attapulgite clay is the silicic acid mineral salt of a kind of layer of chain structure, amount of storage is abundant, widely used, huge
Big specific surface area allows it to possess preferable absorption property.Organosilan is a kind of most popular coupling agent, it can high-ranking military officer
Link aggregation can be rolled into a ball on substrate, to change the surface of C-terminal substrate, chemical bond or phase can be formed between recessed soil
Interreaction force, to enhance the interaction between recessed soil and other substances.Therefore silane-modified recessed soil provided by the invention is answered
When removing residual for medium-height grass medicinal herb grower, the side such as WATER-WASHING METHOD, concocted method, photocatalytic method, Subcritical and supercritical leaching method can be overcome
Time for sample pretreatment existing when pesticide residue is long in method removing Chinese medicinal material extract, is not applicable in generally, security risk etc.
Problem.
Detailed description of the invention
Fig. 1 is the GC-MS/MS comparison diagram of pesticide residue removing front and back in 1 ginseng extract of embodiment；
Wherein, 1 it is Propamocarb, 2 be Mobucin, 3 be pentachloronitrobenzene, 4 be chlopyrifos, 5 is tetramethrin.
Fig. 2 is to purify silane-modified recessed soil FT-IR comparison diagram made from recessed soil, the recessed native and embodiment 1 to 3 of acidification；
Fig. 3 is to purify silane-modified recessed soil XRD comparison diagram made from recessed soil, the recessed native and embodiment 1 to 3 of acidification.
Specific embodiment:
The present invention investigates that silane-modified recessed soil is residual to agriculture to be taken off to remove ginseng, Radix Astragali, in bupleurum extract for pesticide residue
Removing solid capacity.
Embodiment 1:
Recessed soil and water are placed in a beaker in the ratio of 1:20, stirring at normal temperature 2 days, stand 2 days, take centre one to be placed on after precipitating another
In one beaker, in moisturizing to original volume, repeat above step 2-3 times.It finally takes centre one to be placed in 105 DEG C of baking oven to dry
It is dry, it weighs, grinding.To recessed soil after purification and 1 mol L-1Hydrochloric acid be acidified in 1:20 ratio, stirring at normal temperature 2 days, stand 2
It, lower layer's clay solid is repeatedly washed with distilled water, is filtered, dry, grinding, crosses 150 meshes, and recessed mud acidization is completed.Take 10g sour
Change recessed soil and 100mL toluene is placed in 250mL three-necked flask, 0.7g KH-792,1mL triethylamine, magnetic agitation, heating is added
For 24 hours, after reaction, recessed soil is cleaned repeatedly with ethyl alcohol for reflux, until coupling agent elutes completely, for 24 hours in 105 DEG C of dryings, grinding is standby
With.
For precision weighing 50g ginseng extract in conical flask, addition concentration is 2.0mg L-1Pentachloronitrobenzene, 2.0mg L-1Mobucin, 2.0mg L-1Tetramethrin, 2.0mg L-1Propamocarb, 2.0mg L-1The blended aqueous solution 100mL of chlopyrifos, essence
The close silane-modified recessed soil of weighing 5g is added in conical flask, and isothermal vibration adsorbs 2h, in 11000 r min-1It is centrifuged 5min under revolving speed,
Pesticide concentration in supernatant is analyzed using GC-MS/MS, and the pesticide concentration in ginseng extract raw material equally uses GC-MS/
MS analysis.5 kinds of pesticide removal efficiencies are above 77 %, and organochlorine class is more up to 90 %, ginseng extract middle peasant medicine after removing
Residual meets the standard of the maximum Pesticide Residues of countries and regions such as China, European Union and the U.S..
Embodiment 2:
Recessed soil and water are placed in a beaker in the ratio of 1:40, stirring at normal temperature 2 days, stand 2 days, take centre one to be placed on after precipitating another
In one beaker, in moisturizing to original volume, repeat above step 2-3 times.It finally takes centre one to be placed in 105 DEG C of baking oven to dry
It is dry, it weighs, grinding.To recessed soil after purification and 1 mol L-1Hydrochloric acid be acidified in 1:25 ratio, stirring at normal temperature 2 days, stand 2
It, lower layer's clay solid is repeatedly washed with distilled water, is filtered, dry, grinding, crosses 150 meshes, and recessed mud acidization is completed.Take 10g sour
Change recessed soil and 80mL methanol-water is placed in 250mL three-necked flask, addition 0.5g KH-550,0.8mL triethylamine, magnetic agitation,
It is heated to reflux for 24 hours, after reaction, recessed soil is cleaned repeatedly with ethyl alcohol, until coupling agent elutes completely, for 24 hours in 105 DEG C of dryings, is ground
Mill, it is spare.
For precision weighing 50g bupleurum extract in conical flask, addition concentration is 3.0mg L-1Pentachloronitrobenzene, 3.0mg L-1Mobucin, 3.0mg L-1Tetramethrin, 3.0mg L-1Propamocarb, 3.0mg L-1The blended aqueous solution 50mL of chlopyrifos, essence
The close silane-modified recessed soil of weighing 10g is added in conical flask, and isothermal vibration adsorbs 2h, in 11000 r min-1It is centrifuged under revolving speed
5min, the pesticide concentration in supernatant are analyzed using GC-MS/MS, and the pesticide concentration in bupleurum extract raw material equally uses
GC-MS/MS analysis.5 kinds of pesticide removal efficiencies are above 80 %, and organochlorine class is more up to 96 %.Bupleurum extract after removing
Middle pesticide residue meets the standard of the maximum Pesticide Residues of countries and regions such as China, European Union and the U.S..
Embodiment 3:
Recessed soil and water are placed in a beaker in the ratio of 1:50, stirring at normal temperature 2 days, stand 2 days, take centre one to be placed on after precipitating another
In one beaker, in moisturizing to original volume, repeat above step 2-3 times.It finally takes centre one to be placed in 105 DEG C of baking oven to dry
It is dry, it weighs, grinding.To recessed soil after purification and 1 mol L-1Hydrochloric acid be acidified in 1:30 ratio, stirring at normal temperature 2 days, stand 2
It, lower layer's clay solid is repeatedly washed with distilled water, is filtered, dry, grinding, crosses 150 meshes, and recessed mud acidization is completed.Take 10g sour
Change recessed soil and 120mL alcohol-water is placed in 250mL three-necked flask, addition 1g KH-1161,1.2mL triethylamine, magnetic agitation,
It is heated to reflux for 24 hours, after reaction, recessed soil is cleaned repeatedly with ethyl alcohol, until coupling agent elutes completely, for 24 hours in 105 DEG C of dryings, is ground
Mill, it is spare.
50g Astragalus Root P.E is weighed in conical flask, addition concentration is 5.0mg L-1Pentachloronitrobenzene, 5.0mg L-1It is different
Third prestige, 5.0mg L-1Tetramethrin, 5.0mg L-1Propamocarb, 5.0mg L-1The blended aqueous solution 150mL of chlopyrifos, it weighs
The silane-modified recessed soil of 10g is added in conical flask, and isothermal vibration adsorbs 2h, in 11000 r min-15min, supernatant are centrifuged under revolving speed
Pesticide concentration in liquid is analyzed using GC-MS/MS, and the pesticide concentration in astragalus extraction raw material is equally using GC-MS/MS points
Analysis.5 kinds of pesticide removal efficiencies are above 73 %, and organochlorine class is more up to 93 %.Pesticide residue accords in Astragalus Root P.E after removing
Close the standard of the maximum Pesticide Residues of countries and regions such as China, European Union and the U.S..
Claims (10)
1. a kind of preparation method of silane-modified recessed soil, it is characterised in that the following steps are included:
The purification step of recessed soil: recessed soil being mixed with water, -25 DEG C of stirrings 2-3 days of 15 DEG C of room temperature, standing 3-4 days, is taken after precipitating
Between one layer, moisturizing to original volume repeats above step 2-3 time, finally takes in intermediate one baking oven for being placed on 100-120 DEG C and dries
Dry, grinding；
The acidification step of recessed soil: will purify recessed soil and mix with hydrochloric acid solution, -25 DEG C of stirrings 2-3 days of 15 DEG C of room temperature, stand 3-4 days,
Lower layer's solid is washed with water 3-5 times, filters, dry, and 150-200 mesh is crossed in grinding；
The modification procedure of recessed soil: will be acidified recessed soil and mix with medium solution, and silane coupling agent, triethylamine is added, and stirring is heated back
Stream 1-2 days, after reaction, suction filtration, filter cake are dried in 100-120 DEG C of baking oven, are ground to obtain silane with ethanol washing 3-5 time
Modified attapulgite.
2. the preparation method of the silane-modified recessed soil of one kind according to claim 1, it is characterised in that: the purification step of recessed soil
Described in recessed soil and the weight ratio of water be 1:20-50.
3. the preparation method of the silane-modified recessed soil of one kind according to claim 1, it is characterised in that: the acidification step of recessed soil
Described in the recessed soil of purifying and the weight ratio of hydrochloric acid solution be 1:20-30, the concentration of hydrochloric acid solution is 1 mol L-1。
4. the preparation method of the silane-modified recessed soil of one kind according to claim 1, it is characterised in that: the modification procedure of recessed soil
Described in the recessed soil of acidification and the w/v of medium solution be 1:8-12, the additional amount of the silane coupling agent is the recessed soil of acidification
The 5-10wt% of quality, the triethylamine additional amount are the 1% of medium solution volume.
5. the preparation method of the silane-modified recessed soil of one kind according to claim 1 or 4, it is characterised in that: the silane is even
Joining agent is KH-792, KH-550 or KH-1161；The medium solution is alcohol-water, methanol-water, water, acetone or toluene.
6. application of the silane-modified recessed soil of one kind obtained by claim 1 in the residual removing of medium-height grass medicinal herb grower, it is characterised in that packet
Include following steps:
It weighs and is placed in blended aqueous solution without the residual Chinese herbal medicine extract sample of agriculture, silane-modified recessed soil, 15 DEG C -25 DEG C
Isothermal vibration adsorbs 1-2h, in 11000 r min-15-10min is centrifuged under revolving speed, the pesticide concentration in supernatant uses GC-MS/
MS analysis.
7. application of the silane-modified recessed soil of one kind according to claim 6 in the residual removing of medium-height grass medicinal herb grower, it is characterised in that:
The w/v of the Chinese medicinal material extract and blended aqueous solution is 1:1-3, during the additional amount of silane-modified recessed soil is
The 1-2wt% of medicinal material extract amount of substance.
8. application of the silane-modified recessed soil of one kind according to claim 6 or 7 in the residual removing of medium-height grass medicinal herb grower, feature exist
In: the Chinese medicinal material extract is ginseng extract, Astragalus Root P.E or bupleurum extract.
9. application of the silane-modified recessed soil of one kind according to claim 6 or 7 in the residual removing of medium-height grass medicinal herb grower, feature exist
In: the blended aqueous solution is 4 kinds of organochlorine class, organic phosphates, pyrethroids class and carbamate different type pesticides
Mixed solution；Wherein 4 kinds of organochlorine class, organic phosphates, pyrethroids class and carbamate different type pesticides are in blended water
Concentration in solution is 2-5mg L-1。
10. application of the silane-modified recessed soil of one kind according to claim 9 in the residual removing of medium-height grass medicinal herb grower, feature exist
In: the organic chlorine agriculture chemicals are pentachloronitrobenzene；The organophosphorus insecticide is chlopyrifos；The pyrethrin pesticide is amine chrysanthemum
Ester；The carbamate chemicals for agriculture is Mobucin or and Propamocarb.
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Application publication date: 20181225 Assignee: Huai'an Changhao Biomedical Technology Co.,Ltd. Assignor: HUAIYIN INSTITUTE OF TECHNOLOGY Contract record no.: X2023980054729 Denomination of invention: A preparation method of silane modified concave soil and its application in the removal of pesticide residues in traditional Chinese medicine Granted publication date: 20210525 License type: Common License Record date: 20240103 |