WO2024103217A1 - 一种去除桑叶残留农药清洁剂及其制备方法与应用 - Google Patents
一种去除桑叶残留农药清洁剂及其制备方法与应用 Download PDFInfo
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- WO2024103217A1 WO2024103217A1 PCT/CN2022/131711 CN2022131711W WO2024103217A1 WO 2024103217 A1 WO2024103217 A1 WO 2024103217A1 CN 2022131711 W CN2022131711 W CN 2022131711W WO 2024103217 A1 WO2024103217 A1 WO 2024103217A1
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- WIPO (PCT)
- Prior art keywords
- mulberry leaves
- pesticide
- agent
- silkworms
- cleaning agent
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- 240000000249 Morus alba Species 0.000 title claims abstract description 118
- 235000008708 Morus alba Nutrition 0.000 title claims abstract description 118
- 239000012459 cleaning agent Substances 0.000 title claims abstract description 33
- 239000000447 pesticide residue Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims description 6
- 241000255789 Bombyx mori Species 0.000 claims abstract description 77
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- HOBWAPHTEJGALG-JKCMADFCSA-N [(1r,5s)-8-methyl-8-azoniabicyclo[3.2.1]octan-3-yl] 3-hydroxy-2-phenylpropanoate;sulfate Chemical compound [O-]S([O-])(=O)=O.C([C@H]1CC[C@@H](C2)[NH+]1C)C2OC(=O)C(CO)C1=CC=CC=C1.C([C@H]1CC[C@@H](C2)[NH+]1C)C2OC(=O)C(CO)C1=CC=CC=C1 HOBWAPHTEJGALG-JKCMADFCSA-N 0.000 claims abstract description 18
- 229960002028 atropine sulfate Drugs 0.000 claims abstract description 18
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 17
- 235000001453 Glycyrrhiza echinata Nutrition 0.000 claims abstract description 16
- 235000006200 Glycyrrhiza glabra Nutrition 0.000 claims abstract description 16
- 235000017382 Glycyrrhiza lepidota Nutrition 0.000 claims abstract description 16
- 229940010454 licorice Drugs 0.000 claims abstract description 16
- 239000001509 sodium citrate Substances 0.000 claims abstract description 14
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims abstract description 11
- 231100000572 poisoning Toxicity 0.000 claims abstract description 7
- 230000000607 poisoning effect Effects 0.000 claims abstract description 7
- 239000000575 pesticide Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 241000202807 Glycyrrhiza Species 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 11
- 239000003599 detergent Substances 0.000 claims description 10
- 206010008428 Chemical poisoning Diseases 0.000 claims description 9
- 239000003814 drug Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims 1
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 240000004670 Glycyrrhiza echinata Species 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 1
- 235000002639 sodium chloride Nutrition 0.000 abstract 1
- 239000011780 sodium chloride Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000005886 Chlorantraniliprole Substances 0.000 description 5
- PSOVNZZNOMJUBI-UHFFFAOYSA-N chlorantraniliprole Chemical compound CNC(=O)C1=CC(Cl)=CC(C)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl PSOVNZZNOMJUBI-UHFFFAOYSA-N 0.000 description 5
- 230000033001 locomotion Effects 0.000 description 5
- ATROHALUCMTWTB-OWBHPGMISA-N phoxim Chemical compound CCOP(=S)(OCC)O\N=C(\C#N)C1=CC=CC=C1 ATROHALUCMTWTB-OWBHPGMISA-N 0.000 description 5
- 208000024891 symptom Diseases 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000009395 breeding Methods 0.000 description 4
- 230000001488 breeding effect Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000012154 double-distilled water Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000003020 moisturizing effect Effects 0.000 description 4
- 210000003462 vein Anatomy 0.000 description 4
- 241000607479 Yersinia pestis Species 0.000 description 3
- 229960003022 amoxicillin Drugs 0.000 description 3
- LSQZJLSUYDQPKJ-NJBDSQKTSA-N amoxicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=C(O)C=C1 LSQZJLSUYDQPKJ-NJBDSQKTSA-N 0.000 description 3
- AVKUERGKIZMTKX-NJBDSQKTSA-N ampicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=CC=C1 AVKUERGKIZMTKX-NJBDSQKTSA-N 0.000 description 3
- 229960000723 ampicillin Drugs 0.000 description 3
- 229940036735 ceftaroline Drugs 0.000 description 3
- ZCCUWMICIWSJIX-NQJJCJBVSA-N ceftaroline fosamil Chemical compound S([C@@H]1[C@@H](C(N1C=1C([O-])=O)=O)NC(=O)\C(=N/OCC)C=2N=C(NP(O)(O)=O)SN=2)CC=1SC(SC=1)=NC=1C1=CC=[N+](C)C=C1 ZCCUWMICIWSJIX-NQJJCJBVSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- LSQZJLSUYDQPKJ-UHFFFAOYSA-N p-Hydroxyampicillin Natural products O=C1N2C(C(O)=O)C(C)(C)SC2C1NC(=O)C(N)C1=CC=C(O)C=C1 LSQZJLSUYDQPKJ-UHFFFAOYSA-N 0.000 description 3
- 229950001664 phoxim Drugs 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 229930186147 Cephalosporin Natural products 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
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- 208000007101 Muscle Cramp Diseases 0.000 description 2
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- 229940124587 cephalosporin Drugs 0.000 description 2
- 150000001780 cephalosporins Chemical class 0.000 description 2
- 230000009194 climbing Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000019617 pupation Effects 0.000 description 2
- 238000009666 routine test Methods 0.000 description 2
- 238000009366 sericulture Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 102000012440 Acetylcholinesterase Human genes 0.000 description 1
- 108010022752 Acetylcholinesterase Proteins 0.000 description 1
- 208000035742 Air-borne transmission Diseases 0.000 description 1
- 241000255783 Bombycidae Species 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 108010022355 Fibroins Proteins 0.000 description 1
- 102100030643 Hydroxycarboxylic acid receptor 2 Human genes 0.000 description 1
- 108700010041 Nicotinic acid receptor Proteins 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 229940022698 acetylcholinesterase Drugs 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000005557 airborne transmission Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229960004682 cefoperazone Drugs 0.000 description 1
- GCFBRXLSHGKWDP-XCGNWRKASA-N cefoperazone Chemical compound O=C1C(=O)N(CC)CCN1C(=O)N[C@H](C=1C=CC(O)=CC=1)C(=O)N[C@@H]1C(=O)N2C(C(O)=O)=C(CSC=3N(N=NN=3)C)CS[C@@H]21 GCFBRXLSHGKWDP-XCGNWRKASA-N 0.000 description 1
- 229960000484 ceftazidime Drugs 0.000 description 1
- NMVPEQXCMGEDNH-TZVUEUGBSA-N ceftazidime pentahydrate Chemical compound O.O.O.O.O.S([C@@H]1[C@@H](C(N1C=1C([O-])=O)=O)NC(=O)\C(=N/OC(C)(C)C(O)=O)C=2N=C(N)SC=2)CC=1C[N+]1=CC=CC=C1 NMVPEQXCMGEDNH-TZVUEUGBSA-N 0.000 description 1
- 229960004755 ceftriaxone Drugs 0.000 description 1
- VAAUVRVFOQPIGI-SPQHTLEESA-N ceftriaxone Chemical compound S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)\C(=N/OC)C=2N=C(N)SC=2)CC=1CSC1=NC(=O)C(=O)NN1C VAAUVRVFOQPIGI-SPQHTLEESA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 230000004379 myopia Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 239000003987 organophosphate pesticide Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 235000018770 reduced food intake Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/12—Carbonates bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/34—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/40—Products in which the composition is not well defined
- C11D7/44—Vegetable products
Definitions
- the invention belongs to the technical field of residual pesticide cleaning, and in particular relates to the development of a cleaning agent for removing residual pesticides from mulberry leaves, which can remove various residual pesticides and prevent pesticide poisoning of silkworms.
- the silkworm ( Bombyx mori L.) is a holometabolous insect belonging to the family Bombycidae in the order Lepidoptera. It mainly feeds on mulberry leaves and can spin silk and make cocoons.
- the sericulture industry originated, developed and spread in China. To this day, silk products are still widely used, such as silk quilts, silk fabrics, surgical sutures and substrates made of silk fibroin, which have extremely high commercial and cultural value.
- the silkworm is easy to raise, has a short generation cycle and can represent the physiological characteristics of Lepidoptera insects, and has extremely high scientific research value.
- Mulberry leaves are the most ideal feeding material for silkworms. Silkworms mainly feed on fresh mulberry leaves in their young stages to store nutrients for subsequent pupation and moth formation.
- Phoxim also known as oximethion, mainly acts on acetylcholinesterase. It is a classic organophosphorus pesticide. Pesticide residues in mulberry leaves are extremely harmful to silkworms, which will seriously affect the normal physiological activities of silkworms, causing reduced food intake, slow movements, and vomiting of intestinal fluid, resulting in reduced cocoon and silk production. Even if there are trace amounts of pesticides left in mulberry leaves, silkworms will show uneven growth and development, weak constitution, poor resistance, low cocooning rate and low cocooning rate, which seriously affects the economic benefits of silkworm breeding. With the advancement of silkworm breeding, traditional mulberry leaf cleaners and cleaning methods cannot effectively clean mulberry leaf pesticide residues and are environmentally friendly and non-toxic. There is an urgent need to develop a cleaner that can effectively remove pesticide residues in mulberry leaves.
- the purpose of the present invention is to provide a formula for removing pesticide residues in mulberry leaves and a preparation method thereof, so as to reduce pesticide residues and prevent pesticide poisoning of silkworms, and improve the cocooning rate and cocooning rate of silkworms.
- the present invention applies atropine sulfate to the pesticide residue removal detergent, combines with other components, and studies the formula for reducing pesticide residues in mulberry leaves, which plays an important role in ensuring the safety of silkworm breeding.
- the technical solution adopted by the present invention is: a cleaning agent for removing residual pesticides in mulberry leaves, and the preparation method of the cleaning agent for removing residual pesticides in mulberry leaves comprises the following steps: adding the agent to water containing atropine sulfate, and mixing evenly to form a cleaning agent; the agent comprises licorice powder, sodium bicarbonate, citric acid, sodium citrate, ethanol, an antibacterial agent and salt.
- a method for reducing pesticide residues and preventing pesticide poisoning of silkworms based on a pesticide cleaning agent comprising the following steps: using the pesticide cleaning agent to soak and clean mulberry leaves containing residual pesticides, rinsing with clean water for several times and draining, or directly spraying and cleaning the mulberry leaves;
- the agent comprises licorice powder, sodium bicarbonate, citric acid, sodium citrate, ethanol, an antibacterial agent and salt.
- the above-mentioned cleaning agent for removing pesticide residues on mulberry leaves is used in reducing pesticide residues on mulberry leaves or in preparing a cleaning agent for reducing pesticide residues on mulberry leaves.
- the amount of water used is 2.5 to 3.5 times the weight of the agent, and when the spraying method is adopted, the amount of water used is 6 to 8 times the weight of the agent; for example, according to the weight of the basic formula, 2.8 to 3.1 times the weight of the agent (immersion method) or 6.9 to 7.3 times the weight of the agent (spraying method) is measured, preferably pure water, atropine sulfate is added to the water, the agent is added after mixing, and then the mixture is bottled and stored for later use; when the spraying method is adopted, the weight of the mulberry leaves is 1.5 to 2.7 times the weight of the detergent, preferably 2 times; the detergent is stored at a temperature of 20°C ⁇ 3°C, and is kept away from light, and the storage time can reach 40 days.
- the dosage of atropine sulfate is 0.1 g/kg to 0.5 g/kg, and the concentration has an effect on preventing pesticide poisoning of silkworms and preventing toxicity; adding a small amount of atropine sulfate to the detergent can improve the beneficial effect of mulberry leaves on silkworms after cleaning to a certain extent.
- the medicament is composed of licorice powder, sodium bicarbonate, citric acid, sodium citrate, ethanol, antibacterial agent and salt; taking the mass of the medicament as 100%, by mass percentage, the licorice powder is 20-30%, the sodium bicarbonate is 15-20%, the citric acid is 8-15%, the sodium citrate is 8-15%, the ethanol is 25-30%, the antibacterial agent is 2-10%, and the salt is the balance.
- licorice powder refers to fresh licorice after rinsing, chopping, drying and powdering, with a fineness of 100-200 mesh, too large a fineness is easy to precipitate, and too small a fineness increases the powdering cost.
- the antibacterial agent is composed of ampicillin, amoxicillin, and cephalosporins, preferably mixed in a mass ratio of 1:1:1, wherein the cephalosporin is ceftaroline, cefoperazone, ceftriaxone or ceftazidime.
- the present invention provides a formula and preparation method of a cleaning agent for removing pesticide residues from mulberry leaves, and the formula is mostly non-toxic and natural raw materials, which are non-toxic to silkworms.
- the cleaning agent for removing residual pesticides from mulberry leaves developed by the present invention contains a small amount of atropine sulfate, which, combined with the agent, can prevent the toxicity of residual organophosphorus pesticides to silkworms.
- the ethanol used in the cleaning agent for removing residual pesticides from mulberry leaves developed by the present invention can play a bactericidal role, and the volatility of ethanol makes it take a shorter time for the mulberry leaves to drain water.
- the innovation of the present invention is to develop a cleaning agent and cleaning method for removing residual pesticides from mulberry leaves in response to production needs, and use clean mulberry leaves to feed silkworms to avoid silkworm poisoning from the source.
- the preparation method of the cleaning agent for removing residual pesticides from mulberry leaves of the present invention is as follows: the agent is added to water containing atropine sulfate, and mixed evenly to form a cleaning agent; the agent includes licorice powder, sodium bicarbonate, citric acid, sodium citrate, ethanol, antibacterial agent and salt, preferably based on the mass of the agent as 100%, by mass percentage, licorice powder is 20-30%, sodium bicarbonate is 15-20%, citric acid 8-15%, sodium citrate 8-15%, ethanol 25-30%, antibacterial agent 2-10%, and salt is the balance.
- the cleaning agent is sealed in a bottle before shaking to prevent alcohol from volatilizing during the shaking process, and is fully shaken on a shaker so that the agent and water are fully mixed.
- the experimental silkworm variety used was the "Jingsong ⁇ Haoyue” variety, which was purchased from the silkworm breeding farm in Dongtai City, Jiangsu province.
- the larvae were raised with mulberry leaves at a temperature of 25°C ⁇ 1°C, a humidity of 75% to 85%, 12 hours of light and 12 hours of darkness.
- the effectiveness of the detergent is determined by statistically analyzing the full-age morbidity, cocooning rate and cocooning rate of silkworms fed with clean mulberry leaves.
- the statistical methods for the morbidity, cocooning rate and cocooning rate are conventional methods; atropine sulfate, licorice, sodium bicarbonate, citric acid, sodium citrate, ethanol, antibacterial agents and salt are all commercially available conventional products.
- Example 1 Application effect of using the immersion method to clean mulberry leaves with trace amounts of chlorantraniliprole.
- the formula of the drug is: 25% licorice powder (fineness 150 mesh), 17% sodium bicarbonate, 10% citric acid, 10% sodium citrate, 27% ethanol, 7% antibacterial agent, and 4% salt.
- the antibacterial agent is composed of ampicillin, amoxicillin, and ceftaroline mixed in a mass ratio of 1:1:1.
- the collected fresh mulberry leaves with the main veins removed were divided into two groups, with 100 g of mulberry leaves in each group.
- the two groups of mulberry leaves were completely immersed in 0.005 ⁇ g/mL chlorantraniliprole solution according to the "leaf dipping method". After 1 minute, they were taken out and dried and placed in a culture dish with moisturizing filter paper.
- the mulberry leaves of the control group were completely immersed in double distilled water, and the mulberry leaves of the experimental group were completely immersed in the prepared detergent, placed on a 100 r/min shaker for 2 hours, and the mulberry leaves were taken out and rinsed with water once; after drying at room temperature, 30 larvae on the third day of the fifth instar were fed with the treated mulberry leaves, 15 in each control group and experimental group. Feed twice a day, and the remaining mulberry leaves in the silkworm box should be cleaned before each feeding. On the seventh day of the fifth instar, the rate of silkworm cocooning and the rate of cocooning were counted. The experiment was repeated three times, and the average values of the incidence rate, cocooning rate and cocooning rate of the three experiments were obtained.
- the average number of silkworms in the control group was 14, and the average number of silkworms in the experimental group was 2.
- the rate of silkworms in the control group was 83%, and the rate of cocoon formation was 80%, while the rate of silkworms in the experimental group was 95%, and the rate of cocoon formation was 93%.
- Most of the silkworms in the control group showed symptoms such as reduced silkworm feeding and slow movement, while most of the silkworms in the experimental group were active, with normal body stretch and shiny body wall.
- Example 2 Application effect of using the immersion method to clean mulberry leaves with trace amounts of phoxim residues.
- the collected fresh mulberry leaves with the main veins removed were divided into two groups, each with 100 g of mulberry leaves.
- the two groups of mulberry leaves were completely immersed in 0.05 g/L phoxim solution according to the "leaf immersion method". After 1 minute, they were taken out and dried and placed in a culture dish with moisturizing filter paper.
- the mulberry leaves of the control group were completely immersed in double distilled water, and the mulberry leaves of the experimental group were completely immersed in the prepared detergent (Example 1), placed on a 100 r/min shaker for 2 hours, and the mulberry leaves were taken out and rinsed once.
- Example 3 Application effect of using spraying method to clean mulberry leaves with trace amounts of chlorantraniliprole.
- the formula of the medicine is: 30% licorice powder (fineness 150 mesh), 19% sodium bicarbonate, 8% citric acid, 8% sodium citrate, 30% ethanol, 3% antibacterial agent, and 2% salt.
- the antibacterial agent is composed of ampicillin, amoxicillin, and ceftaroline mixed in a mass ratio of 1:1:1.
- the collected fresh mulberry leaves with the main veins removed were divided into two groups, with 100 g of mulberry leaves in each group.
- the two groups of mulberry leaves were completely immersed in 0.005 ⁇ g/mL chlorantraniliprole solution according to the "leaf dipping method". After 1 minute, they were taken out and dried and placed in a culture dish with moisturizing filter paper. 50 g of double distilled water was sprayed on the mulberry leaves of the control group, and the mulberry leaves were completely soaked at this time. 50 g of detergent was sprayed on the mulberry leaves of the experimental group, and the mulberry leaves were completely soaked at this time.
- the average number of cases in the control group was 13, and the average number of cases in the experimental group was 2.
- the rate of silkworms climbing cocoons in the control group was 88%, and the rate of cocooning was 85%, while the rate of silkworms climbing cocoons in the experimental group was 95%, and the rate of cocooning was 94%.
- Most of the silkworms in the control group showed symptoms such as reduced silkworm feeding and slow movement, while most of the silkworms in the experimental group were active, with normal body stretch and shiny body walls.
- atropine sulfate aqueous solution is used, the experimental results are no different from those of the control group. If licorice and atropine sulfate are omitted, the cocooning rate of silkworms drops to 88%. If citric acid and sodium citrate are omitted, the cocooning rate of silkworms drops to 90%. If ethanol and antibacterial agents are omitted, the cocooning rate of silkworms drops to 89%.
- Example 4 Application effect of using spraying method to clean mulberry leaves with trace amounts of phoxim residues.
- the collected fresh mulberry leaves with the main veins removed were divided into two groups, each with 100 g of mulberry leaves.
- the two groups of mulberry leaves were completely immersed in a 0.05 g/L phoxim solution according to the "leaf immersion method". After 1 minute, they were taken out and dried and placed in a culture dish with moisturizing filter paper. 50 g of double distilled water was sprayed on the mulberry leaves of the control group, and the mulberry leaves were completely soaked at this time. 50 g of detergent (Example 3) was sprayed on the mulberry leaves of the experimental group, and the mulberry leaves were completely soaked at this time.
- the average number of cases in the control group was 13, and the average number of cases in the experimental group was 1.
- the rate of silkworms in the control group was 90%, and the rate of cocoon formation was 85%, while the rate of silkworms in the experimental group was 100%, and the rate of cocoon formation was 93%.
- Most of the silkworms in the control group showed symptoms such as slow movement and spasms, while most of the silkworms in the experimental group were active, with normal body stretch and shiny body wall.
- the present invention soaks mulberry leaves with the above-mentioned cleaning agent for removing pesticide residues in mulberry leaves, rinses them with clean water, and dries them to obtain clean mulberry leaves; or sprays mulberry leaves with the cleaning agent for removing pesticide residues in mulberry leaves, and then dries them to obtain clean mulberry leaves; and then uses the clean mulberry leaves to feed silkworms, thereby reducing the poisoning rate of silkworms and preventing pesticide poisoning of silkworms.
- the present invention does not require rinsing when spraying, which can clean mulberry leaves without affecting the growth and development of silkworms. In large-scale production, it can achieve the effects of saving time and labor, saving production costs, having a good cleaning effect, and being substantially harmless to silkworms.
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Abstract
一种去除桑叶残留农药的清洁剂，其特征在于，包括药剂以及硫酸阿托品；药剂包括甘草粉、碳酸氢钠、柠檬酸、柠檬酸钠、乙醇、抗菌剂和食盐。该清洁剂采用天然和无毒原料，避免了清洁剂残留导致的家蚕中毒。
Description
本发明属于残留农药清洁技术领域，具体涉及一种去除桑叶残留农药清洁剂的开发，可以去除各种残留农药和预防家蚕农药中毒。
家蚕（
Bombyx mori L.）属鳞翅目蚕蛾科完全变态昆虫，主要以桑叶为食，能够吐丝结茧。蚕桑产业最早在我国起源、发展和流传，时至今日，蚕丝制品仍然有着广泛的应用，如蚕丝被、丝绸面料、手术缝合线和以丝素蛋白为原料的基材，具有极高的商业价值和文化价值。同时，家蚕作为模式生物，饲养方便、世代周期短并且可代表鳞翅目昆虫的生理特征，具有极高的科研价值。桑叶是家蚕最理想的饲育材料，家蚕在幼龄期主要以新鲜桑叶为食，储存营养物质以供接下来化蛹和化蛾使用。
随着农药在生产上被广泛使用，家蚕农药中毒的事件时有发生，给蚕桑养殖产业带来巨大的损失。常见的农药有：有机磷类农药、有机氮类农药、菊酯类农药和其他类型杀虫剂。农药通过空气传播对周边桑园造成的污染，桑园治虫后所残留的农药以及农具残留农药污染桑园等情况均可导致家蚕农药中毒。氯虫苯甲酰胺，商品名为“康宽”，是一种以鱼尼丁受体为靶标的广谱杀虫剂，主要通过扰乱昆虫细胞的钙离子平衡，引起害虫肌肉调节功能衰弱，从而杀灭害虫。辛硫磷又名肟硫磷，主要作用于乙酰胆碱酯酶，是一种经典的有机磷农药杀虫剂农药桑叶残留对家蚕危害巨大，会严重影响家蚕正常的生理活动，出现食量减少，行动迟缓和吐肠液等现象，使得产茧量和产丝量降低。即使桑叶残留微量农药，家蚕也会表现出生长发育不齐、体质虚弱、抵抗力差、上蔟率和结茧率低的现象，严重影响家蚕饲养的经济效益。随着养蚕规模化的推进，传统的桑叶清洁剂和清洁方法不能达到有效清洁桑叶残留农药且环保无毒的效果，迫切需要开发一种有效去除桑叶残留农药的清洁剂。
本发明的目的是提供一种去除桑叶残留农药清洁剂的配方及其制备方法，减少农药残留以及预防家蚕农药中毒，提高家蚕上蔟率和结茧率。基于上述实际情况，本发明将硫酸阿托品应用于去除残留农药清洁剂，结合其他组分，研究减少桑叶农药残留的配方，对于保障养蚕的安全，具有重要的作用。
为达到上述发明目的，本发明采用的技术方案是：一种去除桑叶残留农药清洁剂，所述去除桑叶残留农药清洁剂的制备方法包括以下步骤：将药剂加入含有硫酸阿托品的水中，混合均匀制成清洁剂；所述药剂包括甘草粉、碳酸氢钠、柠檬酸、柠檬酸钠、乙醇、抗菌剂和食盐。
一种基于农药清洁剂减少农药残留以及预防家蚕农药中毒的方法，包括以下步骤：利用上述农药清洁剂浸泡清洗含有残留农药的桑叶，用清水漂洗数次沥干，或者直接喷洒清洁桑叶；所述药剂包括甘草粉、碳酸氢钠、柠檬酸、柠檬酸钠、乙醇、抗菌剂和食盐。
上述去除桑叶残留农药清洁剂在降低桑叶农药残留中的应用或在制备降低桑叶上农药残留清洁剂中的应用。
本发明中，采用浸泡法时水的用量为药剂质量的2.5～3.5倍，采用喷洒法时水的用量为药剂质量的6～8倍；比如根据基础配方的重量，量取药剂质量2.8~3.1倍的水（浸泡法）或6.9～7.3倍（喷洒法），优选纯净水，在水中加入硫酸阿托品，混匀后加入药剂搅拌后瓶装储存备用；采用喷洒法时，桑叶重量为清洁剂重量的1.5～2.7倍，优选2倍；清洁剂储存的温度为20℃±3℃，避光保存，保存时间可达到40天。
本发明中，以药剂为基准，硫酸阿托品的剂量是0.1 g/kg～0.5 g/kg，浓度对于预防家蚕农药中毒以及防止毒性有影响；在清洁剂中加入少量硫酸阿托品，一定程度上可以提高清洁后桑叶对家蚕的有利影响。
本发明中，药剂由甘草粉、碳酸氢钠、柠檬酸、柠檬酸钠、乙醇、抗菌剂和食盐组成；以药剂质量为100%计，按质量百分数，甘草粉为20~30%，碳酸氢钠为15~20%，柠檬酸8~15%，柠檬酸钠8~15%，乙醇25~30%，抗菌剂2~10%，食盐为余量。
本发明中，甘草粉是指新鲜甘草经漂洗、切碎、烘干和制粉，细度为100~200目，细度太大易沉淀，细度太小增加制粉成本。优选的，抗菌剂由氨苄西林、阿莫西林、头孢类药物组成，优选按照质量比1:1:1混合组成，其中头孢类药物为头孢洛林、头孢哌酮、头孢曲松或者头孢他啶。
影响去除桑叶残留农药清洁技术的实用化的因素较多，主要包括清洁效果不佳、适用范围较小、清洁剂对家蚕有毒性等，目前已公布的果蔬、植物农药清洁剂的有效成分有较强的毒性，会造成家蚕中毒，影响家蚕摄食、结茧和化蛹等。
由于上述技术方案运用，本发明与现有技术相比具有下列优点：1．本发明提供了一种去除桑叶残留农药清洁剂的配方及制备方法，其配方大多为无毒和天然原料，对家蚕无毒性。
2 .本发明开发的去除桑叶残留农药清洁剂中含有少量硫酸阿托品，结合药剂，可以预防残留的有机磷农药对家蚕的毒性。
3．本发明开发的去除桑叶残留农药清洁剂中使用的乙醇，可以起到杀菌作用，而且乙醇的挥发性使得桑叶沥干水分的时间更短。
作为客观现实，桑叶生长过程喷洒农药，导致采摘用以喂食家蚕的桑叶一般存在农药残留。硫酸阿托品被应用于人体急性中毒的治疗，预防及缓解青少年近视，但是对于桑叶，硫酸阿托品去除残留农药的效果未知。本发明的创新，就是针对生产的需要，开发了一种去除桑叶残留农药的清洁剂和清洁方法，利用清洁的桑叶添食家蚕，从源头避免家蚕中毒。
下面结合实施例对本发明作进一步描述：本发明去除桑叶残留农药清洁剂的制备方法如下：将药剂加入含有硫酸阿托品的水中，混合均匀制成清洁剂；所述药剂包括甘草粉、碳酸氢钠、柠檬酸、柠檬酸钠、乙醇、抗菌剂和食盐，优选以药剂质量为100%计，按质量百分数，甘草粉为20~30%，碳酸氢钠为15~20%，柠檬酸8~15%，柠檬酸钠8~15%，乙醇25~30%，抗菌剂2~10%，食盐为余量。本发明中，摇匀前清洁剂装入瓶中密封，防止摇匀过程中酒精挥发，在摇床上充分摇匀，使得药剂和水充分混合。
材料及设备。实验家蚕品种采用“菁松×皓月”品种，购置于江苏东台市蚕种场，幼虫在温度25℃±1℃，湿度75%~85%，12小时光照和12小时黑暗条件下，采用桑叶饲养。本发明中，清洁剂的有效性是通过统计饲喂清洁桑叶的家蚕全龄发病率、上蔟率和结茧率进行判定，发病率、上蔟率和结茧率的统计方法为现有常规方法；硫酸阿托品、甘草、碳酸氢钠、柠檬酸、柠檬酸钠、乙醇、抗菌剂和食盐都为市售常规产品。
实施例一：采用浸泡法清洁残留微量氯虫苯甲酰胺桑叶的应用效果。
按质量百分数，药剂配方：甘草粉25%（细度150目）、碳酸氢钠17%、柠檬酸10%、柠檬酸钠10%、乙醇27%、抗菌剂7%、食盐4%。抗菌剂由氨苄西林、阿莫西林、头孢洛林按照质量比1:1:1混合组成。
将0.2 g硫酸阿托品加入3 kg纯净水中，搅拌均匀后加入1 kg药剂，在混匀机上摇匀使得药剂与纯净水完全混匀，置于阴暗处备用，储存温度为20℃±3℃，并且在四十天后检测清洁剂没有变质（常规检测无霉菌）。
（1）采用桑叶残留农药清洁剂清洁桑叶。
将采集的去除主叶脉的新鲜桑叶均分为两组，每组100 g桑叶。将两组桑叶按照“浸叶法”完全浸入0.005 μg/mL氯虫苯甲酰胺溶液。1分钟后取出晾干置于保湿滤纸的培养皿中。对照组桑叶完全浸泡在双蒸水里，实验组桑叶完全浸泡在制备好的清洁剂里，置于100 r/min摇床上震荡浸泡2小时，取出桑叶用水漂洗1次；室温晾干后，用处理过的桑叶饲养五龄第3天幼虫30头，对照组和实验组各15头。每天饲喂两次，每次饲喂前需将蚕盒中剩余的桑叶清除干净。到五龄第7天，统计家蚕上蔟率和结茧率。重复实验三次，得到三次实验发病率、上蔟率和结茧率的平均值。
（2）发病率统计。
对照组平均发病数为14头，实验组平均发病数为2头。对照组家蚕上蔟率为83%，结茧率为80%，实验组家蚕上蔟率为95%，结茧率为93%。对照组家蚕大多数出现蚕食量减少和行动迟缓等症状，实验组家蚕大多行动活泼，体躯正常舒展，体壁有光泽。
实施例二：采用浸泡法清洁残留微量辛硫磷桑叶的应用效果。
（1）采用桑叶残留农药清洁剂清洁桑叶。
将采集的去除主叶脉的新鲜桑叶均分为两组，每组100 g桑叶。将两组桑叶按照“浸叶法”完全浸入0.05 g/L辛硫磷溶液。1分钟后取出晾干置于保湿滤纸的培养皿中。对照组桑叶完全浸泡在双蒸水里，实验组桑叶完全浸泡在制备好的清洁剂（实施例一）里，置于100 r/min摇床上震荡浸泡2小时，取出桑叶漂洗1次，室温晾干后，用处理过的桑叶饲养五龄第3天幼虫30头，对照组和实验组各15头。每天饲喂两次，每次饲喂前需将蚕盒中剩余的桑叶清除干净。到五龄第7天，统计家蚕发病率、上蔟率和结茧率。重复实验三次，得到三次实验发病率、上蔟率和结茧率的平均值。
（2）发病率统计。
对照组平均发病数为12头，实验组家蚕无发病症状。对照组家蚕上蔟率90%，结茧率为85%，实验组家蚕上蔟率为100%，结茧率为100%。对照组家蚕大多数出现行动缓慢和痉挛等症状，实验组家蚕大多数行动活泼，体躯正常舒展，体壁有光泽。
实施例三：采用喷洒法清洁残留微量氯虫苯甲酰胺桑叶的应用效果。
按质量百分数，药剂配方：甘草粉30%（细度150目）、碳酸氢钠19%、柠檬酸8%、柠檬酸钠8%、乙醇30%、抗菌剂3%、食盐2%。抗菌剂由氨苄西林、阿莫西林、头孢洛林按照质量比1:1:1混合组成。
将0.4 g硫酸阿托品加入7 kg纯净水中，搅拌均匀后加入1 kg药剂，在混匀机上摇匀使得药剂与纯净水完全混匀，置于阴暗处备用，储存温度为20℃±3℃，并且在四十天后检测清洁剂没有变质（常规检测无霉菌）。
（1）采用桑叶残留农药清洁剂清洁桑叶。
将采集的去除主叶脉的新鲜桑叶均分为两组，每组100 g桑叶。将两组桑叶按照“浸叶法”完全浸入0.005 μg/mL氯虫苯甲酰胺溶液。1分钟后取出晾干置于保湿滤纸的培养皿中。在对照组桑叶上喷洒50 g双蒸水，此时完全浸湿桑叶，在实验组桑叶上喷洒50 g清洁剂，此时完全浸湿桑叶，待桑叶上水分自然晾干后，再次喷洒，重复上述步骤3次。用处理过的桑叶饲养五龄大蚕第3天30头，对照组和实验组各15头。每天饲喂两次，每次饲喂前需将蚕盒中剩余的桑叶清除干净。到五龄第7天，统计家蚕发病率、上蔟率和结茧率。重复实验三次，得到三次实验发病率、上蔟率和结茧率的平均值。
（2）发病率统计。
对照组平均发病数为13头，实验组平均发病数为2头。对照组家蚕上蔟率为88%，结茧率为85%，实验组家蚕上蔟率为95%，结茧率为94%。对照组家蚕大多数出现蚕食量减少和行动迟缓等症状，实验组家蚕大多数行动活泼，体躯正常舒展，体壁有光泽。如果仅采用硫酸阿托品水溶液，实验结果与对照组没有差异。如果省略甘草与硫酸阿托品，家蚕结茧率下降为88%。如果省略柠檬酸和柠檬酸钠，家蚕结茧率下降为90%。如果省略乙醇与抗菌剂，家蚕结茧率下降为89%。
实施例四：采用喷洒法清洁残留微量辛硫磷桑叶的应用效果。
（1）采用桑叶残留农药清洁剂清洁桑叶。
将采集的去除主叶脉的新鲜桑叶均分为两组，每组100 g桑叶。将两组桑叶按照“浸叶法”完全浸入0.05 g/L辛硫磷溶液。1分钟后取出晾干置于保湿滤纸的培养皿中。在对照组桑叶上喷洒50 g双蒸水，此时完全浸湿桑叶，在实验组桑叶上喷洒50 g清洁剂（实施例三），此时完全浸湿桑叶，待桑叶上水分自然晾干后，再次喷洒，重复上述步骤3次。用处理过的桑叶饲养五龄大蚕第3天30头，对照组和实验组各15头。每天饲喂两次，每次饲喂前需将蚕盒中剩余的桑叶清除干净。到五龄第7天，统计家蚕发病率、上蔟率和结茧率。重复实验三次，得到三次实验发病率、上蔟率和结茧率的平均值。
（3）发病率统计。
对照组平均发病数为13头，实验组平均发病数为1头。对照组家蚕上蔟率为90%，结茧率为85%，实验组家蚕上蔟率为100%，结茧率为93%。对照组家蚕大多数出现行动缓慢和痉挛等症状，实验组家蚕大多数行动活泼，体躯正常舒展，体壁有光泽。
现有技术针对桑叶的农药清洁剂很少，市面鲜见有售，实验发现，市面上占有率好的几款果蔬清洁剂（说明书记载可有效去除农药残留）效果都不如本发明，喷洒法下，未见家蚕上蔟率大于91%的实验结果。本发明利用上述去除桑叶残留农药清洁剂浸泡桑叶，再用清水漂洗、晾干，得到清洁桑叶；或者利用去除桑叶残留农药清洁剂喷洒桑叶，再晾干，得到清洁桑叶；再利用清洁桑叶饲养家蚕，实现家蚕中毒率的降低，可预防家蚕农药中毒。尤其是，本发明喷洒不需要漂洗，既清洁桑叶又不会影响家蚕生长发育，在规模生产中，可达到省时省力、节约生产成本、清洁效果好且对家蚕基本无伤害的效果。
Claims (10)
- 一种去除桑叶残留农药清洁剂，其特征在于，包括药剂以及硫酸阿托品；所述药剂包括甘草粉、碳酸氢钠、柠檬酸、柠檬酸钠、乙醇、抗菌剂和食盐。
- 根据权利要求1所述去除桑叶残留农药清洁剂，其特征在于，以药剂为基准，硫酸阿托品的剂量是0.1 g/kg～0.5 g/kg。
- 根据权利要求1所述去除桑叶残留农药清洁剂，其特征在于，药剂由甘草粉、碳酸氢钠、柠檬酸、柠檬酸钠、乙醇、抗菌剂和食盐组成；以药剂质量为100%计，按质量百分数，甘草粉为20～30%，碳酸氢钠为15～20%，柠檬酸8～15%，柠檬酸钠8～15%，乙醇25～30%，抗菌剂2～10%，食盐为余量。
- 权利要求1所述去除桑叶残留农药清洁剂的制备方法，其特征在于，将药剂加入含有硫酸阿托品的水中，混合均匀制成清洁剂。
- 一种基于农药清洁剂减少桑叶农药残留的方法，其特征在于，包括以下步骤：利用权利要求1所述去除桑叶残留农药清洁剂浸泡桑叶，再用清水漂洗、晾干，实现桑叶农药残留的减少；或者利用权利要求1所述去除桑叶残留农药清洁剂喷洒桑叶，再晾干，实现桑叶农药残留的减少。
- 根据权利要求5所述基于农药清洁剂减少桑叶农药残留的方法，其特征在于，采用浸泡法时水的用量为药剂质量的2.5～3.5倍，采用喷洒法时水的用量为药剂质量的6～8倍。
- 一种基于农药清洁剂预防家蚕农药中毒的方法，其特征在于，包括以下步骤：利用权利要求1所述去除桑叶残留农药清洁剂浸泡桑叶，再用清水漂洗、晾干，得到清洁桑叶；或者利用权利要求1所述去除桑叶残留农药清洁剂喷洒桑叶，再晾干，得到清洁桑叶；再利用清洁桑叶饲养家蚕，实现家蚕中毒率的降低。
- 根据权利要求5或者7所述的方法，其特征在于，浸泡的时间为1～3小时；漂洗的次数为1～3次。
- 权利要求1所述去除桑叶残留农药清洁剂在减少桑叶农药残留、预防家蚕农药中毒或者提高家蚕上蔟率和结茧率中的应用。
- 权利要求1所述去除桑叶残留农药清洁剂在制备减少桑叶农药残留、预防家蚕农药中毒或者提高家蚕上蔟率和结茧率的试剂中的应用。
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| CN1526462A (zh) * | 2003-03-04 | 2004-09-08 | 中国科学院动物研究所 | 蔬果专用酯类农药降解剂 |
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| CN106566674A (zh) * | 2016-11-15 | 2017-04-19 | 广西大学 | 农药残留清洁剂及其制备方法 |
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| CN1526462A (zh) * | 2003-03-04 | 2004-09-08 | 中国科学院动物研究所 | 蔬果专用酯类农药降解剂 |
| CN105368462A (zh) * | 2015-12-16 | 2016-03-02 | 梁宗贵 | 一种作物土壤净化剂及其生产工艺 |
| CN105647690A (zh) * | 2016-02-03 | 2016-06-08 | 朱仕龙 | 一种用于水果的清洁剂及其生产工艺 |
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