CN113068714A - Monoatomic copper preparation capable of replacing traditional agricultural copper preparation and preparation method thereof - Google Patents
Monoatomic copper preparation capable of replacing traditional agricultural copper preparation and preparation method thereof Download PDFInfo
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- CN113068714A CN113068714A CN202110353113.XA CN202110353113A CN113068714A CN 113068714 A CN113068714 A CN 113068714A CN 202110353113 A CN202110353113 A CN 202110353113A CN 113068714 A CN113068714 A CN 113068714A
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- copper
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 238000002360 preparation method Methods 0.000 title claims abstract description 124
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 119
- 239000010949 copper Substances 0.000 title claims abstract description 119
- 239000000843 powder Substances 0.000 claims abstract description 167
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- 239000000080 wetting agent Substances 0.000 claims abstract description 15
- 239000000375 suspending agent Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- 239000006260 foam Substances 0.000 claims abstract description 6
- 239000003112 inhibitor Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 59
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- 239000007864 aqueous solution Substances 0.000 claims description 45
- 238000000227 grinding Methods 0.000 claims description 44
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000004115 Sodium Silicate Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 27
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 27
- -1 alkyl naphthalene formaldehyde Chemical compound 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- 235000019270 ammonium chloride Nutrition 0.000 claims description 25
- 238000009472 formulation Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000005543 nano-size silicon particle Substances 0.000 claims description 18
- 229920001223 polyethylene glycol Polymers 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 18
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 229910052723 transition metal Inorganic materials 0.000 claims description 13
- 150000003624 transition metals Chemical class 0.000 claims description 13
- 238000009388 chemical precipitation Methods 0.000 claims description 11
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 11
- 239000002518 antifoaming agent Substances 0.000 claims description 10
- PYODKQIVQIVELM-UHFFFAOYSA-M sodium;2,3-bis(2-methylpropyl)naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CC(C)C)C(CC(C)C)=CC2=C1 PYODKQIVQIVELM-UHFFFAOYSA-M 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 8
- 229920002125 Sokalan® Polymers 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 5
- 229920001732 Lignosulfonate Polymers 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 235000019988 mead Nutrition 0.000 claims description 4
- 229920005646 polycarboxylate Polymers 0.000 claims description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229920002357 Sokalan® PA 80 S Polymers 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 238000003889 chemical engineering Methods 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 230000007547 defect Effects 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 239000012847 fine chemical Substances 0.000 claims description 2
- 238000010902 jet-milling Methods 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 150000003871 sulfonates Chemical class 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 16
- 208000035143 Bacterial infection Diseases 0.000 abstract description 9
- 239000003899 bactericide agent Substances 0.000 abstract description 9
- 208000031888 Mycoses Diseases 0.000 abstract description 6
- 201000010099 disease Diseases 0.000 abstract description 6
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 abstract description 6
- 239000000575 pesticide Substances 0.000 abstract description 4
- 230000002265 prevention Effects 0.000 abstract description 4
- 238000001228 spectrum Methods 0.000 abstract description 3
- 230000000361 pesticidal effect Effects 0.000 abstract description 2
- 235000013399 edible fruits Nutrition 0.000 abstract 1
- 235000013311 vegetables Nutrition 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 84
- 238000004519 manufacturing process Methods 0.000 description 49
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 42
- 230000000052 comparative effect Effects 0.000 description 26
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 21
- 239000004810 polytetrafluoroethylene Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 16
- 239000000377 silicon dioxide Substances 0.000 description 14
- 238000005469 granulation Methods 0.000 description 12
- 230000003179 granulation Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 241000196324 Embryophyta Species 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000003093 cationic surfactant Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 238000001599 direct drying Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000002689 soil Substances 0.000 description 3
- 239000004563 wettable powder Substances 0.000 description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 239000005750 Copper hydroxide Substances 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 235000012055 fruits and vegetables Nutrition 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- LITQZINTSYBKIU-UHFFFAOYSA-F tetracopper;hexahydroxide;sulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Cu+2].[Cu+2].[Cu+2].[Cu+2].[O-]S([O-])(=O)=O LITQZINTSYBKIU-UHFFFAOYSA-F 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000005739 Bordeaux mixture Substances 0.000 description 1
- OWNRRUFOJXFKCU-UHFFFAOYSA-N Bromadiolone Chemical compound C=1C=C(C=2C=CC(Br)=CC=2)C=CC=1C(O)CC(C=1C(OC2=CC=CC=C2C=1O)=O)C1=CC=CC=C1 OWNRRUFOJXFKCU-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 244000021273 Peumus boldus Species 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 244000000005 bacterial plant pathogen Species 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000006806 disease prevention Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
Abstract
The application relates to the technical field of pesticide bactericides, in particular to a monoatomic copper preparation capable of replacing a traditional agricultural copper preparation and a preparation method thereof. A single-atom copper preparation capable of replacing a traditional agricultural copper preparation is prepared from the following raw materials in percentage by mass: 2.5-90% of monatomic powder, 1-8% of dispersing agent, 2-4% of wetting agent, 0.5-5% of suspending agent, 0.01% of foam inhibitor, 0.05-2% of stabilizing agent and 0.5-10% of carrier. Compared with the traditional copper preparation, the monatomic copper preparation has the advantages that under the condition of ensuring the same effectiveness, the copper atom content is reduced by more than 70%, meanwhile, the bacterial diseases and the fungal diseases of crops can be effectively prevented and removed, the bactericidal spectrum is enlarged, the cost is reduced, the copper resource is saved, the pollution to the environment is reduced, the copper preparation can be applied to the diseases of fruits, vegetables and crops, the copper preparation can be effectively and uniformly attached to the surfaces of the crops, the large uniform coverage on prevention and control objects can be achieved after the copper preparation is applied, the rain wash resistance is realized, and the pesticide effect is stable and durable.
Description
Technical Field
The application relates to the technical field of pesticide bactericides, in particular to a monoatomic copper preparation capable of replacing a traditional agricultural copper preparation and a preparation method thereof.
Background
The copper preparation is a long-history agricultural bactericide such as Bordeaux mixture, cuprous oxide, copper hydroxide and basic copper sulfate, can still exert good bactericidal effect for centuries, is widely applied to the aspect of disease prevention and control of various crops, and has no drug resistance phenomenon up to now. Since 2009, the copper bactericide is always stably living in the top five of the world bactericide sales, called the fifth world bactericide, and becomes one of the most popular bactericide varieties for the world agricultural users, especially in countries such as the european union, the copper bactericide is listed as the first bactericide throughout the year.
As a big agricultural country, the problem of crop diseases and insect pests is one of the main factors restricting the agricultural development. The crop bacterial diseases in China are characterized by multiple varieties and wide distribution, the annual occurrence area is about 1.2 hundred million acres, and about 300 crop diseases are caused by about 1600 bacteria identified to date. The diseases caused by plant pathogenic bacteria are more than 500, and about more than 100 kinds of frequent, intermittent and regional plant bacterial diseases outbreak and cause disasters. The copper preparation with broad spectrum, difficult resistance generation, lower toxicity and low cost can bring good news for the protection of agricultural bacterial diseases.
The traditional copper preparation only has the copper atoms on the surface which can be contacted to play a role, most of the copper atoms are wrapped in the copper preparation, the copper atoms cannot be utilized, the atom utilization rate of the copper is very low, and the copper atoms are remained in soil after the copper preparation is used to easily cause heavy metal pollution to exceed the standard.
Disclosure of Invention
In order to solve the problems caused by the conventional copper preparation, the application aims to provide a single-atom copper preparation capable of replacing the conventional agricultural copper preparation and a preparation method thereof.
In a first aspect, the application provides a monatomic copper formulation that can replace traditional agricultural copper formulations, and adopts the following technical scheme:
a single-atom copper preparation capable of replacing a traditional agricultural copper preparation is prepared from the following raw materials in percentage by mass: 2.5-90% of monatomic powder, 1-8% of dispersing agent, 2-4% of wetting agent, 0.5-5% of suspending agent, 0.01% of foam inhibitor, 0.05-2% of stabilizing agent and 0.5-10% of carrier.
By adopting the technical scheme, compared with the traditional copper preparation, the monoatomic copper preparation prepared by the method has the advantages that under the condition of ensuring the same effect, the copper atom content is reduced by more than 70%, meanwhile, the bacterial diseases and the fungal diseases of crops can be effectively prevented and removed, the bactericidal spectrum is enlarged, the cost is greatly reduced, the copper resource is saved, the pollution to the environment is reduced, and the monoatomic copper preparation can be applied to all the diseases of fruits and vegetables; and the preparation components of the monoatomic copper preparation can be effectively and uniformly attached to the surfaces of crops, can achieve larger uniform coverage on a control object after being applied, is rain-wash resistant, and has stable and durable pesticide effect.
Preferably, the particle size of the monoatomic copper preparation particles is 0.5-10 mu m; the using method of the monoatomic copper preparation comprises the following steps: diluting the monoatomic copper preparation with water according to the proportion of 1:200, adding the diluted monoatomic copper preparation into a sprayer, and stirring to uniformly distribute the monoatomic copper preparation in the water to form a suspension; the monoatomic copper preparation can be uniformly attached to the surface of crops.
By adopting the technical scheme, special equipment is not needed, the use of the single-atom copper preparation is simpler, and the popularization is convenient; in addition, the particle size of the monoatomic copper preparation is controlled, so that the dispersibility of the suspension can be improved, and the monoatomic copper preparation can be ensured to have better effects of preventing and controlling bacterial diseases and fungal diseases of crops.
Preferably, the dispersant is one or more of lignosulfonate, polycarboxylate, naphthalene and alkyl naphthalene formaldehyde condensate sulfonate and alkylphenol polyoxyethylene ether formaldehyde condensate sulfate.
By adopting the technical scheme, a better dispersion effect can be achieved, so that the monoatomic copper preparation can be effectively and uniformly attached to the surfaces of crops, and the prevention and treatment objects can be greatly and uniformly covered after the monoatomic copper preparation is applied.
Preferably, the wetting agent is one or more of the combination of BX line of Basf Nekal BX Dry powder, Ackso Morwet EFW, Ackso Morwet IP, Ackso PetroAA and Hensman T-1004; lignosulfonate Mead Westvaco: the REAX series; the polycarboxylate is Sokalan HP 25 or Sokalan PA 80S from BASF corporation; naphthalene and alkyl naphthalene formaldehyde condensate sulfonates are Tamol NN or Tamol DN from Pasteur; the alkylphenol polyoxyethylene ether formaldehyde condensate sulfate is SOPA S-270 from the company of the fine chemical engineering of the Chachen Taiwan.
By adopting the technical scheme, better dispersion effect is further achieved, the monoatomic copper preparation can be effectively and uniformly attached to the surfaces of crops, and the prevention and treatment objects can be greatly and uniformly covered after the monoatomic copper preparation is applied.
Preferably, the suspending agent is daran D06; the foam inhibitor is a Wake 811 antifoaming agent; the stabilizer is one or more of polyethylene glycol, glycerol and propylene glycol; the carrier is one or more of talcum powder, activated clay, diatomite, light calcium, white carbon black or kaolin; the particle size of the carrier is 3000-4000 meshes.
By adopting the technical scheme, the suspension adjuvant can better improve the suspension rate, and the monoatomic copper preparation/water suspension with better suspension rate is obtained, thereby facilitating the application; the foam inhibitor is used for eliminating bubbles to achieve a good dispersing effect; (ii) a The carrier plays the roles of dilution and filling, so that the cost can be reduced, and the concentration of active copper ions can be controlled.
In a first aspect, the application provides a preparation method of a monatomic copper preparation capable of replacing the traditional agricultural copper preparation, and the following technical scheme is adopted:
a preparation method of a single-atom copper preparation capable of replacing a traditional agricultural copper preparation comprises the following steps: s1, preparing monatomic powder;
s2, uniformly mixing the accurately measured monatomic powder, the dispersing agent, the wetting agent and the carrier;
s3, performing jet milling treatment, and continuously mixing the obtained powder;
s4, grinding the mixture until the particle size of the powder is 1-5 mu m;
and S5, granulating in a fluidized bed, introducing hot air, spraying the aqueous solution with the stabilizer, granulating, and drying to obtain the monatomic copper preparation.
By adopting the technical scheme, the preparation method is relatively simple, is beneficial to batch production and market promotion, and has good economic efficiency.
Preferably, the monatomic powder consists of nano silicon oxide and copper acetylacetonate; the transition metal of the monoatomic copper preparation is anchored in a defect site on the surface of the carrier in a monoatomic form, and the mass ratio of the transition metal to the carrier in the monoatomic powder of the monoatomic copper preparation is 1:20-1: 250.
By adopting the technical scheme, the monatomic powder with better quality can be prepared, and the production cost is reduced.
Preferably, the preparation of the single atom powder of S1:
s1.1, preparing a nano silicon oxide carrier by a chemical precipitation method;
s1.2, adding 2-8% of copper acetylacetonate aqueous solution into a nano silicon oxide carrier, wherein the mass ratio of transition metal to the carrier is (1: 20-1): 200, performing ultrasonic treatment on the obtained solution under the condition of 100kHz for 30-60min to uniformly disperse the solution, then stirring the mixed solution at the speed of 100-1000r/min for 12-72h, heating the obtained mixed solution to the boiling point of water, volatilizing at high temperature, evaporating the solvent to dryness, and performing ball milling at the rotating speed of 50-600r/min for 0.1-2 h to obtain solid powder;
and S1.3, performing high-temperature activation treatment to obtain monatomic powder.
By adopting the technical scheme, the monatomic powder with higher quality can be prepared.
Preferably, the chemical precipitation method in S1.1 is used for preparing the nano-silica carrier:
s1.1.1, preparing an ethanol water solution with a volume ratio of 1:8, weighing sodium silicate, dissolving the sodium silicate in the ethanol water solution to prepare 0.4mol/L, and adding 0.5g of Cetyl Trimethyl Ammonium Bromide (CTAB);
s1.1.2, preparing 100ml of ammonium chloride solution with the concentration of 1.5mol/L, dripping the sodium silicate solution into the ammonium chloride solution at the speed of 100 mu L/s at the temperature of 40 ℃ and the speed of 400-500rpm until the pH value reaches 8.5, and continuing to stir for reaction for 1.0-2.0 h;
s1.1.3, obtaining a precipitate, and centrifugally washing the obtained precipitate by using an ethanol water solution added with cetyl trimethyl ammonium bromide CTAB to obtain white powder;
s1.1.4, drying the obtained white powder at 100 ℃, calcining the white powder for 2 to 8 hours at 800 ℃ in a muffle furnace, and ball-milling the white powder until the granularity of the powder is less than or equal to 100nm to obtain the nano silicon oxide carrier.
By adopting the technical scheme, the nano silicon oxide carrier can be prepared and used for synthesizing higher-quality monatomic powder.
Preferably, the S1.3 high-temperature activation treatment is: and (3) heating the solid powder in the S1.2 for 0.5-24h under the conditions of air atmosphere and temperature of 200-1000 ℃, cooling to room temperature, and carrying out ball milling for 5-60min at the rotating speed of 50r/min to obtain the monatomic powder.
By adopting the technical scheme, the prepared high-activity monatomic powder has a good antibacterial effect.
In summary, the present application has the following advantages:
1. the monatomic copper preparation in this application, what adopted is the monatomic catalyst of the agricultural copper preparation of replacement that independently develops, all copper atoms in the monatomic catalyst can divide evenly on the surface of carrier, compare with traditional agricultural copper preparation, the monatomic copper preparation of this application can reduce copper atom content more than 70%, reduce cost by a wide margin, save copper resource, reduce the pollution to the environment, can high-efficient prevention and cure the bacterial disease and the fungal disease of crops, the atomic utilization ratio of copper is high, the pollution of heavy metal to soil has still been reduced simultaneously, open up new way for the utilization of the resource of industrial and agricultural discarded object in the soil restoration treatment field.
2. This application sprays can extend with faster speed behind crops, evenly covers on crops surface, has better adhesion, is difficult for dropping or droing, and the control effect is more durable and distribute evenly, can not produce the phytotoxicity, can not induce the outbreak of mite class, and the security is higher.
Drawings
FIG. 1 is a schematic diagram of the structure of the monatomic powder in the present application.
FIG. 2 is a transmission electron microscope photograph showing the spherical aberration correction of the monoatomic powder used in preparation example 1 of the present application.
FIG. 3 is a diagram showing the status of plants not sprayed with monatomic agent of example 3 before the water resistance test of the present application.
FIG. 4 is a diagram showing the status of plants sprayed with monatomic agent of example 3 in the water resistance test of the present application.
FIG. 5 is a diagram showing the status of plants sprayed with monatomic agent of example 3, when tested for water resistance according to the present application.
FIG. 6 is a diagram showing the status of plants sprayed with monatomic agent of example 3 and simulated spraying rainwater for 3h in the water resistance test of the present application.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples.
Raw materials
Preparation example
Preparation example 1
The preparation method of the monatomic powder comprises the following steps:
s1, preparing the nano silicon oxide carrier by adopting a chemical precipitation method:
s1.1, preparing an ethanol aqueous solution with a volume ratio of 1:8, weighing sodium silicate, dissolving the sodium silicate in the ethanol aqueous solution to prepare 0.4mol/L, and adding 0.5g of cationic surfactant cetyl trimethyl ammonium bromide CTAB.
S1.2, preparing 100ml of ammonium chloride solution with the concentration of 1.5mol/L, placing the ammonium chloride solution on a constant-temperature magnetic stirrer, controlling the rotation speed to be 500rpm and the temperature to be 40 ℃, dropping the sodium silicate solution prepared in the S1.1 into the ammonium chloride solution at the speed of 100 mu L/S until the pH value reaches 8.5, and continuing stirring and reacting for 1h to obtain a precipitate.
S1.3, centrifuging and washing the obtained precipitate by using an ethanol aqueous solution (0.1mol) added with CTAB to obtain white powder, wherein the content of CTAB in the ethanol aqueous solution of CTAB is 0.1mol/L, and the volume ratio of ethanol to water in the ethanol aqueous solution is 1: 8.
S1.4, placing the obtained white powder in an oven to be dried at 100 ℃, calcining the white powder for 4 hours at 500 ℃ in a muffle furnace, and grinding the white powder to be less than or equal to 100nm by using a planetary ball mill (the inner container is made of polytetrafluoroethylene, and a grinding ball is made of zirconia balls) to obtain a nano-silica carrier;
s2, adding a 2% copper acetylacetonate aqueous solution into the nano silica carrier prepared in S1.4, wherein the mass ratio of the transition metal to the carrier is 1:200, performing ultrasonic treatment on the obtained solution under the condition of 100kHz for 30min to uniformly disperse the solution, and then stirring the mixed solution for 12h at the speed of 500 r/min; heating the obtained mixed solution to the boiling point of water, volatilizing at high temperature, evaporating the solvent to dryness, and fully grinding for 0.5 hour at the rotating speed of 600r/min by using a planetary ball mill (the inner container is made of polytetrafluoroethylene, and a grinding ball is made of zirconia balls) to obtain solid powder.
S3, heating the solid powder for 2h under the conditions of air atmosphere and 400 ℃, cooling to room temperature, and grinding for 20min at the rotating speed of 50r/min by using a planetary ball mill (the inner container is made of polytetrafluoroethylene, and the grinding ball is made of zirconia balls) to obtain the required monatomic powder. Referring to fig. 1 and 2, the active metal in the monatomic powder is supported on the surface of the carrier, and the interior of the carrier does not contain the active metal.
Preparation example 2
The preparation method of the monatomic powder comprises the following steps:
s1, preparing the nano silicon oxide carrier by adopting a chemical precipitation method:
s1.1, preparing an ethanol aqueous solution with a volume ratio of 1:8, weighing sodium silicate, dissolving the sodium silicate in the ethanol aqueous solution to prepare 0.4mol/L, and adding 0.5g of cationic surfactant cetyl trimethyl ammonium bromide CTAB.
S1.2, preparing 100ml of ammonium chloride solution with the concentration of 1.5mol/L, placing the ammonium chloride solution on a constant-temperature magnetic stirrer, controlling the rotation speed to be 500rpm and the temperature to be 40 ℃, dropping the sodium silicate solution prepared in the S1.1 into the ammonium chloride solution at the speed of 100 mu L/S until the pH value reaches 8.5, and continuing stirring and reacting for 1h to obtain a precipitate.
S1.3, centrifuging and washing the obtained precipitate by using an ethanol aqueous solution added with CTAB to obtain white powder, wherein the content of CTAB in the ethanol aqueous solution of CTAB is 0.1mol/L, and the volume ratio of ethanol to water in the ethanol aqueous solution is 1: 8.
S1.4, placing the obtained white powder in an oven to be dried at 100 ℃, calcining the white powder for 4 hours at 500 ℃ in a muffle furnace, and grinding the white powder to be less than or equal to 100nm by using a planetary ball mill (the inner container is made of polytetrafluoroethylene, and a grinding ball is made of zirconia balls) to obtain a nano-silica carrier;
s2, adding a 3% copper acetylacetonate aqueous solution into the nano silica carrier prepared in S1.4, wherein the mass ratio of the transition metal to the carrier is 1: 100, carrying out ultrasonic treatment on the obtained solution under the condition of 100kHz for 30min to uniformly disperse the solution, and then stirring the mixed solution at the speed of 450r/min for 48 h; heating the obtained mixed solution to the boiling point of water, volatilizing at high temperature, evaporating the solvent to dryness, and fully grinding for 0.1 hour at the rotating speed of 600r/min by using a planetary ball mill (the inner container is made of polytetrafluoroethylene, and a grinding ball is made of zirconia balls) to obtain solid powder.
S3, heating the solid powder for 1.5h under the conditions of air atmosphere and temperature of 300 ℃, cooling to room temperature, and grinding for 20min at the rotating speed of 50r/min by using a planetary ball mill (the inner container is made of polytetrafluoroethylene, and the grinding ball is made of zirconia balls) to obtain the required monatomic powder.
Preparation example 3
The preparation method of the monatomic powder comprises the following steps:
s1, preparing the nano silicon oxide carrier by adopting a chemical precipitation method:
s1.1, preparing an ethanol aqueous solution with a volume ratio of 1:8, weighing sodium silicate, dissolving the sodium silicate in the ethanol aqueous solution to prepare 0.4mol/L, and adding 0.5g of cationic surfactant cetyl trimethyl ammonium bromide CTAB.
S1.2, preparing 100ml of ammonium chloride solution with the concentration of 1.5mol/L, placing the ammonium chloride solution on a constant-temperature magnetic stirrer, controlling the rotation speed to be 500rpm and the temperature to be 40 ℃, dropping the sodium silicate solution prepared in the S1.1 into the ammonium chloride solution at the speed of 100 mu L/S until the pH value reaches 8.5, and continuing stirring and reacting for 1h to obtain a precipitate.
S1.3, centrifuging and washing the obtained precipitate by using an ethanol aqueous solution added with CTAB to obtain white powder, wherein the content of CTAB in the ethanol aqueous solution of CTAB is 0.1mol/L, and the volume ratio of ethanol to water in the ethanol aqueous solution is 1: 8.
S1.4, placing the obtained white powder in an oven to be dried at 100 ℃, calcining the white powder for 4 hours at 500 ℃ in a muffle furnace, and grinding the white powder to be less than or equal to 100nm by using a planetary ball mill (the inner container is made of polytetrafluoroethylene, and a grinding ball is made of zirconia balls) to obtain a nano-silica carrier;
s2, adding a 6% copper acetylacetonate aqueous solution into the nano silica carrier prepared in S1.4, wherein the mass ratio of the transition metal to the carrier is 1: 150, carrying out ultrasonic treatment on the obtained solution under the condition of 100kHz for 30min to uniformly disperse the solution, and then stirring the mixed solution at the speed of 500r/min for 12 h; heating the obtained mixed solution to the boiling point of water, volatilizing at high temperature, evaporating the solvent to dryness, and fully grinding for 0.2 h at the rotation speed of 500r/min by using a planetary ball mill (the inner container is made of polytetrafluoroethylene, and the grinding ball is made of zirconia balls) to obtain solid powder.
S3, heating the solid powder for 3h under the conditions of air atmosphere and temperature of 300 ℃, cooling to room temperature, and grinding for 30min at the rotating speed of 100r/min by a planetary ball mill (the inner container is made of polytetrafluoroethylene, and the grinding ball is made of zirconia balls) to obtain the needed monatomic powder.
Preparation example 4
The preparation method of the monatomic powder comprises the following steps:
s1, preparing the nano silicon oxide carrier by adopting a chemical precipitation method:
s1.1, preparing an ethanol aqueous solution with a volume ratio of 1:8, weighing sodium silicate, dissolving the sodium silicate in the ethanol aqueous solution to prepare 0.4mol/L, and adding 0.5g of cationic surfactant cetyl trimethyl ammonium bromide CTAB.
S1.2, preparing 100ml of ammonium chloride solution with the concentration of 1.5mol/L, placing the ammonium chloride solution on a constant-temperature magnetic stirrer, controlling the rotation speed to be 500rpm and the temperature to be 40 ℃, dropping the sodium silicate solution prepared in the S1.1 into the ammonium chloride solution at the speed of 100 mu L/S until the pH value reaches 8.5, and continuing stirring and reacting for 1h to obtain a precipitate.
S1.3, centrifuging and washing the obtained precipitate by using an ethanol aqueous solution added with CTAB to obtain white powder, wherein the content of CTAB in the ethanol aqueous solution of CTAB is 0.1mol/L, and the volume ratio of ethanol to water in the ethanol aqueous solution is 1: 8.
S1.4, placing the obtained white powder in an oven to be dried at 100 ℃, calcining the white powder for 4 hours at 500 ℃ in a muffle furnace, and grinding the white powder to be less than or equal to 100nm by using a planetary ball mill (the inner container is made of polytetrafluoroethylene, and a grinding ball is made of zirconia balls) to obtain a nano-silica carrier;
s2, adding an 8% copper acetylacetonate aqueous solution into the nano silica carrier prepared in S1.4, wherein the mass ratio of the transition metal to the carrier is 1:250, carrying out ultrasonic treatment on the obtained solution under the condition of 100kHz for 30min to uniformly disperse the solution, and then stirring the mixed solution at the speed of 600r/min for 10 h; heating the obtained mixed solution to the boiling point of water, volatilizing at high temperature, evaporating the solvent to dryness, and fully grinding for 0.5 hour at the rotating speed of 100r/min by using a planetary ball mill (the inner container is made of polytetrafluoroethylene, and a grinding ball is made of zirconia balls) to obtain solid powder.
S3, heating the solid powder in air atmosphere at 500 ℃ for 2h, cooling to room temperature, and grinding for 30min at a rotation speed of 100r/min by using a planetary ball mill (the inner container is made of polytetrafluoroethylene, and the grinding ball is made of zirconia balls) to obtain the required monatomic powder.
Preparation example 5
The preparation method of the monatomic powder comprises the following steps:
s1, preparing the nano silicon oxide carrier by adopting a chemical precipitation method:
s1.1, preparing an ethanol aqueous solution with a volume ratio of 1:8, weighing sodium silicate, dissolving the sodium silicate in the ethanol aqueous solution to prepare 0.4mol/L, and adding 0.5g of cationic surfactant cetyl trimethyl ammonium bromide CTAB.
S1.2, preparing 100ml of ammonium chloride solution with the concentration of 1.5mol/L, placing the ammonium chloride solution on a constant-temperature magnetic stirrer, controlling the rotation speed to be 500rpm and the temperature to be 40 ℃, dropping the sodium silicate solution prepared in the S1.1 into the ammonium chloride solution at the speed of 100 mu L/S until the pH value reaches 8.5, and continuing stirring and reacting for 1h to obtain a precipitate.
S1.3, centrifuging and washing the obtained precipitate by using an ethanol aqueous solution (0.1mol) added with CTAB to obtain white powder, wherein the content of CTAB in the ethanol aqueous solution of CTAB is 0.1mol/L, and the volume ratio of ethanol to water in the ethanol aqueous solution is 1: 8.
S1.4, placing the obtained white powder in an oven to be dried at 100 ℃, calcining the white powder for 4 hours at 500 ℃ in a muffle furnace, and grinding the white powder to be less than or equal to 100nm by using a planetary ball mill (the inner container is made of polytetrafluoroethylene, and a grinding ball is made of zirconia balls) to obtain a nano-silica carrier;
s2, adding 1% of copper acetylacetonate water solution into the nano silicon oxide carrier prepared in S1.4, wherein the mass ratio of the transition metal to the carrier is 1: 50, carrying out ultrasonic treatment on the obtained solution under the condition of 100kHz for 30min to uniformly disperse the solution, and then stirring the mixed solution at the speed of 500r/min for 12 h; heating the obtained mixed solution to the boiling point of water, volatilizing at high temperature, evaporating the solvent to dryness, and fully grinding for 0.5 hour at the rotating speed of 600r/min by using a planetary ball mill (the inner container is made of polytetrafluoroethylene, and a grinding ball is made of zirconia balls) to obtain solid powder.
S3, heating the solid powder in air atmosphere at 400 ℃ for 2h, cooling to room temperature, and grinding for 40min at 50r/min by a planetary ball mill (the inner container is made of polytetrafluoroethylene, and the grinding ball is zirconia ball) to obtain the required monatomic powder.
Preparation example 6
The preparation method of the monatomic powder comprises the following steps:
s1, preparing the nano silicon oxide carrier by adopting a chemical precipitation method:
s1.1, preparing an ethanol aqueous solution with a volume ratio of 1:8, weighing sodium silicate, dissolving the sodium silicate in the ethanol aqueous solution to prepare 0.4mol/L, and adding 0.5g of cationic surfactant cetyl trimethyl ammonium bromide CTAB.
S1.2, preparing 100ml of ammonium chloride solution with the concentration of 1.5mol/L, placing the ammonium chloride solution on a constant-temperature magnetic stirrer, controlling the rotation speed to be 500rpm and the temperature to be 40 ℃, dropping the sodium silicate solution prepared in the S1.1 into the ammonium chloride solution at the speed of 100 mu L/S until the pH value reaches 8.5, and continuing stirring and reacting for 1h to obtain a precipitate.
S1.3, centrifuging and washing the obtained precipitate by using an ethanol aqueous solution (0.1mol) added with CTAB to obtain white powder, wherein the content of CTAB in the ethanol aqueous solution of CTAB is 0.1mol/L, and the volume ratio of ethanol to water in the ethanol aqueous solution is 1: 8.
S1.4, placing the obtained white powder in an oven to be dried at 100 ℃, calcining the white powder for 4 hours at 500 ℃ in a muffle furnace, and grinding the white powder to be less than or equal to 100nm by using a planetary ball mill (the inner container is made of polytetrafluoroethylene, and a grinding ball is made of zirconia balls) to obtain a nano-silica carrier;
s2, adding a 0.5% copper acetylacetonate aqueous solution into the nano silica carrier prepared in S1.4, wherein the mass ratio of the transition metal to the carrier is 1:20, carrying out ultrasonic treatment on the obtained solution under the condition of 100kHz for 30min to uniformly disperse the solution, and then stirring the mixed solution at the speed of 500r/min for 12 h; heating the obtained mixed solution to the boiling point of water, volatilizing at high temperature, evaporating the solvent to dryness, and fully grinding for 0.5 hour at the rotating speed of 600r/min by using a planetary ball mill (the inner container is made of polytetrafluoroethylene, and a grinding ball is made of zirconia balls) to obtain solid powder.
S3, heating the solid powder in air atmosphere at 400 ℃ for 2h, cooling to room temperature, and grinding for 40min at 50r/min by a planetary ball mill (the inner container is made of polytetrafluoroethylene, and the grinding ball is zirconia ball) to obtain the required monatomic powder.
Preparation example 7
The preparation method of the monatomic powder comprises the following steps:
s1, preparing the nano silicon oxide carrier by adopting a chemical precipitation method:
s1.1, preparing an ethanol aqueous solution with a volume ratio of 1:8, weighing sodium silicate, dissolving the sodium silicate in the ethanol aqueous solution to prepare 0.4mol/L, and adding 0.5g of cationic surfactant cetyl trimethyl ammonium bromide CTAB.
S1.2, preparing 100ml of ammonium chloride solution with the concentration of 1.5mol/L, placing the ammonium chloride solution on a constant-temperature magnetic stirrer, controlling the rotation speed to be 500rpm and the temperature to be 40 ℃, dropping the sodium silicate solution prepared in the S1.1 into the ammonium chloride solution at the speed of 100 mu L/S until the pH value reaches 8.5, and continuing stirring and reacting for 1h to obtain a precipitate.
S1.3, centrifuging and washing the obtained precipitate by using an ethanol aqueous solution (0.1mol) added with CTAB to obtain white powder, wherein the content of CTAB in the ethanol aqueous solution of CTAB is 0.1mol/L, and the volume ratio of ethanol to water in the ethanol aqueous solution is 1: 8.
S1.4, placing the obtained white powder in an oven to be dried at 100 ℃, calcining the white powder for 4 hours at 500 ℃ in a muffle furnace, and grinding the white powder to be less than or equal to 100nm by using a planetary ball mill (the inner container is made of polytetrafluoroethylene, and a grinding ball is made of zirconia balls) to obtain a nano-silica carrier;
s2, adding a 10% copper acetylacetonate aqueous solution into the nano silica carrier prepared in S1.4, wherein the mass ratio of the transition metal to the carrier is 1: 300, carrying out ultrasonic treatment on the obtained solution under the condition of 100kHz for 30min to uniformly disperse the solution, and then stirring the mixed solution at the speed of 500r/min for 12 h; heating the obtained mixed solution to the boiling point of water, volatilizing at high temperature, evaporating the solvent to dryness, and fully grinding for 0.5 hour at the rotating speed of 600r/min by using a planetary ball mill (the inner container is made of polytetrafluoroethylene, and a grinding ball is made of zirconia balls) to obtain solid powder.
S3, heating the solid powder in air atmosphere at 400 ℃ for 2h, cooling to room temperature, and grinding for 40min at 50r/min by a planetary ball mill (the inner container is made of polytetrafluoroethylene, and the grinding ball is zirconia ball) to obtain the required monatomic powder.
Examples
Example 1
The single-atom copper preparation capable of replacing the traditional agricultural copper preparation disclosed by the application is prepared from the following raw materials in percentage by mass: 80% of monatomic powder, 8% of Sokalan HP 25 dispersant, 4% of Basff Nekal BX Dry powder wetting agent, 5% of D06 suspending agent, 0.01% of Wake 811 antifoaming agent, 1% of polyethylene glycol and 1.99% of 4000 mesh diatomaceous earth carrier in preparation example 1.
A preparation method of a single-atom copper preparation capable of replacing a traditional agricultural copper preparation comprises the following steps:
1) according to the formula, the weighed monatomic powder, the dispersing agent (Sokalan HP 25), the wetting agent (Basff Nekal BX Dry powder), the Darun D06 suspending agent, the Wake 811 antifoaming agent, the polyethylene glycol and the diatomite are put into an air flow mixing pulverizer to be fully and uniformly mixed.
2) Starting the jet mill, the materials are collided and crushed under the action of air flow, the coarse and fine materials are separated, and the fineness can reach d100 less than 10 mu m.
3) After the completion of the pulverization, the mixture is continuously mixed in another jet mixing pulverizer until the product is uniform, the product is milled to 1 mu m and then enters a fluidized bed for granulation, the obtained powdery material is added into the fluidized bed granulator, hot air is introduced, water with polyethylene glycol is sprayed into the material at the same time, granulation is carried out, and direct drying is carried out, the granulation particle size is 0.8mm, and the monoatomic copper preparation is formed.
Example 2
The single-atom copper preparation capable of replacing the traditional agricultural copper preparation disclosed by the application is prepared from the following raw materials in percentage by mass: 85% of monatomic powder, 5% of Sokalan HP 25 dispersing agent, 3% of Basff Nekal BX Dry powder wetting agent, 4% of Darun D06 suspending agent, 0.01% of Wake 811 antifoaming agent, 1.5% of polyethylene glycol and 1.49% of 3000-mesh white carbon black carrier in preparation example 1.
A preparation method of a single-atom copper preparation capable of replacing a traditional agricultural copper preparation comprises the following steps:
1) according to the formula, the weighed monatomic powder, the dispersing agent (Sokalan HP 25), the wetting agent (Basff Nekal BX Dry powder), the Darun D06 suspending agent, the Wake 811 antifoaming agent, the polyethylene glycol and the white carbon black are put into an air flow mixing pulverizer to be fully and uniformly mixed.
2) Starting the jet mill, the materials are collided and crushed under the action of air flow, the coarse and fine materials are separated, and the fineness can reach d100 less than 10 mu m.
3) After the completion of the pulverization, the mixture is continuously mixed in another jet mixing pulverizer until the product is uniform, the product is milled to 2 mu m and then enters a fluidized bed for granulation, the obtained powdery material is added into the fluidized bed granulator, hot air is introduced, water with polyethylene glycol is sprayed into the material at the same time, granulation is carried out, and direct drying is carried out, the granulation particle size is 0.8mm, and the monoatomic copper preparation is formed.
Example 3
The single-atom copper preparation capable of replacing the traditional agricultural copper preparation disclosed by the application is prepared from the following raw materials in percentage by mass: the monatomic powder of preparation example 1 was 75%, Sokalan HP 25 dispersant was 4%, basf Nekal BX Dry dusting wetting agent was 4%, wetter D06 suspending agent was 4%, wacker 811 antifoam agent was 0.01%, polyethylene glycol was 2%, and carbolite powder carrier was 6.99% of 4000 mesh.
A preparation method of a single-atom copper preparation capable of replacing a traditional agricultural copper preparation comprises the following steps:
1) according to the dosage unit, the metered monatomic powder, the dispersing agent (Sokalan HP 25), the wetting agent (Basff Nekal BX Dry powder), the Darun D06 suspending agent, the Wake 811 antifoaming agent, the polyethylene glycol and the talcum powder are put into an air flow mixing pulverizer to be fully and uniformly mixed.
2) Starting the jet mill, the materials are collided and crushed under the action of air flow, the coarse and fine materials are separated, and the fineness can reach d100 less than 10 mu m.
3) After the completion of the pulverization, the mixture is continuously mixed in another jet mixing pulverizer until the product is uniform, the product is milled to 3 mu m and then enters a fluidized bed for granulation, the obtained powdery material is added into the fluidized bed granulator, hot air is introduced, water with polyethylene glycol is sprayed into the material at the same time, granulation is carried out, and direct drying is carried out, the granulation particle size is 0.8mm, and the monoatomic copper preparation is formed.
Example 4
The single-atom copper preparation capable of replacing the traditional agricultural copper preparation disclosed by the application is prepared from the following raw materials in percentage by mass: monatomic powder 70% in preparation example 1, Mead Westvaco: 8% of REAX series dispersing agent, 4% of Basf Nekal BX Dry powder wetting agent, 5% of Darun D06 suspending agent, 0.01% of Wake 811 antifoaming agent, 2% of polyethylene glycol and 10.99% of diatomite powder carrier.
A preparation method of a single-atom copper preparation capable of replacing a traditional agricultural copper preparation comprises the following steps:
1) the metered monatomic powder, dispersant (Mead Westvaco: REAX series), wetting agent (Basff Nekal BX Dry powder), Darun D06 suspending agent, Wake 811 antifoaming agent, polyethylene glycol, and diatomaceous earth by feeding into an air-flow mixing pulverizer, and mixing thoroughly.
2) Starting the jet mill, the materials are collided and crushed under the action of air flow, the coarse and fine materials are separated, and the fineness can reach d100 less than 10 mu m.
3) After the completion of the pulverization, the mixture is continuously mixed in another jet mixing pulverizer until the product is uniform, the product is milled to 1.5 mu m and then enters a fluidized bed for granulation, the obtained powdery material is added into the fluidized bed granulator, hot air is introduced, water with polyethylene glycol is sprayed into the material at the same time, granulation is carried out, and direct drying is carried out, the particle size of the granulation is 0.8mm, so as to form the monoatomic copper preparation.
Example 5
Example 5 differs from example 1 in that: 1% polyethylene glycol was replaced with 0.3% polyethylene glycol and 0.7% isopropylene glycol.
Example 6
Example 6 differs from example 1 in that: 1% polyethylene glycol was replaced with 0.4% polyethylene glycol, 0.1% glycerol and 0.5% isopropylene glycol.
Example 7
Example 7 differs from example 1 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 2.
Example 8
Example 8 differs from example 2 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 2.
Example 9
Example 9 differs from example 3 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 2.
Example 10
Example 10 differs from example 4 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 2.
Example 11
Example 11 differs from example 1 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 3.
Example 12
Example 12 differs from example 2 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 3.
Example 13
Example 13 differs from example 3 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 3.
Example 14
Example 14 differs from example 4 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 3.
Example 15
Example 15 differs from example 1 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 4.
Example 16
Example 16 differs from example 2 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 4.
Example 17
Example 17 differs from example 3 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 4.
Example 18
Example 18 differs from example 4 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 4.
Example 19
Example 19 differs from example 1 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 5.
Example 20
Example 20 differs from example 2 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 5.
Example 21
Example 21 differs from example 3 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 5.
Example 22
Example 22 differs from example 4 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 5.
Example 23
Example 23 differs from example 1 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 6.
Example 24
Example 24 differs from example 2 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 6.
Example 25
Example 25 differs from example 3 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 6.
Example 26
Example 26 differs from example 4 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 6.
Comparative example
Comparative example 1
Comparative example 1 is boldo liquid.
Comparative example 2
Comparative example 2 is polarmanganese zinc.
Comparative example 3
Comparative example 3 is cuprous oxide.
Comparative example 4
Comparative example 4 is copper hydroxide.
Comparative example 5
Comparative example 5 was basic copper sulfate.
Comparative example 6
Comparative example 6 differs from example 1 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 7.
Comparative example 7
Comparative example 7 differs from example 2 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 7.
Comparative example 8
Comparative example 8 differs from example 3 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 7.
Comparative example 9 differs from example 4 in that: the monatomic powder in production example 1 was replaced with the monatomic powder in production example 7.
Detection method
1. And (3) testing the copper content: the test was carried out in accordance with examples 1 to 26 and comparative examples 1 to 9 of GB/T5451-2001 "method for measuring wettability of wettable powder for agricultural chemicals".
2. Antibacterial testing: antibacterial tests were carried out for examples 1 to 26 and comparative examples 1 to 9 in accordance with GB/T5451-2001 "method for measuring wettability of wettable powder for agricultural chemicals".
3. And (3) testing the suspension rate: the suspension percentage tests were carried out on examples 1 to 26 and comparative examples 1 to 9 according to the method for measuring the suspension percentage of pesticide described in GB/T5451-2001 "method for measuring wettability of wettable powder of pesticide".
4. The wetting time test method comprises the following steps: 100 mL. + -.1 mL of standard hard water was poured into a 250mL beaker, and 5 g. + -.0.1 g of each of the samples of examples 1 to 26 and comparative examples 1 to 9 (which should be typically uniform powders and should not be allowed to agglomerate or cake) was weighed while the beaker was placed at 25. + -. 1 ℃ and placed on a watch glass, and the whole sample was poured uniformly onto the liquid surface of the beaker at once from a position flush with the mouth of the beaker without excessively disturbing the liquid surface. The sample was added immediately and a stopwatch was used until the sample was completely wetted (the film of fine powder remaining on the surface of the liquid was negligible). The wet time (to the nearest second) is noted. This was repeated 5 times, and the average value was taken as the wetting time of the sample.
5. Rain wash resistance test: by using shower setsThe method comprises the steps of (3) carrying out square large top spraying (brand new Gulong) to simulate rainwater washing, carrying out square 2.0m of sprayed plants, simulating rainfall to be medium rain and 20mm/1d of rainfall, respectively carrying out copper ion detection on plant leaves subjected to 0h, 1h, 3h, 6h, 12h and 24h, and obtaining the measured rainwater resistance P (C) by using a copper content analyzer (model DP-14A Beijing Asia Oudepeng science and technology Limited company)Measuring/C(0h)100, wherein C(0h)Is the copper ion concentration of plant leaves in the initial state, CMeasuringIs the concentration of copper ions of plant leaves after spraying for 1h, 3h, 6h, 12h or 24 h.
Data analysis
Table 1 shows the test parameters of examples 1 to 26 and comparative examples 1 to 9
Table 2 shows the rainfastness test parameters of examples 1 to 26 and comparative examples 1 to 9
By combining the examples 1 to 26 and the comparative examples 1 to 9 and combining the table 1, the monoatomic copper preparation prepared by the method can reduce the copper atom content by more than 70% and effectively prevent and remove bacterial diseases and fungal diseases of crops under the condition of ensuring the same effect, expand the bactericidal spectrum, greatly reduce the cost, save copper resources, reduce the pollution to the environment and be applied to diseases of fruits and vegetables.
By combining examples 1-26 and comparative examples 1-9 with table 2 and fig. 3-6, it can be seen that the monatomic copper preparation prepared by the method can be effectively and uniformly attached to the surface of crops, can achieve large uniform coverage on a control object after application, is rain-wash resistant, has stable and durable drug effect, can effectively control bacterial diseases and fungal diseases of crops, reduces cost, saves copper resources and reduces environmental pollution.
The embodiments of the present invention are preferred embodiments of the present application, and the scope of protection of the present application is not limited by the embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (10)
1. A single atom copper preparation capable of replacing the traditional agricultural copper preparation is characterized in that: the single-atom copper preparation is prepared from the following raw materials in percentage by mass: 2.5-90% of monatomic powder, 1-8% of dispersing agent, 2-4% of wetting agent, 0.5-5% of suspending agent, 0.01% of foam inhibitor, 0.05-2% of stabilizing agent and 0.5-10% of carrier.
2. The monoatomic copper formulation that can replace the traditional copper formulation for agricultural use as claimed in claim 1, wherein: the particle size of the monoatomic copper preparation particles is 0.5-10 mu m; the using method of the monoatomic copper preparation comprises the following steps: diluting the monoatomic copper preparation with water according to the proportion of 1:200, adding the diluted monoatomic copper preparation into a sprayer, and stirring to uniformly distribute the monoatomic copper preparation in the water to form a suspension; the monoatomic copper preparation can be uniformly attached to the surface of crops.
3. The monoatomic copper formulation that can replace the traditional copper formulation for agricultural use as claimed in claim 1, wherein: the dispersant is one or more of lignosulfonate, polycarboxylate, naphthalene and alkyl naphthalene formaldehyde condensate sulfonate and alkylphenol polyoxyethylene formaldehyde condensate sulfate.
4. A monatomic copper formulation alternative to conventional agricultural copper formulations, as defined in claim 1 or 3, wherein: the wetting agent is one or more of a BX line of Basfu Nekal BX Dry powder, Acksu Morwet EFW, Acksu Morwet IP, Acksu PetroAA and Henscman T-1004; lignosulfonate Mead Westvaco: the REAX series; the polycarboxylate is Sokalan HP 25 or Sokalan PA 80S from BASF corporation; naphthalene and alkyl naphthalene formaldehyde condensate sulfonates are Tamol NN or Tamol DN from Pasteur; the alkylphenol polyoxyethylene ether formaldehyde condensate sulfate is SOPA S-270 from the company of the fine chemical engineering of the Chachen Taiwan.
5. The monoatomic copper formulation that can replace the traditional copper formulation for agricultural use as claimed in claim 1, wherein: the suspending agent is Darun D06; the foam inhibitor is a Wake 811 antifoaming agent; the stabilizer is one or more of polyethylene glycol, glycerol and propylene glycol; the carrier is one or more of talcum powder, activated clay, diatomite, light calcium, white carbon black or kaolin; the particle size of the carrier is 3000-4000 meshes.
6. The method for preparing a monatomic copper formulation as described in any of claims 1 to 5, which can replace conventional agricultural copper formulations, characterized in that: the method comprises the following steps:
s1, preparing monatomic powder;
s2, uniformly mixing the accurately measured monatomic powder, the dispersing agent, the wetting agent and the carrier;
s3, performing jet milling treatment, and continuously mixing the obtained powder;
s4, grinding the mixture until the particle size of the powder is 1-5 mu m;
and S5, granulating in a fluidized bed, introducing hot air, spraying the aqueous solution with the stabilizer, granulating, and drying to obtain the monatomic copper preparation.
7. The method for preparing a monatomic copper formulation as defined in claim 6, which can replace conventional agricultural copper formulations, wherein: the monatomic powder consists of nano silicon oxide and copper acetylacetonate; the monoatomic copper preparation transition metal is anchored in a defect site on the surface of the carrier in a monoatomic form; the mass ratio of the transition metal to the carrier in the monatomic powder of the monatomic copper preparation is 1:20-1: 250.
8. The method for preparing a monatomic copper formulation as defined in claim 6, which can replace conventional agricultural copper formulations, wherein: preparation of single atom powder in S1:
s1.1, preparing a nano silicon oxide carrier by a chemical precipitation method;
s1.2, adding 2-8% of copper acetylacetonate aqueous solution into a nano silicon oxide carrier, wherein the mass ratio of transition metal to the carrier is (1: 20-1): 200, performing ultrasonic treatment on the obtained solution under the condition of 100kHz for 30-60min to uniformly disperse the solution, then stirring the mixed solution at the speed of 100-1000r/min for 12-72h, heating the obtained mixed solution to the boiling point of water, volatilizing at high temperature, evaporating the solvent to dryness, and performing ball milling at the rotating speed of 50-600r/min for 0.1-2 h to obtain solid powder;
and S1.3, performing high-temperature activation treatment to obtain monatomic powder.
9. The method for preparing a monatomic copper formulation as defined in claim 7, which can replace conventional agricultural copper formulations, wherein: the preparation of the nano silicon oxide carrier by the chemical precipitation method in the S1.1 comprises the following steps:
s1.1.1, preparing an ethanol water solution with a volume ratio of 1:8, weighing sodium silicate, dissolving the sodium silicate in the ethanol water solution to prepare 0.4mol/L, and adding 0.5g of Cetyl Trimethyl Ammonium Bromide (CTAB);
s1.1.2, preparing 100ml of ammonium chloride solution with the concentration of 1.5mol/L, dripping the sodium silicate solution into the ammonium chloride solution at the speed of 100 mu L/s at 40 ℃ and 400-500rpm until the pH value is =8.5, and continuing to stir for 1.0-2.0 h;
s1.1.3, obtaining a precipitate, and centrifugally washing the obtained precipitate by using an ethanol water solution added with cetyl trimethyl ammonium bromide CTAB to obtain white powder;
s1.1.4, drying the obtained white powder at 100 ℃, calcining the white powder for 2 to 8 hours at 800 ℃ in a muffle furnace, and ball-milling the white powder until the granularity of the powder is less than or equal to 100nm to obtain the nano silicon oxide carrier.
10. The method for preparing a monatomic copper formulation as defined in claim 6, which can replace conventional agricultural copper formulations, wherein: the S1.3 high-temperature activation treatment comprises the following steps: and (3) heating the solid powder in the S1.2 for 0.5-24h under the conditions of air atmosphere and temperature of 200-1000 ℃, cooling to room temperature, and carrying out ball milling for 5-60min at the rotating speed of 50r/min to obtain the monatomic powder.
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