CN112806390B - Compound pesticide for smoke storage, fumigation and insect killing in smoke plant and preparation method and application thereof - Google Patents
Compound pesticide for smoke storage, fumigation and insect killing in smoke plant and preparation method and application thereof Download PDFInfo
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- CN112806390B CN112806390B CN202011634712.0A CN202011634712A CN112806390B CN 112806390 B CN112806390 B CN 112806390B CN 202011634712 A CN202011634712 A CN 202011634712A CN 112806390 B CN112806390 B CN 112806390B
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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
- A01N59/26—Phosphorus; Compounds thereof
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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
- 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
- A01N25/10—Macromolecular compounds
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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
- 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
- A01N25/18—Vapour or smoke emitting compositions with delayed or sustained release
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- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The application relates to the technical field of tobacco storage and pest killing, and particularly discloses a composite pesticide for tobacco plant tobacco storage, fumigation and steaming and pest killing, and a preparation method and application thereof. The application discloses a compound insecticide for smoke storage, fumigation and insect killing in a smoke plant comprises an agent A and an agent B, wherein the agent A is prepared from the following raw materials in parts by weight: 55-90 parts of main insecticide, 150 parts of carrier, 250 parts of diluent and 80-120 parts of pore-forming agent; the main insecticide is aluminum phosphide; the carrier comprises a first carrier starch and a second carrier, and the second carrier is at least one of paraffin, paraffin oil and oleic acid; the diluent is at least one of ammonium carbamate, ammonium bicarbonate, sodium bicarbonate and urea; the pore-forming agent is at least one of methyl phthalate, sodium chloride and zinc chloride; the agent B is at least one of glycol, ethanol and water. The application discloses compound insecticide for smoke storage, fumigation and insect killing in cigarette factory is more even with hydrogen phosphide release rate when using.
Description
Technical Field
The application relates to the technical field of tobacco storage and pest killing, in particular to a composite pesticide for tobacco plant tobacco storage, fumigation and pest killing, and a preparation method and application thereof.
Background
Most of the tobacco leaves used in cigarette factories are stored for a long time, and many tobacco leaf raw materials are stored in warehouses for more than one year. How to ensure that the quality of the tobacco leaves is not reduced in the storage process is an important work of tobacco factory storage. The main factor causing the quality of tobacco leaves to be reduced when they are stored is the infestation of pests. The stored tobacco pests not only can eat tobacco shreds, but also can pollute tobacco leaves. Most cigarette factories kill pests in tobacco warehouses every year, and fumigation is generally carried out by adopting medicaments with strong toxicity such as aluminum phosphide.
When the aluminum phosphide fumigation is adopted, the aluminum phosphide is mainly used for reacting with water vapor in the air to generate phosphine, and the phosphine is scattered in a closed space for storing tobacco leaves to kill pests. Because the volume of the pests is generally small and the diffusion rate of the phosphine to the tobacco stack is influenced by various factors, the short-time fumigation hardly has a good killing effect. In order to improve the killing effect, a method for prolonging the killing time is adopted in many tobacco factories during killing insects. When the aluminum phosphide tablet sold on the market at present is used, along with the contact reaction of water vapor in the air and aluminum phosphide in the aluminum phosphide tablet, the tablet can be gradually pulverized, so that the speed of releasing phosphine by the aluminum phosphide becomes uneven, and the leakproofness of an insecticidal space is poor, thereby greatly reducing the killing effect.
The Chinese invention patent application with the application publication number of CN108208010A discloses a fumigating medicament suitable for stored pests, which comprises the following components in parts by weight: 80-120 parts of aluminum phosphide, 150-220 parts of bentonite, 60-100 parts of soda lime and 40-60 parts of expanded perlite.
In view of the above-mentioned related technologies, the inventor believes that the aluminum phosphide, bentonite, soda lime (or a substance generated after reaction of soda lime) and expanded perlite in the fumigation medicament are mixed in a powder state, so that contact between water vapor in the air and the aluminum phosphide cannot be sufficiently slowed down, and the slow release effect is limited.
Disclosure of Invention
In order to improve the slow release performance of the fumigation insecticide, the application provides a compound insecticide for smoke storage, fumigation and insect killing in a tobacco plant and a preparation method and application thereof.
In a first aspect, the application provides a compound pesticide for smoke storage, fumigation and insect killing in a smoke plant, which adopts the following technical scheme:
a compound pesticide for smoke storage, fumigation and insect killing in a cigarette factory comprises an agent A and an agent B, wherein the agent A is prepared from the following raw materials in parts by weight: 55-90 parts of main insecticide, 150 parts of carrier, 250 parts of diluent and 80-120 parts of pore-forming agent; the main insecticide is aluminum phosphide; the carrier comprises a first carrier and a second carrier, wherein the first carrier is starch, and the second carrier is at least one of paraffin, paraffin oil and oleic acid; the diluent is at least one of ammonium carbamate, ammonium bicarbonate, sodium bicarbonate and urea; the pore-forming agent is at least one of methyl phthalate, sodium chloride and zinc chloride; the agent B is at least one of glycol, ethanol and water.
Through adopting above-mentioned technical scheme, the smoking is stored up in smoke of cigarette factory of this application and is fumigated insecticidal compound insecticide has set up A agent and B agent, after mixing A agent and B agent, the hydrogen phosphide gas is emitted, wherein first carrier is starch, can be with aluminium phosphide intensive dispersion, and utilize paraffin oil etc. in the second carrier to bond each raw materials together, form comparatively compact structure, the contact velocity of vapor and aluminium phosphide has been reduced, after being in outside aluminium phosphide and vapor contact reaction, can form tiny hole in A agent, vapor further with aluminium phosphide contact reaction after entering through the hole. These fine pores are very fine and do not allow sufficient reaction of water vapor with aluminum phosphide. The A agent is also added with a pore-forming agent, and after the A agent is contacted with the B agent, the pore-forming agent is dissolved in the B agent, so that larger pores are formed in the A agent, and the water vapor is favorably fully contacted with the aluminum phosphide after entering. The compound pesticide can release phosphine more only after the agent A contacts with the agent B, so that the safety of the pesticide tablet is improved, the transportation and the storage are facilitated, and the pesticide effect is also improved. The first carrier is starch, can provide supporting action and shaping action for the A agent, and the starch also has certain water absorption capacity, can keep water vapor inside the A agent, slowly reacts with aluminum phosphide, and further enhances the slow release action.
Preferably, the mass ratio of the first carrier to the second carrier is 70-80: 75-120.
By adopting the technical scheme, after the A agent absorbs water, the first carrier starch can have better cohesiveness, the probability that the pesticide in the A agent becomes loose powder after releasing phosphine is reduced, the release of the phosphine becomes controllable, the amount of the second carrier is slightly larger than that of the first carrier, so that the raw materials can be conveniently molded when the composite pesticide is prepared, other raw materials can be better wrapped by the starch, and the required shape can be conveniently manufactured.
Preferably, the diluent consists of ammonium carbamate, ammonium bicarbonate and sodium bicarbonate according to the mass ratio of 3-4:1-2: 1-2.
Through adopting above-mentioned technical scheme, the effect of diluent mainly is that other gases that utilize the diluent to release dilute phosphine, and the diluent of this application adopts multiple composition to mix to constitute, can all have more gaseous release under the condition of difference, has guaranteed the dilution effect. Because the ammonium carbamate can release ammonia and carbon dioxide after reacting with water, the amount of the ammonium carbamate is large, and the ammonia and the carbon dioxide in the diluent gas can be ensured to have large amounts.
Preferably, the pore-forming agent is composed of a first pore-forming agent and a second pore-forming agent according to a mass ratio of 20-30:40-90, the first pore-forming agent is methyl phthalate, and the second pore-forming agent is at least one of sodium chloride and zinc chloride.
By adopting the technical scheme, the pore-forming agent mainly has the effect of generating pores after the agent A and the agent B are mixed, the first pore-forming agent is methyl phthalate, and can be well dissolved with a carrier during the preparation of the composite insecticide, the distribution in the agent A is relatively continuous, so that the pores with strong continuity are formed after subsequent contact with the agent B, and the sodium chloride and the like are distributed in the agent A in a dispersed manner and combined with the first pore-forming agent, so that the pores with complex structures can be formed, and the passage for water vapor to enter is expanded.
In a second aspect, the application provides a preparation method of a composite pesticide for smoke storage, fumigation and pest killing in a tobacco plant, which adopts the following technical scheme:
the preparation method of the composite pesticide for smoke storage, fumigation and insect killing in the smoke plant comprises the following steps:
1) the main insecticide and the first carrier are mixed evenly in a dry mixing mode under the inert atmosphere to obtain a mixture;
2) uniformly mixing the mixture prepared in the step 1) with a second carrier, and then uniformly mixing the mixture with a diluent and a pore-forming agent to prepare an A agent.
By adopting the technical scheme, the main insecticide and the first carrier are both solid and are mixed firstly, so that the main insecticide can be uniformly dispersed in the first carrier firstly, and the uneven dispersion caused by the early adhesion of the liquid components in the second carrier to the main insecticide is reduced.
Preferably, the main insecticide and the first carrier are mixed uniformly in step 1) by dry mixing at a rotation speed of 120-150r/min for 2-3 min.
By adopting the technical scheme, when the main insecticide and the first carrier are uniformly mixed, the lower stirring speed is adopted, so that the uniform mixing of the main insecticide and the first carrier can be ensured, and the reaction of residual water vapor and aluminum phosphide in a mixing environment is reduced.
Preferably, the temperature of the mixture mixed with the second carrier in the step 2) is 35-55 ℃.
By adopting the technical scheme, the temperature can keep the second carrier to have better fluidity, and the second carrier is mixed with the mixture more uniformly.
Preferably, the mixture is uniformly mixed with the diluent and the pore-forming agent in the step 2), then the mixture is injected into a mold, the temperature is cooled to 5-15 ℃, and the mold is removed to obtain the tablet, namely the A agent.
By adopting the technical scheme, the mixed material is injected into the die and then cooled at low temperature, so that compact tablets can be obtained, and subsequent transportation and use are facilitated.
In a third aspect, the application provides an application of the composite pesticide for smoke storage, fumigation and insect killing in a tobacco plant in the aspect of insect killing, and the following technical scheme is adopted:
the application of the composite pesticide for smoking storage, steaming and insect killing in the tobacco plant comprises the following steps: the agent A is placed in a closed space, and then the agent B is dripped on the agent A.
Through adopting above-mentioned technical scheme, on dropping the A agent with the B agent, only need with the pore-forming agent dissolution back in a small amount of B agent in with the A agent, form comparatively complicated pore structure in A agent inside, the vapor of being convenient for gets into and reacts with the aluminium phosphide in the hole, also is convenient for control aluminium phosphide reaction's speed.
In summary, the present application has the following beneficial effects:
1. the composite insecticide for smoke storage, fumigation and insect killing in a smoke plant is composed of the agent A and the agent B, when the composite insecticide is used, the agent B and the agent A are mixed, a pore forming agent in the agent A is dissolved to form a pore in the agent A, water vapor enters the pore and reacts with the aluminum phosphide insecticide main agent to release phosphine, the opportunity that the agent A starts to release the phosphine can be conveniently controlled, and the rate of the phosphine release is conveniently controlled.
2. This application smoke is stored up in smoke of cigarette factory and is evaporated insecticidal and further adopt two kinds of pore-forming agents complex in the raw materials of compound insecticide, and a pore-forming agent can improve the continuity in hole, and another kind of pore-forming agent distributes more in A agent, and the two cooperation can make the pore structure of formation more complicated, has improved the transmission of vapor in the hole.
Detailed Description
The present application will be described in further detail with reference to examples.
In the raw materials of the composite pesticide for smoke storage, fumigation and insect killing in the smoke plant, the starch is corn starch. The paraffin wax is 42# or 52# paraffin wax. The paraffin oil is 150# or 200# liquid paraffin.
The particle size of the sodium chloride and the zinc chloride is 50-150 μm, preferably, the particle size of the sodium chloride is 50 μm. The particle size of the zinc chloride was 125. mu.m.
Preferably, the second pore-forming agent is formed by mixing sodium chloride and zinc chloride according to the mass ratio of 6: 1.
Preferably, the mass ratio of the first carrier to the second carrier is 105-115: 80-90.
The A preparation of the compound pesticide for smoke storage, fumigation and insect killing in the smoke plant can be prepared into pills (granules) or tablets.
Furthermore, the preparation raw materials of the agent A also comprise 6 parts of polymethyl methacrylate powder, 15 parts of polyvinyl alcohol and 3 parts of activated carbon powder. Furthermore, the preparation raw material of the agent A also comprises 5 parts of maleic anhydride.
In the preparation method of the composite pesticide for smoke storage, fumigation and steaming disinsection in the smoke plant, the inert gas is nitrogen or argon when the main pesticide is mixed with the first carrier. Further, the mixing of the mixture and the second carrier is also carried out under the protection of inert gas.
And uniformly mixing the prepared mixture with a second carrier, and stirring for 8-10 min. Adding the diluent and the pore-forming agent, and uniformly mixing for 2-3 min. The rotation speed during the two times of stirring is 45 r/min.
Example 1
The composite pesticide for storing, smoking and steaming to kill insects in the smoke plant comprises an agent A and an agent B, wherein the agent A is a tablet and is prepared from the following raw materials in parts by weight: 55g of main insecticide, 150g of carrier, 50g of diluent and 80g of pore-forming agent; the main insecticide is aluminum phosphide powder, the carrier is obtained by mixing starch and paraffin oil according to the mass ratio of 1:1, the diluent is ammonium carbamate, and the pore-forming agent is sodium chloride.
The agent B is obtained by mixing ethanol and water in a mass ratio of 5: 1.
The preparation method of the compound pesticide for smoke storage, fumigation and insect killing in the smoke plant comprises the following steps:
1) dry-mixing the main insecticide and starch for 2min at a rotating speed of 150r/min under the protection of nitrogen to obtain a mixture;
2) heating paraffin oil to 35 ℃, adding the mixture obtained in the step 1), stirring at a rotating speed of 45r/min for 10min, adding a diluent and a pore-forming agent, stirring at a rotating speed of 45r/min for 2min, injecting into a mold, and cooling to 10 ℃;
3) demolding to obtain preparation A, which is tablet with weight of 3.0 + -0.2 g;
4) uniformly mixing ethanol and water in a mass ratio of 5:1, and then placing the mixture in a closed container for later use.
The application of the composite pesticide for smoke storage, fumigation and insect killing in the tobacco plant comprises the following steps: placing the A agent tablets in an open plastic tray, placing the tablet in an area to be insecticidal, then dripping 5 drops of the B agent on the surface of the tablet, and sealing the insecticidal area.
Example 2
The composite pesticide for storing, smoking and steaming to kill insects in the smoke plant comprises an agent A and an agent B, wherein the agent A is a tablet and is prepared from the following raw materials in parts by weight: 90g of main insecticide, 250g of carrier, 70g of diluent and 120g of pore-forming agent; the insecticidal main agent, the carrier, the diluent, the pore-forming agent and the agent B are the same as those in example 1.
The preparation method and application of the composite pesticide for smoke storage, fumigation and insect killing in the cigarette factory are the same as those in example 1.
Example 3
The composite pesticide for storing, smoking and steaming to kill insects in the smoke plant comprises an agent A and an agent B, wherein the agent A is a tablet and is prepared from the following raw materials in parts by weight: 80g of main insecticide, 210g of carrier, 55g of diluent and 105g of pore-forming agent; the insecticidal main agent, the carrier, the diluent, the pore-forming agent and the agent B are the same as those in example 1.
The preparation method and application of the composite pesticide for smoke storage, fumigation and insect killing in the cigarette factory are the same as those in example 1.
Example 4
The composite pesticide for storing, smoking and steaming to kill insects in the smoke plant comprises an agent A and an agent B, wherein the agent A is a tablet and is prepared from the following raw materials in parts by weight: 68g of main insecticide, 190g of carrier, 60g of diluent and 96g of pore-forming agent; the insecticidal main agent, the carrier, the diluent, the pore-forming agent and the agent B are the same as those in example 1.
The preparation method and application of the composite pesticide for smoke storage, fumigation and insect killing in the cigarette factory are the same as those in example 1.
Comparative example
Comparative example 1
The composite pesticide for smoke storage, fumigation and insect killing in a cigarette factory of the comparative example is different from the composite pesticide in the example 1 in that the preparation raw material of the agent A does not comprise a pore-forming agent. The rest is the same as in example 1.
Comparative example 2
The composite insecticide for smoke storage, fumigation and insect killing in a cigarette factory of the present comparative example is different from example 1 in that the preparation raw material of the agent A does not include a diluent. The rest is the same as in example 1.
Comparative example 3
The composite pesticide for smoke storage, fumigation and insect killing in a cigarette factory of the comparative example is different from the composite pesticide in example 1 in that the preparation raw material of the agent A does not comprise a diluent and a pore-forming agent. The rest is the same as in example 1.
Performance test
The composite insecticide for smoke storage, fumigation and insect killing in the smoke plant in the examples 1 to 4 and the comparative examples 1 to 3 was used for testing in the following way:
placing 1 tablet A in the center of the plastic plate, and placing in the enclosed space surrounded by plastic film, the internal volume of the enclosed space is approximately 0.5m3The agent B was dropped 5 drops onto the surface of the agent A, and the closed space was closed to measure the concentration of phosphine in the air therein at regular intervals. The temperature at the time of the test was 13.5 ℃ and the humidity was 55%.
The test results are shown in table 1.
TABLE 1 comparison of the Performance of the composite insecticide for smoke storage, fumigation and disinsection in the smokehouse in examples 1-4 and comparative examples 1-3
Comparing example 1 with comparative example 1 with reference to table 1, it can be seen that the composite pesticide has a very low release rate of phosphine and a low release amount when no pore-forming agent is added, and thus a good pesticidal effect cannot be achieved.
Comparing example 1 with comparative example 2 with Table 1, it can be seen that the concentration of phosphine is slightly affected and the release rate is relatively smooth when no diluent is added.
As can be seen by comparing example 1 with comparative example 3 with reference to Table 1, the amount of phosphine released was low and the release rate was low and less uniform without adding a diluent and a pore-forming agent.
To sum up, the compound insecticide of this application slowly-releasing effect is very good, and phosphine releases evenly, can both keep the insecticidal space to have higher phosphine concentration in the longer time, and insecticidal effect is good.
Claims (6)
1. The compound pesticide for smoke storage, fumigation and insect killing in a tobacco factory is characterized by comprising an agent A and an agent B, wherein the agent A is a tablet or a pill; the agent A is prepared from the following raw materials in parts by weight: 55-90 parts of main insecticide, 150 parts of carrier, 250 parts of diluent and 80-120 parts of pore-forming agent; the main insecticide is aluminum phosphide; the carrier comprises a first carrier and a second carrier, wherein the first carrier is starch, and the second carrier is at least one of paraffin, paraffin oil and oleic acid; the agent B is at least one of glycol, ethanol and water;
the diluent consists of ammonium carbamate, ammonium bicarbonate and sodium bicarbonate according to the mass ratio of 3-4:1-2: 1-2;
the pore-forming agent is composed of a first pore-forming agent and a second pore-forming agent according to the mass ratio of 20-30:40-90, wherein the first pore-forming agent is methyl phthalate, and the second pore-forming agent is at least one of sodium chloride and zinc chloride; the mass ratio of the first carrier to the second carrier is 70-80: 75-120;
when the compound insecticide for smoke storage, fumigation and insect killing in a cigarette factory is used, the agent A is placed in a closed space, and then the agent B is dripped on the agent A.
2. The preparation method of the compound pesticide for smoke storage, fumigation and disinsection in the smoke plant as claimed in claim 1, which comprises the following steps:
1) the main insecticide and the first carrier are mixed evenly in a dry mixing mode under the inert atmosphere to obtain a mixture;
2) uniformly mixing the mixture prepared in the step 1) with a second carrier, and then uniformly mixing the mixture with a diluent and a pore-forming agent to prepare an A agent.
3. The method as claimed in claim 2, wherein the step 1) of mixing the insecticide and the first carrier uniformly is performed by dry-mixing at a rotation speed of 120-.
4. The method for preparing the composite pesticide for smoke storage, fumigation and insect disinfestation in the cigarette factory according to claim 2, wherein the temperature for uniformly mixing the mixture and the second carrier in the step 2) is 35-55 ℃.
5. The method as claimed in claim 4, wherein the step 2) of mixing with diluent and pore-forming agent, injecting into a mold, cooling to 5-15 deg.C, and demolding to obtain tablet A.
6. The application of the composite pesticide for smoke storage, fumigation and insect killing in a smoke plant as claimed in claim 1 in the aspect of insect killing is characterized by comprising the following steps: the agent A is placed in a closed space, and then the agent B is dripped on the agent A.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS542331A (en) * | 1977-06-08 | 1979-01-09 | Taisho Pharmaceut Co Ltd | Insecticidal fumigant |
CN88100644A (en) * | 1987-01-05 | 1988-11-02 | 德西亚弗赖堡股份有限公司 | The hydrolysis of delayed metal phosphoride |
CN1104997A (en) * | 1992-06-05 | 1995-07-12 | 联邦科学和工业研究组织 | Formulations, method and apparatus for the controlled generation of phosphine |
CN1395838A (en) * | 2002-07-20 | 2003-02-12 | 金劲松 | Release-controlled hydrogen phosphide capsule for preventing and eliminating pests in tobacco storage and its preparing process |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1303883C (en) * | 2005-11-14 | 2007-03-14 | 王春录 | Green multifunctional pesticidan anti-mildew agent for tobacco leaves |
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2020
- 2020-12-31 CN CN202011634712.0A patent/CN112806390B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS542331A (en) * | 1977-06-08 | 1979-01-09 | Taisho Pharmaceut Co Ltd | Insecticidal fumigant |
CN88100644A (en) * | 1987-01-05 | 1988-11-02 | 德西亚弗赖堡股份有限公司 | The hydrolysis of delayed metal phosphoride |
CN1104997A (en) * | 1992-06-05 | 1995-07-12 | 联邦科学和工业研究组织 | Formulations, method and apparatus for the controlled generation of phosphine |
CN1395838A (en) * | 2002-07-20 | 2003-02-12 | 金劲松 | Release-controlled hydrogen phosphide capsule for preventing and eliminating pests in tobacco storage and its preparing process |
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