Fungicidal preparation for plant protection and method thereof (options)

 

(57) Abstract:

Describes fungicidal preparation for plant protection comprising, by weight. %: fine cloroxed copper 20-30, ammonium or ammonium calcium nitrate 10-40, dextrin 1-2, wetting 5-7, water - the rest. Also described is a method of obtaining this drug by treatment with stirring a mixture of nitrate and chloride copper (II) with the molar ratio of copper ions and chlorine equal to 2:1, aqueous ammonia and subsequent mixing with dextrin and wetting or by processing chloridoideae substances a mixture of waste copper-base or copper-ammonia etching of printed circuit boards with copper nitrate (II) and lateral ammonia ratio of copper ions and chloride 2:1, the resulting product is mixed with dextrin and wetting. The technical result is an increase in the fungicidal activity of the drug, reduced consumption, increased frost resistance. 3 C. and 10 C.p. f-crystals.

The present invention relates to the chemical industry, namely the acquisition of chemical plant protection products, and can be used to obtain antifungal reagent for protection of plants and foliar feeding.

Known drug DL is copper (Germany, application 2180002, 01 G 3/06, 1968).

The closest analogue for the requested drug is a drug for plant protection comprising an aqueous solution of compounds containing the elements: nitrogen, phosphorus, potassium, and copper and sulfur (France, application 2485517, 05 G 3/02, 1981).

A known method of producing drug for protection of plants by treating compounds of copper, including copper oxides concentrated hydrochloric acid (RF, 2004497, 01 G 3/06, 1993).

There is also known a method of producing drug for protection of plants by treating the spent solution from the production of printed circuit boards hydrogen peroxide, followed by mixing with the spent alkaline etching solution for the production of printed circuit boards (RF patent 2051104, 01 G 3/06, 1995).

The closest analogue to the claimed method is a method of producing drug for protection of plants by treating copper scrap, including those containing oxides of copper, an aqueous solution of sodium chloride and hydrochloric acid with subsequent processing of the received chloridoideae substances aqueous ammonia, filtering, drying and grinding (UK, 1374078, 01 G3/06, 1976).

A disadvantage of the known technical regicides activity the decrease in the consumption of the drug, increasing its hardiness, the solution of environmental problems due to waste disposal and reduce the amount of harmful impurities in the product, the waste products of the process of its receipt.

The problem is solved in the preparation of plant protection agents containing fertilizer and fungicide, as it contains fungicide fine cloroxed copper, as fertilizer - ammonium or ammonium calcium nitrate, and optional adhesive in the form of dextrin and lubricant, in the following ratio, wt.%:

Fine cloroxed copper - 20 - 30

Ammonium or ammonium-calcium nitrate - 10 - 40

Dextrin - 1 - 2

Lubricant - 5 - 7

Water - the Rest

The task is also solved in the method of producing drug for protection of plants by treating with stirring chloridoideae substances aqueous ammonia due to the fact that as chloridoideae substances, a mixture of nitrate and chloride copper (II) with the molar ratio of copper ions and chlorine equal to 2:1, respectively, and received after the above processing, the product is mixed with an adhesive and wetting. Moreover, the mixture of nitrate is nitric acid with ammonium nitrate and a mixture of hydrochloric acid with ammonium nitrate, or the reaction product of electrical copper or copper oxides with a mixture of nitric acid with ammonium nitrate and waste copper chloride etching of printed circuit boards, or is a reaction product of copper or electrical copper or copper oxides from nitric and hydrochloric acids are a molar ratio of 3:1, respectively, and ammonium nitrate, or nitric acid, waste copper chloride etching of printed circuit boards and ammonium nitrate, and these nitric and hydrochloric acids or waste is fed to the reaction as a mixture or sequentially. In the used aqueous ammonia may be added chalk up to 90% and the addition of this mixture of nitrate and chloride of copper in quantities of from 0 to 50%, as the adhesive used, for example, dextrin, and as a wetting agent, for example, a lignosulfonate or other surface-active substances (surfactants).

Also the problem is solved in that in the method of producing drug for protection of plants by treating chloridoideae substances admixtures substance, which is used as the mixture of waste copper-base or copper-ammonia etching of printed circuit boards with nitrate processing the product, if necessary, filtered and mixed with an adhesive and wetting agent, moreover, as the adhesive used, for example, dextrin, and as a wetting agent, for example, the lignosulfonate or other surfactants.

The interaction of the components is carried out by the reactions represented by the following formula:

2HNO3+NH4NO3+Cu=Cu(NO3)2+3H2O+N2< / BR>
2HCl+NH4NO3+Cu=CuCl2+3H2O+N2< / BR>
2HCl+Cu=CuCl2+H2O

2HNO3+CuO=Cu(NO3)2+H2O

4HNO3+NH4NO3+Cu2O=2Cu(NO3)2+4H2O+N2< / BR>
4HCl+NH4NO3+Cu2O=2CuCl2+4H2O+N2< / BR>
< / BR>
< / BR>
< / BR>
6[si(NH3)4]2++Si2++8l-+28N2O=4[si(OH)2ul2H2O]+24NH4+< / BR>
4H[ul2]-+O2=4CuCl2+2H2O

4[si(NH3)2]CL+4N4CL+4N3+O2=4[C(NH3)4]Cl2+2H2O

Practically the method is as follows.

Take a mixture of nitrate and chloride copper (II) in a molar ratio of copper ions and chlorine equal to 2:1, respectively (mixture 1).

As such a mixture is used:

- a mixture of nitrate of copper, which receive resternotomy, obtained by dissolution of the electrical copper or copper oxides in a mixture of hydrochloric acid and ammonium nitrate or which use waste copper chloride etching of printed circuit boards containing mainly copper chloride;

solution electrical copper or copper oxides in a mixture of nitric and hydrochloric acids and ammonium nitrate, and the molar ratio of these acids must be equal to 3:1, respectively, and the amount of ammonium nitrate - stoichiometric (according to the reaction equation) or to excess.

To the mixture add 1 under vigorous stirring a mixture of 2. Mix 2 contains aqueous ammonia and possibly chalk (from 0 to 90%), and possibly an additive mixture of 1 (from 0 to 50%). Supplements are necessary for lowering the temperature of the reaction and improve homogenization aggregated particles chloroxine copper. As reaction the viscosity of the mixture increases. A sign of the end of the reaction is the cessation of carbon dioxide emissions, the purchase of a slightly blue color. Get a mixture of fine chloroxine copper (II), water and ammonia or ammonium calcium nitrate. If necessary, the resulting suspension is filtered over a drum vacuum filter with return filtered is ASEE substance and lubricant. An adhesive may be dextrin or other bonding agent, and the wetting agent is a lignosulfonate or other surfactants. After homogenization receive the drug in the form of a viscous liquid. The ratio of water and other components, as well as the viscosity of the drug depend on the initial concentration of copper in the mix 1.

Example 1.

Charged to the reactor 190,62 kg electrical copper and dissolve it in a mixture of 515 l 55% nitric acid, 900 l of water 240 kg of ammonium nitrate. Then in the same reactor dissolved 63,54 kg electrical copper in a mixture of 171 l of 36% hydrochloric acid, 300 liters of water and 80 kg of ammonium nitrate. The resulting solutions of nitrate and copper chloride are mixed, and the molar ratio of copper ions and chlorine is 2:1, respectively. The resulting mixture is 1.

Prepare a mixture of 2. For this mix 460 l of 25% aqueous ammonia and 500 l of mixture 1. The remaining mixture of 1 and the resulting mixture 2 mix when pumping in a centrifugal pump, and serves to filter. The composition of the filtered suspension: 2035 litres or 68.75 kilopascals% water, 445 kg or 15,03% chloroxine copper, 480 kg or 16,21% ammonium nitrate. Filtering produce drum vacuum filter hole size of 5 μm to concentration chloroxine copper not less than 35%. The filtrate is. asset is conducted without taking into account the evaporation of water in the reactor, therefore, the amount of water and the filtration degree should be adjusted according to the balance equations. The paste of chloroxine copper type 14,83 kg of dextrin, 74,15 kg of lignosulfonate and water to the concentration of chloroxine copper 30%. After homogenization get 1483 kg of a mixture containing 30% of fine chloroxine copper (II), 10% ammonium nitrate, 1% dextrin, 5% lignosulfonate and 54% water. As can be seen from the above technology, completely no waste, wastewater and emissions of harmful substances into the atmosphere. The output of copper is 100%. Requires minimal energy consumption. The resulting preparation contains ammonium nitrate for nakorovou plant nutrition, dextrin to improve the adhesiveness of chloroxine copper sheets and lignosulfonate to improve colloidal stability and wettability of leaves working solution.

The composition of the drug for example 1:

Chlorosis copper (II) - 30%

Ammonium nitrate - 10%

Dextrin - 1%

Lignosulfonate - 5%

Water - 54%

Example 2.

Differs from example 1 in that the reactor load 10 t electrical copper and include the submission of a mixture 685 l 55% nitric acid, 120, is received when filtering the suspension chloroxine copper, prepared in two plastic containers. Supply lead with a speed of 100-200 l/h. After downloading all of the mixture from the reactor is pumped out half of a solution of nitrate of copper, and in containers to prepare a new mixture of nitric acid and ammonium nitrate solution, and continuing the injection of the mixture at the same speed. After injection, half of the cooked mixture is pumped from the reactor half received nitrate of copper. Synthesis lead to the dissolution of almost all the copper, and then repeat in the same sequence with hydrochloric acid. Then prepare a mixture of three volumes of the obtained nitrate copper (II) and one volume of the obtained chloride copper (II), and the ratio of copper ions in the resulting solution to ions of chlorine is 2:1, respectively.

The drug composition for example 2:

Chlorosis copper (II) - 30%

Ammonium nitrate - 10%

Dextrin - 1%

Lignosulfonate - 5%

Water - 54%

Example 3.

Differs from example 2 in that cook the mixture 515 l 55% nitric acid, 171 l of 36% hydrochloric acid and 1200 l of 20% aqueous ammonium nitrate solution obtained after filtration. After synthesis, get ready-mix 1.

The composition of the drug for example 3:

/BR> Example 4.

In a reactor with a diameter of 2 m and a height of 3 m, with air intake and bottom of the Packed column at the top, load 10 tons of copper and 320 kg of ammonium nitrate. Then include the air with a speed of 10-20 m3/hour and 55% nitric acid with a speed of 30-50 l/h. After downloading a certain amount of nitric acid (100-200 l) include circulation resulting nitrate of copper through the nozzle in the reactor. Nitric acid is injected 515 l, and then with the same speed download 171 l of 36% hydrochloric acid. After downloading all of the acid from the reactor is pumped half the volume of the resulting mixture of 1 add 320 kg of ammonium nitrate in the reactor and continuing the injection of the acid in the manner described above.

At the same time preparing a mixture of 2, consisting of 25% aqueous ammonia, chalk and a mixture of 1, and the amount of chalk in the ammonia water can range from 0 to 90%, the number of mixture 1 can vary from 0 to 50%. In the mixture 1 at careful hashing (in the mixer) add the mixture 2. The feed rate of the mixture 2 is determined by the intensity of mixing and the rate of movement of the foam formed during the reaction with a mixture of chalk 1. By passing the reaction the viscosity of the resulting suspension chloroxine copper in plants is carbon dioxide and slightly blue color of the mixture. In the resulting paste is coupled to microparticles of chloroxine copper in a solution of ammonium calcium nitrate added dextrin to 1% lignosulfonate to 5% and water up to concentrations of chloroxine copper 30%.

The composition of the drug for example 4:

Chlorosis copper (II) - 30%

Ammonium nitrate - 33%

Dextrin - 1%

Lignosulfonate - 5%

Water - 31%

Example 5.

Differs from example 4 that for the synthesis of a mixture of 1 do not add ammonium nitrate.

The composition of the drug for example 5:

Chlorosis copper (II) - 30%

Ammonium nitrate - 33%

Dextrin - 1%

Lignosulfonate - 5%

Water - 31%

Example 6.

Differs from example 4 that the mixture 1 and mixture 2 take for the reaction at a temperature of 25oC.

The composition of the drug for example 6:

Chlorosis copper (II) - 30%

Ammonium nitrate - 33%

Dextrin - 1%

Lignosulfonate - 5%

Water - 31%

Example 7.

Differs from examples 1-4 and 6 in that instead of electrical copper use copper slag in an amount equivalent to pure copper used in examples 1-4 and 6, and ammonium nitrate is added in an amount equivalent to the oxidation of copper and cuprous oxide contained in the copper dross, to the 0%

Dextrin - 1%

Lignosulfonate - 5%

Water - 54%

The composition of the drug for example 7:

Chlorosis copper (II) - 30%

Ammonium nitrate - 33%

Dextrin - 1%

Lignosulfonate - 5%

Water - 31%

Example 8.

Differs from example 5 in that instead of electrical copper use copper slag in an amount equivalent to pure copper used in example 5.

The composition of the drug for example 8:

Chlorosis copper (II) - 30%

Ammonium nitrate - 33%

Dextrin - 1%

Lignosulfonate - 5%

Water - 31%

Example 9.

Differs from example 2 in that instead of the solution of chloride of copper (II) use waste copper chloride etching of printed circuit boards in such quantity that the ratio in the resulting mixture of 1 ions of copper and chlorine was equal to 2:1, respectively.

The composition of the drug for example 9:

Chlorosis copper (II) - 30%

Ammonium nitrate - 10%

Dextrin - 1%

Lignosulfonate - 5%

Water - 54%

Example 10.

Differs from example 3 in that instead of hydrochloric acid add waste copper chloride etching of printed circuit boards in an amount equivalent to chloride ion contained in the waste pickling in hydrochloric CIS in the waste copper chloride etching.

The composition of the drug for example 10:

Chlorosis copper (II) - 30%

Ammonium nitrate - 10%

Dextrin - 1%

Lignosulfonate - 5%

Water - 54%

Example 11.

Differs from examples 2, 3, 7, 9, 10 the fact that instead of a mixture of 2 use waste copper-alkaline copper-ammonium) etching of printed circuit boards with the addition of nitrate of copper (II) and aqueous ammonia to the ratio of copper ions and chloride 2:1 respectively.

The composition of the drug for example 11:

Chlorosis copper (II) - 30%

Ammonium nitrate - 10%

Dextrin - 1%

Lignosulfonate - 5%

Water - 54%

Example 12.

Differs from examples 1-11 fact that instead of lignosulfonate use concentrate sulphite yeast brew.

The composition of the drug for example 12:

Chlorosis copper (II) - 30%

Ammonium nitrate - 10%

Dextrin - 1%

Lignosulfonate - 5%

Water - 54%

The composition of the drug for example 12:

Chlorosis copper (II) - 30%

Ammonium nitrate - 33%

Dextrin - 1%

Lignosulfonate - 5%

Water - 31%

The proposed drug is hardy to -20oC.

When tested for fungicidal activity of the drug on the late blight isolates, isolated from local communities phytopathogen µg/ml;

ED50 for the proposed drug (30% chlorosis copper sun) 90 - 180 µg/ml.

Data are in current substance chlorosis copper, 90% of the JV (in terms of chlorosis copper).

1. Antifungal drug for the protection of plants containing fertilizer and fungicide, characterized in that as a fungicide it contains fine cloroxed copper, and as fertilizer - ammonium or ammonium calcium nitrate, and additionally an adhesive substance in the form of dextrin and lubricant in the following ratio, wt.%:

Fine cloroxed copper - 20-30

Ammonium or ammonium-calcium nitrate - 10-40

Dextrin - 1-2

The wetting - 5-7

Water - the Rest

2. Preparation according to one of paragraphs.1 and 2, characterized in that as wetting it contains lignosulfonate or sulphite yeast mash.

3. The method of producing drug for protection of plants, characterized in PP. 1 and 2, by treatment with stirring chloridoideae substances aqueous ammonia, characterized in that as chloridoideae substances, a mixture of nitrate and chloride copper (II) with the molar ratio of copper ions and chlorine equal to 2:1, and received after the specified the specified mixture of nitrate and chloride copper (II) obtained by mixing the reaction products electrical copper or copper oxides with a mixture of nitric acid with ammonium nitrate and a mixture of hydrochloric acid with ammonium nitrate.

5. The method according to p. 3, characterized in that the mixture of nitrate and chloride copper (II) obtained by mixing the reaction product of electrical copper or copper oxides with a mixture of nitric acid with ammonium nitrate and waste copper chloride etching of printed circuit boards containing mainly copper chloride.

6. The method according to p. 3, characterized in that the mixture of nitrate and chloride copper (II) is the reaction product of copper, or electrical copper or copper oxides from nitric and hydrochloric acids are a molar ratio of 3: 1 and ammonium nitrate or nitric acid, waste copper chloride etching of printed circuit boards and ammonium nitrate.

7. The method according to p. 6, characterized in that the said nitric and hydrochloric acid or waste is fed to the reaction as a mixture or sequentially.

8. The method according to one of paragraphs.3-7, characterized in that the used aqueous ammonia added chalk up to 90%.

9. The method according to any of paragraphs.3-7, characterized in that the used aqueous ammonia have been added to Supplement the above-mentioned mixture of nitrate and chloride copper (II) in an amount up to 50%.

10. The method according to one of paragraphs.3-9, characterized in that the quality is of Ephrata for plant protection, characterized in PP.1 and 2, by processing chloridoideae substances admixtures substance, characterized in that as leakagerough substance use mixture of waste copper-base or copper-ammonia etching of printed circuit boards with copper nitrate (II) and lateral ammonia ratio of copper ions and chloride 2:1, respectively, and received after the above processing, the product is mixed with dextrin and wetting.

12. The method according to p. 13, characterized in that the resulting product before mixing with dextrin and wetting filter.

13. The method according to one of paragraphs.13-15, characterized in that the wetting agent used lignosulfonate or sulphite yeast mash.

 

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