RO126401A2 - Process for preparing two component nutritive fluids with multiple biologic action - Google Patents

Abstract

The present invention relates to a process for preparing two component nutritive fluids with multiple biologic action, of a first fluid A formulated as nitrous foliar fertilizer, form amide nitrogen saturated with calcium and magnesium salts of aliphatic carboxylic acids with low molecular weight, and a second fluid B formulated as emulsified admixture between a liquid NPK fertilizer and an alcohol solution containing ammonium and potassium super-basic naphthenates and oleates, together with micronutrients. For compatibilization, the two fluids contain non-ionic tensides, antifoaming agents and additives for controlling the pH and the carbonation rate.

Description

The invention relates to a process for the manufacture of two complementary nutritional fluids, applicable foliar, successively or in mixture, after dilution with hard water. The first fluid is a foliar nitrogen fertilizer (contains as ammonium nitrogen as a macronutrient) saturated with calcium and magnesium salts (meso-nutrients) of low molecular weight aliphatic carboxylic acids (growth stimulants), containing micronutrients as non-ionic complexes, respectively. and antifoams for compatibility with the second complementary fluid or with other classes of foliarly applicable substances such as fungicides or growth stimulants. The second fluid is an emulsified mixture between a liquid fertilizer NPK (macronutrients are in the form of completely assimilable compounds) and an alcoholic solution containing naphthenes and super-base oils of ammonium and potassium (growth stimulants and fungicides), together with micronutrients. the form of ionic complexes with urea or of supernatants and naphthenic oils (growth stimulants and fungicides). In order to be compatible with the first complementary fluid or with other classes of foliar-applicable substances such as fungicides or growth stimulants, the fluid contains non-ionic surfactants, antifoam and other additives to control alkalinity and the rate of carbonation in the air after dilution and foliar application. The components of this fluid hydrolyze when diluted with hard water, and after carbonation with atmospheric carbon dioxide release the biologically active entities as micelles associated with macronutrients and micronutrients dispersed as amorphous nanoparticles, which easily penetrate the cuticle of the leaf and cell membranes. The two nutritional fluids, applied sequentially or in combination, provide at the leaf level balanced doses of macronutrients, meso-nutrients, micronutrients, growth stimulants and fungicides, in the form of entities generated directly on the leaf, which are in synergistic relationships, without the risk of overdose or induction imbalance. of assimilation. The coupling of the two complementary fluids allows to obtain a complete foliar nutritional product, assimilated by plants through a new mechanism, without the typical saline stress of the foliar nutrition and without the danger of overdosing on the biologically active components.

The known foliar products act on the plant in a unidirectional way, supplying it, either nutrients as inorganic synthetic products with or without organic additions containing macro and micronutrients, or growth stimulants or fungicides. Mixing those

, .ν-2 00? -7 η; 2 a - I 5 09; i009 three product classes substantially reduce the application costs, but the introduction of compatibilization agencies can unreasonably change the properties of the obtained products, and the mixing is most often debatable in terms of the individual effectiveness of each category of compounds. chemicals in the applied mixture. The individual components, carrying nutrients or functions capable of interfering with the biological processes involved in the metabolism and physiology of the plant are known and can be found in the usual formulations of nutritional fluids with or without the addition of biostimulators or fungicides. US Patent Nos. 2005235718, GB 1327092 and IT 1243694 describe processes for chelating microelements and emulsifying inorganic compositions to avoid application phytotoxicity. In the patents RO 116080, US 4125395 and US 4243676, the neutral and super-supernatants of copper, manganese, iron, zinc and molybdenum are conditioned as water-dilutable emulsions or as solutions in mineral oils to exploit their function as micronutrients. It is clear from US 4003994, GB 1532085 and JP 61233606 that the same supernatural naphthenes can be conditioned as fungicides with or without the addition of usual macronutrient carriers. Also, as fungicides, oleic acids can be conditioned, respectively their salts with micronutrients, with or without additions of superbasic naphthenates and alkaline bicarbonates, according to the processes described by the patents US5518987, WO 9418831 and JP 57131708. Another class of macro-active substances as a fungus. and the usual micronutrients are those of aliphatic carboxylic acids and their derivatives. The processes for conditioning the compounds of this class in the form of liquid foliar products are described by US Patents 4507142, AU 2169583 and JP 61233606. The main disadvantages of the processes described above are related to ensuring the chemical and thermal stability, respectively the homogeneity, of both the concentrate. during storage, as well as the diluted solution before application. Even the current processes for manufacturing the simplest formulations of N or NP foliar liquid fertilizers include a stabilization phase of micronutrients with various organic compounds, whose role is precisely to ensure product homogeneity and avoid segregation or inertization of components before application or after application of the diluted solution on the leaves. Thus, stabilization of the phosphorus content in NP leaf products requires not only the use of additives for the control of physical properties, but also the fine regulation of the pH within a narrow range of variation, according to the procedures described by US patents 6929673, EP 1386897 and CA 1250445. Moreover, the introduction of calcium and magnesium as mesonutrients in the foliar product formula excludes phosphorus and some micronutrients, and compatibility with fungicides and growth stimulants is practically compromised. The NP and NPK assortments available on the market for foliar fertilizers are not compatible with the addition of organic or inorganic substances containing calcium and magnesium in ionic form, meso-nutrients useful in

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2009Ό0724-1 5 -09- 2009 the processes of plant growth, and, even less, of biostimulators and fungicides. The major disadvantage of all the foliar assortments of nutritional fluids, described above, is the formulation of the ratios between the active components more in accordance with the specific physical properties of the foliar products and less in accordance with the ability of the plant to absorb them through the leaves and metabolize them. Alternative variants of sequential application of two or more assortments to provide a complete nutritional formula, according to the patent RO 120064, can solve the problem of leaf availability of all the active entities required by the plant. However, this method of application has a questionable advantage, since, in principle, all the applied fluids should act simultaneously and create synergies in order to reduce the saline stress caused at the leaf level. On the other hand, the separate application of several fluids involves prohibitive costs.

The process according to the invention removes the disadvantages of foliar fertilizers containing macro and micronutrients, respectively containing nutrients, biostimulators and fungicides, whereby all active components are incorporated into two complementary fluids containing all macronutrients, one micronutrient and one micronutrient particle. of components with the role of growth stimulants and fungicides, so that after dilution and mixing of the two complementary fluids a dilute emulsion applicable as foliar is obtained as partial hydrolysis product, in which the ratios between the biologically active components are those compatible with the foliar nutrition and the content in the biologically active components and the ratio between them can be adjusted according to the vegetation period, by the variation of the ratio of water / concentrate to dilution, of the ratio between fluid 1 and fluid 2 at mixing, respectively by the number of apply successive individual or mixed reactions of the two fluids.

The process according to the invention consists in the formulation of the first nutrient fluid, hereinafter referred to as nutrient fluid A, by mixing, at 20 - 50 ° C, a solution of urea with a concentration of 20-50% with 1 molar solutions of calcium salts and of magnesium of aliphatic carboxylic acids with 1 - 4 carbon atoms in the molecule and with a concentrated solution containing boron in the form of boric acid or borax, respectively manganese, zinc, copper, molybdenum and iron as inorganic salts - nitrates or sulphates - or, better as salts of aliphatic carboxylic acids with 1 to 4 carbon atoms in the molecule, so that the mass ratios of amide nitrogen / calcium ions and amide nitrogen / magnesium ions are between 5/1 and 15/1, and mass ratios between amide nitrogen and any micronutrients should be between 100/1 and 600/1. The surface tension of the obtained solution is adjusted to values between 20 and 40 mN / m with additions of nonionic and antifoam surfactants, the pH of the solution is brought to the value 5.5 - 7.0 with additions of ammonia, hydroxide or potassium carbonate, monoethanolamine. or triethanolamine, and finally dilute with demineralized water to a content of 30-140 g / 1 urea.

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The process according to the invention consists in the formulation of the second nutrient fluid, hereinafter referred to as nutrient fluid B, by mixing, at 20 - 50 ° C, a solution of urea with a concentration of 20 - 50% with a hydroxide solution of potassium or potassium carbonate with a concentration of 30 - 50% until a mass ratio of amide nitrogen / potassium 60/40 - 60/80 and with a solution 100 - 200 g / 1 naphthenic acids with molecular mass 150-300 and 100-200 g / 1 oleic acids with molecular weight 280 - 340 in a mixed solvent monoethanol amine triethanolamine - ethyl alcohol to a mass ratio of amide nitrogen / organic acids 56/60, after which the reaction mixture is well homogenized at a temperature of less than 50 ° C is neutralized with a mono-ammoniacal or mono-potassium phosphate IM solution to pH 10.0 - 11.0, when a mass ratio of amide nitrogen / phosphorus 56/15 - 56/20 is reached. The micronutrient content of fluid B is adjusted by the addition of a concentrated solution containing boron in the form of boric acid or borax, respectively zinc, copper, molybdenum and iron in the form of inorganic salts nitrogen or sulphates - or, better, as salts of acids. aliphatic carboxylics with 1 - 4 carbon atoms in the molecule so that the mass ratios of amide nitrogen / calcium ions and amide nitrogen / magnesium ions are between 5/1 and 15/1, and the mass ratios between amide nitrogen and any of the micronutrients or between 100/1 and 600/1. The surface tension of the obtained fluid is adjusted to values between 20 and 40 mN / m with additions of nonionic and antifoam surfactants, and finally it is diluted with demineralized water to a content of 60-140 g / 1 urea.

The process according to the invention allows the manufacture of two complementary nutrient fluids, stable for an indefinite period of storage in hermetically sealed containers, applicable sequentially or in mixture after dilution in proportion of 10 parts fluid Β / 1 part fluid A up to 10 fluid parts B / 3 fluid parts A, so that the N / P / K ratio can be varied in the proportions required by the plant in various vegetation phases, and the NPK / micronutrient, NPK / mid-nutrient, NPK / growth stimulating and NPK / fungicide ratios be varied within limits sufficiently wide to ensure complete assimilation of all nutrients and synergistic action of other classes of products useful for plant growth.

The process according to the invention consists in the initial formulation of a common solvent, consisting of water, urea, nonionic surfactants and antifoams, capable of sequentially dissolving all the inorganic and organic components of the two complementary nutrient fluids, according to a defined dosage schedule of each component. in part or each class of components, until the particular composition of each of the two nutrients is reached, so that the N / P / K molar ratios can take any value from 10 - 0.6 - 1 to 1 - 0,6 - 2, at a total concentration of amide nitrogen of maximum 4 moles / liter.

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The process according to the invention uses classes of substances, such as naphthenes and emulsified superbasic oils, whose fundamental properties allow the complete solubilization of the usual carriers of macro, mezo and micro nutrients in multiphase fluids, capable of generating the typical properties of foliar products, such as be the adhesion, the dispersion capacity on the applied foliar surfaces, the penetration power of the cuticle of the leaf and of the cell membranes at a convenient concentration and at a moderate pH, the chemical stability and compatibility with the hard waters when diluting, regardless of the nature and the concentration of the saline components.

The process according to the invention allows the pH to be adjusted to suitable values in the range 5.5 -7.0 for fluid A and 10.0 - 11.0 for fluid B, independent of the nitrogen / phosphorus / potassium ratio, concentration and final composition. on components of the two fluids, so that the hydrolysis threshold of the mixtures of super-base oils and naphthenates is reached by simply diluting the fluid B with hard water to a mass ratio 1/400, both in the case of its direct application, as well as in case of applying mixtures of the two fluids previously diluted.

The process according to the invention allows the hydrolysis and partial or complete carbonation of mixtures of superazole oils and naphthalenes, respectively the partial carbonation of alkaline compounds containing potassium and ammonium ions directly on the leaf when the diluted B fluid is applied up to a 1/400 mass ratio or mixtures. of the two fluids diluted before mixing up to 1/100 mass ratios, processes after which biologically active entities are generated in the form of micelles associated with dispersed macronutrients as amorphous nanoparticles, metabolized by the leaf without the typical stress of foliar nutrition and without danger overdose of biologically active components.

The process according to the invention has the following advantages:

- allows to obtain nutritional fluids with variable formula N - P - K, so that by simply mixing fluid A with fluid B in different proportions, specific nitrogen-rich assortments can be prepared for periods of vegetative growth of plants and potassium-rich assortments specific the ripening and ripening periods of the crops;

- by correlating the composition factors and the control factors of the physical properties of the emulsion hydrolyzed by dilution with hard water and natural carbonation on the leaves, the two complementary fluids provide in balanced doses a complete nutritional mixture (macronutrients, meso-nutrients, micronutrients, growth stimulants and fungicides), evenly distributed on the surface of the leaves as an adherent film, in which the effect of NPK / micronutrient ratios, tc-l 0 0 9 - 0 0 7 2 4-1 5 09/2009

NPK / mezonutrients, NPK / growth stimulants and NPK / fungicides is maximized by the synergy of biologically active components,

- through the wide possibilities of adjusting the surface tension and the pH without affecting the composition and the ratio between the components, the entities with nutritive action, biostimulators and fungicide are generated in an activated form after the proper application, so that their action manifests without the saline stress typical of the foliar products, and the probability of overdose is excluded, since the organic film of the hydrolysis products progressively releases the active entities as they are consumed at the foliar level;

- both nutrient fluids are independently compatible with all classes of growth stimulants and fungicides, as well as with all classes of liquid fertilizers N and NK, increasing their nutritional value through the contribution of macro, meso and micronutrients, growth stimulants and compounds with fungicidal properties.

The following are 8 examples illustrating the invention:

Example 1. An amount of 400 grams of urea solution 30% in demineralized water is heated to 40-50 ° C and, under stirring, mixed with 20 ml aqueous solution 100g / l alcohololipolyethoxylates with 6 and 9 ethoxy groups in the molecule, 0 , 1 ml silicone non-foaming solution 10% in ethyl alcohol and 13.0 grams of manganese nitrate 50% aqueous solution, obtaining the solvent for the preparation of fluid A, called intermediate 1. in 500 ml demineralized water, at 60-70 ° C, 45.8 grams of boric acid, 36.4 grams of crystallized zinc nitrate with 6 crystallization water molecules and 3.7 grams of ammonium molybdate are dissolved, then the mixture is brought to a volume of one liter with demineralized water, obtaining micronutrient solution called intermediate intermediate 2. Mix the whole amount of intermediate 1 with 50 ml intermediate 2 until homogenized and then slowly add 200 ml of magnesium acetate IM solution and 200 ml of calcium formate. After stirring and stirring for 15 minutes to complete the chemical reactions, the mixture is diluted with demineralized water up to 1 liter or up to a density of 1.045 g / ml, obtaining Fluid A. The pH of the fluid A is adjusted to 5.5 -7.0 with a dilute solution of ammonia in demineralized water. Fluid A has a concentration of 120 g / 1 urea, 8.0 g / 1 Ca ²⁺ (as formate), 4.8 g / 1 Mg ² (as acetate), 0.4 g / 1 B (as boric acid), 0.4 g / 1 Zn ²⁺ , 0.1 g / 1 Mn ²⁺ and 0.1 g / 1 Mo (as ammonium molybdate) and 2-4 g / 1 other components.

Example 2. An amount of 400 grams of 30% urea solution in demineralized water is heated to 40-5 0 ° C and, under stirring, mixed with 20 ml aqueous 100g / l alcohololipolyethoxylates with 6 and 9 ethoxyl groups in the molecule, 0.1 ml silicone non-foaming solution 10% in ethyl alcohol and 2 ml aqueous copper nitrate 200 g / 1 metallic copper,

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5 ί 1 019 yielding the solvent for the preparation of the fluid Bl, called intermediate 3. Intermediate 4 is prepared by mixing and homogenizing at 50-60 ° C 30 grams of naphthenic acids with molecular mass 150-300, 30 grams of oleic acids with molecular weight 280 - 340, 20 grams monoethanolamine, 25 grams triethanolamine and 50 grams ethyl alcohol. Intermediate 3 is mixed until complete homogenization with 140 grams of 40% potassium hydroxide solution, and then the intermediate 4 is added completely. The reaction mixture is stirred for 30 minutes to complete the chemical reactions and to form the emulsion of the potassium naphthenates and super-base oils. The reaction is terminated when the liquid becomes transparent. Then, in the emulsion formed, cooled to 35-40 ° C, 272 grams of 30% solution of monopotassium phosphate and 50 ml of intermediate 2, prepared as in Example 1, containing micronutrients, is slowly added under intense stirring. After complete emulsion clarification, the mixture is diluted with demineralized water to 1 liter or to the density of 1,100 g / ml, obtaining Fluid Bl. The pH of fluid B is adjusted to 10.0 - 10.5 by adding diluted solution. ammonia in demineralized water or 10% orthophosphoric acid. Fluid Bl has the concentration 120 g / l urea, 18.4 g / l P (as orthophosphate), 62.4 g / l K ⁺ , 0.4 g / l B (as boric acid), 0.4 g / l Zn ²⁺ , 0.4 g / l Cu ²⁺ , 0.1 g / l Mo (as ammonium molybdate), 30 g / l naphthenic acids, 30 g / l oleic acids, 20 g / l monoethanolamine, 25 g / l triethanolamine and 2-4 g / l other components.

Example 3. An amount of 100 grams solution of urea 30% in demineralized water is heated to 40-50 ° C and, under stirring, mixed with 20 ml aqueous solution 100g / l alcohololipolyethoxylates with 6 and 9 ethoxyl groups in the molecule, 0 , 1 ml silicone antifoam solution 10% in ethyl alcohol and 2 ml aqueous solution of copper nitrate 200 g / l metallic copper, obtaining the solvent for the preparation of the fluid B2 called intermediate 5. Intermediate 4 is prepared as in example 2. Intermediate 5 mix until 552 grams of potassium carbonate solution is completely homogenized, then add intermediate 4. The reaction mixture is stirred for 60 minutes to complete the chemical reactions and to form the emulsion of potassium naphthenates and superbasic oils. The reaction is terminated when the liquid becomes transparent. Then, in the emulsion formed, cooled to 35-40 ° C, 272 grams of 30% solution of monopotassium phosphate and 50 ml of intermediate 2, prepared as in Example 1, containing micronutrients, is slowly added under intense stirring. After complete emulsion clarification, the mixture is diluted with demineralized water to 1 liter or to a density of 1,170 g / ml to obtain Fluid B2. The pH of fluid B2 is adjusted to 10, 0 - 10.5 by adding diluted ammonia solution in demineralized water or 10% orthophosphoric acid. Fluid B has a concentration of 60 g / l urea, 18.4 g / l P ( caortophosphate), 78.0, g / l K ⁺ , 0.4 g / l B (as boric acid), 0.4 g / l Zn ²⁺ , 0.4 g / l Cu ²⁺ , 0.1 g / l Mo (as ammonium molybdate), 30 g / l

CV- 2 Ο Ο 9 - Ο Ο 7 2 4 - 1 5 09- 2009 naphthenic acids, 30 g / 1 oleic acids, 20 g / 1 monoethanolamine, 25 g / 1 triethanolamine and 2-4 g / 1 other components.

Example 4. Dilute the fluids A, prepared as in example 1, Bl, prepared as in example 2 and B2, prepared as in example 3, with hard water, about 10 ° Ge, in the proportion of 1/100 and 1/200, and carbonate to pH 7.5-8.5. Fluid A forms a stable carbonate solution, which does not separate crystalline or amorphous compounds after 7 days of standing outdoors at ambient temperature. Fluid B forms a stable emulsion after 7 days of standing outdoors at ambient temperature, without the separation of crystalline / amorphous compounds or the separation of a second liquid phase, although the formation of the superazine naphthenic micelles and the amorphous particles of inorganic combinations is visible. The variation of the particle size in the diluted and carbonated emulsion of the fluid B1 as a function of the dilution rate is shown in Figure 1. This example illustrates the stability of the foliar applied liquids between the time of dilution and the moment of application, as well as the mechanism of formation of the stable film on the leaf surface.

Example 5. Nutrient fluids A and Bl are diluted with hard water, about 10 ° Ge, in the proportion of 1/100, not carbonated as in Example 4. The two diluted solutions mix rapidly, in the proportions A (l / 100 ) / Bl (l / 100): 1/9, 2/8 and 3/10, under moderate agitation. The resulting emulsions remain stable after 7 days, standing outdoors at room temperature, without separating a second liquid phase or precipitating calcium or magnesium salts, although the formation of super-small naphthalene and amorphous particles of inorganic combinations is visible. This example illustrates the compatibility of the two fluids with each other.

Example 6. Fluid A concentrate mixes with concentrated UAN fertilizer in proportions: fluid A / fertilizer UAN: 1/9, 3/17, 5/5, 7/3 and 9/1. The resulting solutions are clear. Dilution with hard water and carbonation does not destabilize the solutions of the two types of nutrients. This example illustrates the compatibility of fluid A with UAN liquid manure, respectively the possibility of increasing the effectiveness of UAN liquid manure applied foliar by enrichment with micronutrients and similar calcium and magnesium compounds.

Example 7. An amount of 1 liter of UAN liquid fertilizer is ammoniacised with ammonia gas or 20% ammoniacal solution in hard water to a pH 10.5 -11. Then, the buffered UAN liquid reservoir is mixed in a proportion of 100 parts UAN / 5 parts nutrient B. A clear stable emulsion is obtained, which hirolizes when diluting with hard water in a proportion greater than 1/100, forming a sheet-emulsifiable fluid. . This example illustrates the compatibility of fluid B with UAN liquid fertilizer, respectively the possibility of increasing the effectiveness of UAN liquid fertilizer applied foliar by the contribution of macro, mezo and micronutrients, growth stimulants and compounds with fungicidal properties.

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Example 8. The complementary nutritional fluids A and B were applied to the foliar fertilization of apple crops of the Idared variety, following the scheme of successive treatments at 24 hours intervals, first with product A and then with product B, solutions diluted with hard water in 1/100 ratio. The experimental data are presented in Tables 1 and 2. From Table 1 it follows that the application of dual nutritional fluids leads to the highest ratio between the fruits remaining after the physiological fall and the related fruits. This ratio increases when foliar treatment is associated with the application of nitrogenous fertilizers to the soil. Moreover, the growth stimulating effect is selective with respect to the fruit in relation to the vegetative growths associated with the development of annual shoots. From the same table it is observed that the comparison product, containing nutrients and biostimulators, has lower performances of dual nutrient fluids, in that in the comparison product the growth stimulator acts equally on the development of annual shoots and on the development of fruits in number and mass. (see Table 2). From table 2, the application of dual nutrient fluids leads to the highest production (estimated in tonnes / ha) and to the fruits with the largest size. The association of the foliar treatment with the application of the nitrogenous fertilizers to the soil has significant positive effects from the point of view of the production of the fruit size. Expressing the quality of apples only by the specific color indicator, from Table 2 it is observed that foliar treatment with dual nutrient fluids accelerates the process of chlorophyll degradation and the conversion of degradation products into anthocyanins.

The results, presented in tables and 2, as well as other results obtained on experimental batches in vegetable crops, demonstrate the effectiveness of the dual nutrient fluids applied after the variant of example 8 or after a variant with the mixing of the two fluids after dilution, in all application conditions, with or without soil NPK fertilizer intake. Production gains and quantified gains from quality indicators are real and justify the profitability of using these fluids.

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Table 1. Results collected during the period of vegetative growth

Variant parameter The total number of flowers / tree Total number of fruit related / tree Total number of fruits after physiological / tree fall Length of annual shoots, cm Version 1 (untreated control) 556 236 106 54.7 Version 2 (control treated with nitrogen fertilizers on the ground) 482 301 129 54.6 Variant 3 (treated with dual nutrient fluids) 487 248 166 54.4 Version 4 (treated with soil nitrogen fertilizers and dual nutrient fluids) 596 264 181 58.6 Variant 5 (treated with comparative foliar product containing nutrients and biostimulators) 523 1 - 201 148 73.0

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Table 2. Results collected during the harvesting period

parameter Alternative Amount of apples harvested, tonnes / ha Average mass of fruits, g / fruit The fraction of the total surface covered by the red color,% Version 1 (untreated control) 38.4 140 10 Version 2 (control treated with nitrogen fertilizers on the ground) 47.2 146 30 Variant 3 (treated with dual nutrient fluids) 65.2 154 80 Version 4 (treated with soil nitrogen fertilizers and dual nutrients) 79.1 194 70 Variant 5 (treated with foliar product containing nutrients and biostimulators) 48.9 147 40

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Bibliography

1. AU 2169583, 1984;

2. CA 1250445, 1989;

3. EP 0968981, 2000;

4. EP 1386897, 2004;

5. GB 1,327,092, 1973 ;;

6. GB 1,520,752, 1978;

7. GB 1,532,085, 1978;

8. IT 1243694, 1994;

9. JP 57131708, 1982;

10. JP 61233606, 1986;

11. RO 120064, 2005;

12. RO 116080, 2000;

13. U.S. 3,661,550, 1972;

14. U.S. 3,854,923, 1974;

15. U.S. 4003994, 1977;

16. U.S. 4,125,395, 1978;

17. U.S. 4,243,676, 1981;

18. U.S. 4,652,294, 1987;

19. U.S. 4507142, 1985;

20. U.S. 5,199,967, 1993;

21. U.S. 5,435,822, 1995;

22. US 5518987, 1996,

23. U.S. 6929673, 2005;

24. U.S. 2005235718, 2005;

25. WO 9418831, 1994 (V 2 Ο Ο 9 - ο ο Ί 2 4 - - fa

Claims (3)

1. Process for the manufacture of dual nutritional fluid A with multiple biological action, characterized by the fact that, after mixing, at 20 - 50 ° C, a solution of urea with a concentration of 20 - 50% with 1 molar solutions of the salts of calcium and magnesium of aliphatic carboxylic acids with 1 to 4 carbon atoms in the molecule and with a concentrated solution containing molybdenum in the form of ammonium molybdate and boron in the form of boric acid or borax, respectively manganese, zinc, copper, and iron below form of inorganic salts - nitrates or sulphates or, more preferably, salts of aliphatic carboxylic acids with 1 - 4 carbon atoms in the molecule, so that the mass ratios of amide nitrogen / calcium ions and amide nitrogen / magnesium ions are between 5 / 1 and 15/1, and the mass ratios between amide nitrogen and any of the micronutrients to be between 100/1 and 600/1, give an emulsified concentrate whose surface tension it is adjusted to values between 20 and 40 mN / m with additions of non-ionic surfactants and antifoam, and the pH of the concentrate is brought to the value of 5.5 - 7.0 with additions of ammonia, potassium hydroxide or carbonate, monoethanolamine or triethanolamine , after which the concentrate is diluted with demineralized water to a content of 30-140 g / 1 urea, resulting in a stable product, dilutable with hard water in any proportion, able to exert a combined action of foliar nutrient, biostimulator and fungicide. application at moderate doses throughout the vegetation period of cereals, vegetables and fruit trees. 2. Process for the manufacture of dual nutrient fluid B with multiple biological action, characterized by the fact that, after mixing, at 20 - 50 ° C, a solution of urea with a concentration of 20 - 50% with a solution of potassium hydroxide or potassium carbonate with a concentration of 30 - 50% until a mass ratio of amide nitrogen / potassium 60/40 - 60/80 and a solution of 100 - 200 g / 1 naphthenic acids with molecular weight 150-300 and 100-200 g / 1 oleic acids with molecular weight 280 - 340 in a mixed solvent monoethanol amine - triethanolamine - ethyl alcohol up to a mass ratio nitrogen amide / organic acids 56/60, homogenizing the reaction mixture at a temperature below 50 ° C and neutralization with a mono-ammoniacal or monopotassium IM phosphate solution to pH 10.0 - 11.0, when a mass ratio of amide nitrogen / phosphorus 56/15 - 56/20 is reached, followed by mixing with a solution containing molybdenum as molybdate of ammonium and boron in the form d it is boric acid or borax, respectively manganese, zinc, copper, and iron in the form of inorganic salts - nitrates or sulphates or, better, as salts of aliphatic carboxylic acids with 1 - 4 carbon atoms in the molecule, so that mass ratios amide nitrogen / calcium ions and amide nitrogen / magnesium ions to be between 5/1 and 15/1, and the mass ratios between amide nitrogen and any of the micronutrients to be between 100/1 and 600/1, an emulsified concentrate is obtained whose 1 O O 9 - o o 7 2 '* 1 5 -09- 20 (19 surface tension is adjusted to values between 20 and 40 mN / m with additions of nonionic and antifoam surfactants, and finally the concentrate is diluted with demineralized water to a content of 60-140 g / 1 urea, resulting in a stable product, dilutable with hard water in any proportion, capable of exerting a combined action of foliar nutrient, biostimulator and fungicide following the application in moderate doses throughout the vegetation period of cereals, vegetables and fruit trees. 3. Process for the manufacture of two complementary nutritional fluids A and B with multiple biological action applicable to the foliar, characterized in that, due to the common solvent used in the formulation of these fluids and a compatibility complex based on the synergy of the components selected as carriers of biologically active substance and tensides used for the control of the physical-chemical properties, after mixing the two fluids after diluting them with hard water, a reactive product with atmospheric carbon dioxide is obtained, capable of generating at the surface of the surface entities active in the nascent state whose nanometric dimensions. combined biological action allows the simultaneous supply to the surface of the leaf of NPK macronutrients, calcium and magnesium monomerrients, molybdenum micronutrients, boron, manganese, zinc, copper and iron, as well as biostimulators and fungicides in the form of hydrated carbonates of naphthenes and olefins OF THE superbasic potassium, ammonium, calcium, magnesium, copper, zinc, manganese and iron.