BRPI1100314A2 - liquid fertilizer compositions containing high concentration mineral chelates, preparation process and method for the treatment of plants - Google Patents

Abstract

LIQUID FERTILIZING COMPOSITIONS CONTAINING HIGH CONCENTRATION MINERAL CHELATES, PREPARATION PROCESS AND METHOD FOR PLANT TREATMENT. This invention relates to novel liquid fertilizer compositions which have high concentration minerals in the form of chelates prepared with amino acid salts, or in the form of chelates prepared with amino acids with basic functional groups and acids. The invention also discloses processes for obtaining liquid fertilizer compositions and methods for treating plants.

Description

"FIELD FERTILIZING COMPOSITIONS CONTAINING HIGH CONCENTRATION MINERAL CHELATES, PREPARATION PROCESS AND METHOD FOR PLANT TREATMENT" FIELD OF THE INVENTION This invention relates to novel fertilizer compositions

liquid, with pH values close to neutrality, which present high concentration minerals in the form of chelates prepared with salts of lysine or arginine and at least one other naturally occurring amino acid. Other compositions are characterized in that they contain mineral chelates prepared with aspartic acid or glutamic acid salts or prepared with amino acids containing acidic and basic functional groups. The invention also discloses processes for obtaining liquid fertilizer compositions and methods for treating plants. BACKGROUND OF THE INVENTION Plants need a variety of nutrients in order to have

proper growth and absorption occurs naturally through the soil. However, when the availability of these compounds in the soil is not optimal, it is necessary to perform treatments using fertilizers so that the plants present the desired growth by the farmers. Among the nutrients necessary for good plant growth, we highlight the minerals selected from phosphorus, potassium, calcium, magnesium, iron, boron, manganese, copper, molybdenum, cobalt and zinc, which can be administered in solid form or as aqueous solutions. When they are administered in their solid form, the minerals are mixed in the soil and their absorption occurs in the roots of plants. When they are administered in the form of aqueous solutions they are called foliar fertilizers because absorption occurs predominantly through the leaves of plants. In other cases, absorption occurs by the administration of aqueous solutions via fertigation or hydroponics procedures. Leaf fertilizers may contain compounds other than minerals of interest, such as surfactants and preservatives for the purpose of enhancing product performance. However, regardless of the formulation used, an essential condition for the preparation of foliar fertilizers is that they have acceptable levels of the mineral, to enable its industrial production, as well as reduce transportation costs and ease of handling during its use in crops. In addition to presenting high concentrations of minerals, leaf fertilizers must be stable for long periods of storage, even under different temperatures, and have compatible physical and chemical characteristics to be used as agricultural fertilizers.

Minerals perform specific functions for the good development of plants. For example, zinc is an enzymatic activator, responsible for the maturation and growth of plant species and its deficiency brings evident morphological changes, especially in younger parts of the plant. These alterations can be cited: internerval chlorosis of young leaves, bronze-colored leaves, necrotic spots, smaller and lanceolate leaves, short internodes and retarded growth. Therefore, zinc deficiency causes retardation of plant growth, which prevents leaf evolution and stem elongation. Inadequate zinc content consequently causes also deficient grains, which negatively reflects their quality as feed for animals and humans.

Other minerals such as calcium, magnesium, molybdenum, copper,

Iron, manganese and cobalt are also fundamental for the good development of plant organisms, and each of these elements has a specific phytological function at each stage of plant evolution.

Currently, the administration of minerals in plants as foliar fertilizers is still mostly in the form of aqueous solutions of their inorganic salts, such as chlorides or sulfates. This is due to the possibility of obtaining high content compositions of these minerals at comparatively low prices. However, one of the inherent disadvantages of these products is the low bioavailability of the mineral, as it takes several days for these inorganic forms to be absorbed in relatively significant amounts by plants. During this period, these fertilizers are subject to weathering, such as wind and rain, which can carry fertilizers to the soil, making them unavailable to plants. In order to increase the rate of absorption of the mineral, fertilizers can be prepared by dissolving chelates of the mineral prepared with ethylenediaminetetraacetic acid, its salts or correlates, commonly known as acronyms such as EDTA, DTPA, DDTA, EDDA and EDDHA. In some of these cases, solutions containing moderate mineral concentrations in the form of these chelates may also be obtained, but because this class of compounds do not consist of substances naturally found in nature and the energy expenditure involved in the absorption of minerals chelated in this way by plants, Its use is also not the most desired in agricultural crops. Moreover, the absorption rates of these compounds is not the most desired either.

One way to overcome the problems associated with EDTA1 derivatives is to reduce the energy expenditure of plants during organisms' absorption of minerals and, above all, to increase the rate of absorption of minerals, by administering compounds that have greater homology. with those found naturally in plants. This can be achieved by the use of mineral-containing fertilizers in the form of naturally occurring amino acid chelates if it is possible to circumvent the low solubility of these compounds when prepared with the minerals needed for plant nutrition.

In general, mineral chelates prepared with naturally occurring amino acids have low solubility and, more specifically, iron, manganese, cobalt, zinc and copper chelates are particularly problematic for the preparation of foliar fertilizers due to the low solubility inherent in These compounds make it difficult or impossible to prepare the products.

In a recent document filed under US Patent No. 7,022,351 B2, the authors show how to prepare liquid compositions with high mineral concentrations in the form of amino acid complexes. In this paper the authors explain the difficulties encountered in obtaining liquid compositions containing significant levels of minerals that remain stable. Thus, it is mentioned by the authors from the last paragraph of column 3 that "... the preparation of liquid compositions of amino acid complexes presents special challenges due to the fundamental chemical properties of these complexes, especially if a stable solution is required. When a salt of a mineral is mixed with a solution of an amino acid, a balance is struck between the various amino acid species, including the mineral complexes. The relative concentrations of these species depend on the pH of the solution, amino acid concentration, mineral complex, constant of stability of complexes and pKa of amino acids (...) at higher pH values, metal complexes: 1: 2 amino acids begin to form as well as mineral hydroxides. : 1: 2 amino acids are poorly soluble in water (...) A solution of an amino acid complex that is formulated to have a pH between 2 and 5 may not be stable due to precipitation of amino acid ... "

Thus, it is of great interest to describe new aqueous compositions containing minerals in high concentrations and which do not have technical disadvantages such as those already reported when used as agricultural foliar fertilizers, such as slow plant uptake and phytotoxicity.

Thus, it is an object of this invention to describe stable liquid fertilizer compositions containing minerals at high comparative concentrations, characterized in that the minerals are in the form of amino acid chelates in a mineral: amino acid stoichiometric ratio that meets the valence of the metal, such as a ratio. mineral molar: amino acid equal to 1: 2 for bivalent metals. In another aspect of this invention, it is also of interest to show that the novel compositions can be efficiently prepared at near neutral pH values or even at alkaline pH values between 5.0 and 10.0 where neutral chelated species prevail. only amino acids as mineral binders. In yet another aspect of this invention, it is also of interest to show that the novel compositions can be efficiently used as plant treatment fertilizers.

CheLates are the products resulting from the binding of a specific organic molecule, called a binder, to a metal ion by more than one functional group to form a heterocyclic structure. Chelates may be naturally occurring or synthetic. Examples of products prepared with synthetic precursors are EDTA1 DTPA, DDTA1 EDDA1 EDDHA chelates or similar compounds. Examples of products prepared with natural precursors are chelates formed by the coordination of a metal center, called minerals, with hemoglobin, chlorophyll or even amino acids. When minerals are coordinated with the peptide mixture resulting from hydrolysis of protein sources, the resulting products are more aptly termed as proteinates.

In the specific case of chelates prepared exclusively with amino acids and which do not contain inorganic anions in their structure directly linked to the mineral, the compounds are characterized by having at least two heterocyclic rings formed by coordination with the amino acids used in the process. Structure 1 below shows a general chemical structure for amino acid chelates of divalent minerals such as iron (ll), zinc, copper, manganese, calcium, magnesium and cobalt.

STRUCTURE 1

In structure 1 the dotted lines represent ionic or covalent bonds and when R1 and R2 are equal to H1 the linker is glycine, the simplest of the essential amino acids. However, Ri β R2 may represent any other side chains to result in one of more than twenty naturally occurring amino acids, selected from L-lysine1 L-alanine, L-phenylalanine, L-leucine, L-isoleucine, L-proline, L -hydroxyproline, L-arginine, L-methionine, L-aspartic acid, L-glutamic acid, L-valine, L-threonine, L-isotreonine, L-histidine, L-tryptophan, L-serine and L-glutamine. Depending on the valence and mineral, the metallic cation may be coordinated to two, three or even eight amino acids, but preferably should be coordinated to two or three ligands. Certain minerals may form more bonds than their oxidation state allows due to the filling of the metal's free d orbitals, as in the case of iron.

There are several documents in the literature that teach how to prepare free amino acid chelates. We recently filed a patent document under BRPI 0603256A where we teach how to prepare new oxidation resistant iron amino acid chelates. Other ways to prepare amino acid chelates can be found in US 4,599,152, US 4,830,716, US 6,166,071 and US 5,516,925. It is very important to clarify that the amount of mineral

Incorporated into a given amino acid chelate is directly proportional to the molecular weight of the amino acids involved in the chelation process and the atomic weight of the mineral of interest. For example, the maximum calcium content in the form of an chemically achievable amino acid chelate occurs when calcium is reacted with glycine, which has the lowest molecular weight of naturally occurring amino acids. In this case, it is possible to obtain a product called calcium bis (glycinate) which has a calcium content of not more than 21% and more commonly around 20% depending on the number of hydration water molecules present in the product. which may vary according to the method employed in preparing the compound. Thus, calcium chelates prepared with any of the other naturally occurring amino acids can only have calcium contents of less than 20%, since the percentage by weight of calcium is proportionally lower in relation to the molecular weight of the final product and therefore In general, calcium content is inversely proportional to the molecular weight of amino acids used in chelation processes. Of course, these considerations also apply to all other minerals in the form of amino acid chelates.

As described above, in the case of foliar fertilizers, it is of great interest that liquid formulations have the highest possible concentration of minerals to minimize their costs of material production and transport to crops. Unfortunately, aqueous solutions containing high concentration amino acid chelates are not easily prepared depending on the mineral of interest.

In addition, as stated above, it is clear that the

Mineral concentrations in aqueous solutions in the form of amino acid chelates depend not only on the solubility of the compound of interest, but also on the mineral content present in the chelate.

In other cases, although not preferred, it is possible to obtain higher mineral liquid compositions by combining chelates, proteinates and mineral salts. For example, in the document filed under US2005 / 235718A1 patent application, the authors claim the preparation of liquid foliar fertilizer compositions with high comparative concentrations. However, in view of the chemically tangible mineral content for amino acid chelate minerals, it is clear to those skilled in the art that proteinates prepared from protein hydrolysates cannot have comparatively high mineral contents as The average molecular weight of the ligands does not allow such mineral concentrations to be reached exclusively in the form of amino acid chelates, especially after dilution in water. OBJECTIVES OF THE INVENTION

It is an object of this invention to describe liquid compositions containing high concentration minerals in the form of amino acid chelates prepared with at least one amino acid in the form of one of their salts, wherein these amino acid salts are selected from lysine, arginine salts. or ornithine. In another aspect of this invention, liquid compositions are characterized in that they contain mineral chelates prepared with aspartic acid or glutamic acid salts. In yet another aspect of this invention, it is an object to show that the compositions preferably have pH values ranging from 5 to 10 and do not contain inorganic or organic counterions in an amount greater than necessary for the formation of amino acid salts. In yet another aspect of this invention, one object is to show liquid fertilizer compositions which contain minerals in the form of amino acid chelates prepared by combining an amino acid containing an acid functional group and an amino acid containing a basic functional group. Another objective is to show that the compositions are stable even after dilution in water under different storage conditions and that they can be efficiently used as fertilizers for plant treatment. DESCRIPTION OF THE INVENTION

Amino acid chelates of minerals are especially difficult to present in the form of commercially acceptable aqueous solutions of minerals, as the water solubility of these compounds is usually low, even in cases where isolated chelates have high minerals. For example, zinc chelate prepared with two glycine molecules and referred to as zinc bis (glycinate) has a zinc content of 30%. However, their low water solubility does not allow solutions of these compounds with zinc content higher than 6% zinc to be obtained. The low solubility of zinc amino acid chelates is also evident when other compounds are used for the preparation of leaf fertilizers, such as zinc bis (lysinate), zinc bis (alaninate), zinc bis (phenylalaninate), bis (leucinate). ) zinc, zinc bis (isoleucinate), zinc bis (prolinate), zinc bis (hydroxyprolinate), zinc bis (arginate), zinc bis (methioninate), zinc bis (aspartate), bis (glutamate) zinc, zinc bis (valinate), zinc bis (threoninate), zinc bis (isotreoninate), zinc bis (histidinate), zinc bis (tryptophanate), zinc bis (serinate) and bis (glutaminate) zinc. When dextrogens or even racemate isomers of amino acids are used for the preparation of chelates, products which do not have the required water solubility for the preparation of foliar fertilizers are also obtained. Undesirable results are also obtained when compounds are prepared from the combination of these amino acids and preferably by the combination of glycine, lysine, alanine, phenylalanine, leucine, isoleucine, proline, hydroxyproline, arginine, methionine, aspartic acid, glutamic acid, valine, threonine, isotreonine, histidine, tryptophan, serine and glutamine, and preferably by combining glycine with at least other naturally occurring amino acids to provide relatively higher zinc compounds. Similar undesirable results are also observed.

with copper, manganese, cobalt, calcium, magnesium and nickel, which characteristically have low solubility when they are in the form of amino acid chelates.

We have surprisingly found that it is possible to obtain mineral-containing liquid foliar fertilizer compositions in the form of an amino acid chelate when at least one of the amino acids used for the preparation of the chelate are lysine, arginine, aspartic acid or glutamic acid in the form of their salts. Examples of salts of lysine or arginine suitable for the preparation of the liquid fertilising compositions object of the invention are selected from hydrochlorides, sulfates, nitrates, acetates, formates, gluconates, tartrates, lactates, citrates, among other organic salts. The other amino acid selected for the preparation of the chelate of interest may also be lysine or arginine in base form or also in the form of salts thereof among the other naturally occurring amino acids mentioned above, although glycine is preferably used. The reason for the preferred use of glycine is that chelates obtained with this amino acid have a higher comparative content of the mineral due to the low molecular weight of glycine. Examples of salts of aspartic or glutamic acid suitable for the preparation of the liquid fertilising compositions object of the invention are selected from ammonium, sodium, potassium or organic amines salts, which may be selected from primary, secondary or tertiary amines. The compounds present in the compositions of interest may be described according to structures 2, 3, 4, 5 and 6.

STRUCTURE 4 STRUCTURE 5

THE

THE

STRUCTURE 6

In structure 2 the chelates prepared with

lysine salts, structure 3 represents chelates prepared with arginine salts, structure 4 represents chelates prepared with aspartic acid salts and structure 5 represents chelates prepared with glutamic acid salts. The dashed lines represent ionic or covalent bonds and X can be selected from chloride, sulfate, hydrogen sulfate, nitrate, acetate, lactate, gluconate, tartrate, citrate anions, while Y can be selected from ammonia, sodium, potassium or amines. primary, secondary or tertiary. R 1 may be H, in which case it represents the amino acid glycine, or any other side chains representing a naturally occurring or synthetic α-amino acid selected from L-lysine, L-alanine, L-phenylalanine, L-leucine, L- isoleucine, L-proline, L-hydroxyproline, L-arginine, L-methionine, L-valine, L-threonine, L-isotreonine, L-histidine, L-tryptophan, L-serine and L-glutamine. When the group R1 represents the amino acids lysine or arginine, these may be in the form of their salts selected from their hydrochlorides, sulfates, nitrates, acetates, formates, gluconates, tartrates, lactates, citrates, among other organic salts R2 may be H, and in which case it represents the amino acid glycine, or any other side chains representing a naturally occurring or synthetic α-amino acid selected from, L-alanine, L-phenylalanine, L-leucine, L-isoleucine, L-proline, L-hydroxyproline , L-methionine, L-aspartic acid, L-glutamic acid, L-valine, L-threonine, L-isotreonine, L-histidine, L-tryptophan, L-serine and L-glutamine. When the group R2 represents the amino acids L-aspartic acid or L-glutamic acid, these may be in the form of their ammonium, sodium, potassium or primary, secondary or tertiary amine salts, although ammonium or potassium salts are preferably used. as they are also nutrients for plants.

In other cases, the compounds present in the compositions are

represented by structure 6, which are chelates formed by combining a mineral with an amino acid containing an acid group, such as L-aspartic acid or L-glutamic acid, and an amino acid containing a basic group, such as L-lysine, L- arginine or L-ornithine. In such cases, it is possible to obtain compositions with a large amount of mineral in solution because a salt formation occurs between the acidic and basic amino acid groups which increase the solubility of these compounds in aqueous solutions. Thus, R3 is selected from L-aspartic acid or L-glutamic acid and R4 is selected from L-lysine, L-arginine or L-ornithine. Through the use of minerals in the form of chelates containing

Amino acid salts It is possible to obtain liquid compositions which are stable after dilution in water, remaining in solution form and can be stored for long periods of time without formation of undesirable precipitates. Above all, it is possible to obtain liquid compositions with the above characteristics at concentrations of up to 15% mineral.

It is important to clarify that the liquid compositions described in this invention contain the mineral essentially in the form of amino acid chelates. This could only be achieved, as can be seen in the prior art, by combining amino acids with mineral in a stoichiometric amino acid: mineral ratio of less than 2: 1 and in such cases the products present in the compositions are characterized by having ions. inorganic compounds bound directly to the mineral.

More specifically, it is also very important to clarify that compositions already described in the prior art are characterized by containing substances which have inorganic anions attached directly to the mineral. For example, commercial or other products described in the state of the art are characterized by having an amino acid: mineral stoichiometric ratio of less than 2: 1 for bivalent minerals, which results in the formation of complexes represented by MYAA, where M represents the mineral. Y is usually an inorganic anion selected from chloride, sulfate, nitrate and phosphite and phosphate or an organic anion selected from formates, acetates, among other organic acids and AA represents one of the naturally occurring amino acids or protein hydrolysates described above.

In other cases, the compositions described in the state of the art are characterized by a simple mixture of salts of minerals with amino acids. In such cases it is possible to use amino acid: mineral stoichiometric ratios of 2: 1 or greater, keeping the compositions stable since they are simple mixtures of their components, although commercial products are commonly prepared with significantly lower amounts of amino acids or protein hydrolysates than necessary to achieve this relationship. In such cases, the salts are selected from chlorides, sulfates, nitrates or other organic salts and the pH values of the fertilizer compositions are low and compatible with the solution pH values of the selected inorganic or organic salt. In general, artisans prepare fertilizer compositions using salts having pH values in aqueous solutions of less than 4, and more specifically salts having pH values ranging from 1 to 3, which are also the pH values of compositions containing them, which make them easily differentiable from the liquid fertilizer compositions object of this invention.

In another aspect, the compositions object of the invention have pH values greater than 4.0. Generally, the pH values of the compositions object of the invention may range from 4.5 to 11 and preferably from 5 to 10 and more preferably from 6 to 9. Thus, it is apparent to those skilled in the art. It is known in the art that the subject compositions of the invention are not mixtures of inorganic or organic salts of the mineral of interest with amino acids and, in turn, consist of aqueous solutions of minerals in the form of amino acid chelates prepared with amino acid salts containing, where desired, another amino acid of interest in a stoichiometric amino acid: mineral ratio of 2: 1 or greater.

In another aspect, the compositions object of the invention contain sufficient inorganic or organic anions only for the formation of the aforementioned salts of lysine or arginine. These anions can be selected from chloride, sulfate, hydrogen sulfate, nitrate, phosphate, phosphite, acetate, gluconate, tartrate, citrate, among other organic or inorganic anions. In yet another aspect, the compositions object of the invention contain inorganic or organic cations in sufficient quantity for the formation of the previously described salts of L-aspartic acid or L-glutamic acid. These cations may be selected from ammonium, sodium, potassium or protonated primary, secondary or tertiary amines.

Thus, it is established that inorganic or organic anions or cations should be present only in an amount sufficient for the formation of amino acid salts, ie amounts stoichiometrically less than or equal to the amount of lysine, arginine, L-aspartic acid and L acid. glutamic acids present in the composition so that they do not exist in larger quantities than set forth herein. Using such determined amounts, formation of salts or complexes resulting from the binding of these anions directly to the minerals present in the compositions is impossible. However, when ammonia is used for the formation of the amino acid salts of interest, there may be an excess over the amount of L-aspartic acid or L-glutamic acid, if desired, as nitrogen coordinates in the metal through valence orbitals by covalent bonds.

Higher concentrations of mineral in the compositions object of

The invention can be achieved by combining it with other sources of the same mineral, such as chlorides, sulfates, nitrates, other organic salts or combinations thereof. However, liquid fertilizer compositions prepared in this way are not desirable since such mineral salts have low agronomic efficacy and the levels achieved with the compositions of interest are suitable for the proposed purpose.

In another aspect of this invention, the liquid compositions of interest may be prepared according to one of several forms described in the prior art. One method may be to dilute previously prepared chelates of the invention until the desired mineral concentration is reached. In other cases, liquid fertilizer compositions may be prepared by reacting a source of the mineral with lysine, arginine, L-aspartic acid or L-glutamic acid or their salts and another amino acid in an amino acid: mineral ratio at least equal to. 2: 1. Mineral sources are selected from oxides, hydroxides, carbonates, sulphates, nitrates, phosphites and phosphates and preferably selected from oxides and hydroxides when possible.

Irrespective of the mineral source selected, if pre-preparation and isolation of the chelate and further dilution of the chelate is desired to adjust the planned concentration or by combining the mineral and amino acid sources directly in water, the starting materials should be reacted in a stoichiometric amino acid: mineral ratio of 2: 1 or more, with at least one equivalent of lysine, arginine, L-aspartic acid or L-glutamic acid or salts thereof and at least one equivalent of another amino acid being used the amount of mineral present in the composition. In the case of compositions prepared with L-aspartic acid or L-glutamic acid the starting materials are reacted at a stoichiometric amino acid: mineral ratio of 2: 1 or greater. Where preparation of the compositions of interest is desired directly by reaction of their components, this may be done at room temperature by simply combining the starting materials, provided that the stoichiometric relationships described in this invention are met.

Another object of the present invention is a method for administering minerals to plants. The compositions object of the invention have high stability, remaining soluble even when kept under low temperatures. The compositions are especially suitable for use as fertilizers for the treatment of agricultural crops, as they have high solubility when diluted with water, such as during the preparation of formulations to be applied to crop fields. After preparation, the compositions object of the invention can be used as fertilizers in different ways and can be applied to plants in the soil or through foliar application. Finally, the compositions of the invention may also be combined with other liquid leaf fertilizers prior to application to plants. When the use of the compositions is via foliar application, adjuvants may be added to improve the performance of the formulations, which are selected from adhesive spreading, pH reducing, defoaming, antifoaming, wetting, among others.

Fertilizers with which the compositions of this invention may be combined include any liquid containing at least one of the nutrients required for plants, which are selected from nitrogen, phosphorus, potassium, calcium, magnesium, sulfur, iron, manganese, copper, boron, molybdenum, chlorine or even zinc. The nutrients may be in the form of inorganic salts, chelates prepared with EDTA and similar compounds, lignosulfonates, or even as organic compounds such as urea. However, the liquid fertilizer compositions object of the invention are preferably used with other leaf fertilizers in the form of aqueous amino acid chelate solutions. The composition of the formulations to be applied to plants depends on the crop to be treated and the stage of plant growth, and various combinations of nutrients are possible for each particular case. The concentrations of minerals in the final formulations depend on their concentration in the soil where the crop is located and the plant species to be treated and are also determined according to the interest in each particular case. In still other cases, the compositions object of the invention may also be combined with herbicides, fungicides such as glyphosate, among others.

Another aspect of the inventiveness of the compositions is the presence of nitrogen in highly available forms by plants as it is in the form of a naturally occurring amino acid that can be metabolized as a nutrient. This reduces nitrogen requirements from other sources used as fertilizers, thereby reducing the costs of applying these nutrients. In addition, the compositions are especially suitable for use on agricultural crops classified as organic by the certifying bodies, as they consist of components approved as inputs for that product category,

Mentioned below are merely illustrative examples of preparation and use of the compositions of interest of this invention, once again emphasizing that they do not impose any limitation on the scope of the invention other than those set forth in the appended claims. Examples of plant treatment methods are also shown, and they should not be considered as limiting this invention either, as various variations can be practiced or performed by those skilled in the art in a variety of ways, it being understood that the mentioned examples have the purpose of description and not limitation. EXAMPLES Example 1

A fertilizer composition is prepared by reacting between 800 g of sodium hydroxide and 2,800 g of zinc sulfate heptahydrate at room temperature in 2.0 liters of water. Then 3,600 g of L-lysine hydrochloride are added and the solution is stirred for 30 min and the reaction medium cooled with an ice bath. After cooling, zinc chelate is crystallized and filtered off. 1,500 g of zinc chelate is hot dissolved in 3 liters of water to obtain a liquid composition containing 5% zinc w / w with Ph of 7.1 which can be used as a foliar fertilizer for plant treatment. . Example 2

A copper-containing composition is prepared by reacting between 1.8 kg L-lysine hydrochloride, 0.75 kg glycine and 2.0 kg copper sulfate and 0.45 kg calcium oxide at room temperature in 3, 0 kg of water. After the process, the salt is filtered off and a liquid composition containing 10% copper w / w is obtained which can be used as a foliar fertilizer for the treatment of plants with Ph of 7.6. Example 3

A manganese-containing composition in the form of L-arginine sulphate chelate is prepared by reaction between 0.4 kg L-arginine, 1.5 kg sodium aspartate and 1.5 kg manganese sulfate under reflux for 4 h. . After cooling the solution, the chelate obtained is separated by filtration. A liquid composition containing 5% manganese w / w, which can be used as a foliar fertilizer for the treatment of plants with Ph of 6.7, is prepared by dissolving 0.6 kg of L-arginine sulfate chelate. previously obtained in 0.8 kg of water. Example 4

A calcium-containing composition in the form of lysine hydrochloride chelate is prepared by the reaction between 1.8 kg L-lysine sulfate, 0.7 kg glycine and 0.5 kg calcium oxide at room temperature at 1.5 kg of water. After the process a liquid composition containing 8% calcium w / w is obtained which can be used as a foliar fertilizer for the treatment of plants with Ph equal to 8.7. Example 5

A magnesium chelate containing composition of lysine hydrochloride chelate is prepared by the reaction between 1.8 kg L-lysine hydrochloride, 0.7 kg glycine, 0.4 kg sodium hydroxide and 1.2 kg water. . After holding for 2 h, the salt formed is filtered and 1.1 kg of magnesium chloride is added to the obtained solution. The mixture is kept under stirring for 45 min until a solids free solution is obtained. After the process a liquid composition containing 5% magnesium w / w is obtained which can be used as a foliar fertilizer for the treatment of plants with Ph of 7.9. Example 6

A manganese-containing composition in the form of potassium L-aspartate chelate is prepared by reaction between 2.6 kg L-aspartic acid and 1.1 kg potassium hydroxide. After reacting for 1 h under reflux, 1.7 kg of 31% manganese sulfate is added at room temperature dissolved in 5.0 kg of water. The obtained solution is cooled and the manganese chelate is filtered and dried. 1.0 kg of this manganese chelate is hot dissolved in 1.8 kg of water to obtain soluble at room temperature and has 5% w / w manganese. Example 7

A cobalt-containing composition in the form of potassium L-glutamate chelate is prepared by the reaction between 2.9 kg L-glutamic acid, 0.75 kg cobalt chloride, 1.3 kg potassium hydroxide 85% at 80 ° C. ° C in 1.9 kg of water. After complete dissolution of the solids, the reaction mixture is kept at rest and the chelate formed is crystallized in an ice bath. 500 g of cobalt chelate is dissolved in water to obtain a liquid composition containing 8% cobalt w / w which can be used as a foliar fertilizer for the treatment of plants with a pH of 9.1. Example 8

A fertilizer formulation for foliar application in a creeping tomato crop using equipment with a storage capacity of 1000 liters of syrup, which is set at a flow rate of 400 liters / hectare, is prepared by diluting 15 liters of the composition prepared according to with example 2 in 1,000 liters of water. Subsequently, the application is performed until the tank tank solution in the desired area is exhausted.

Claims (24)

1.) - "LIQUID FERTILIZING COMPOSITIONS," characterized in that they have pH values ranging from 4 to 11 and preferably from 5 to more preferably from 6 to 9 and comprise water and at least one mineral chelate prepared with salts. of lysine or arginine according to the formula: where M is selected from zinc, copper, iron, cobalt, nickel, manganese, calcium, magnesium or combinations thereof. R1 is equal to (CH2) 4NHs + -X "or (CH2) 3NHCNH2NH2 + .X-, where X- is an anion selected from chloride, hydrogensuitate, suirate, nitrate, rosite, phosphate, acetate, citrate, gluconate, salicylate, salts fulvic acid, tartrate and preferably chloride or sulfate R2 is equal to H or any side chain of a naturally occurring α-amino acid in its L-, D- or D, L enantiomeric forms representing alanine, phenylalanine, leucine, isoleucine, proline, hydroxyproline, arginine, methionine, valine, threonine, isotreonine, histidine, tryptophan, serine, glutamine and preferably H. 2.) - "LIQUID FERTILIZING COMPOSITIONS", characterized in that they have pH values ranging from 4 to 11 and preferably from 5 to 10 and more preferably from 6 to 9 and comprise water and at least one prepared mineral chelate. with salts of L-aspartic acid or L-glutamic acid according to the formula: where M is selected from zinc, iron, cobalt, nickel, manganese, calcium, magnesium or combinations thereof. R1 is equal to (CH2) COO -Y + "or (CH2) 2COO - Y +, where Y + represents a cation selected from ammonium, sodium, potassium or primary, secondary or tertiary amines, and preferably ammonium or potassium. R2 is equal to H or any side chain of a naturally occurring α-amino acid in its enantiomeric forms L-, D- or D, L which represents alanine, phenylalanine, leucine, isoleucine, proline, hydroxyproline, methionine, valine, threonine isotreonine, histidine, tryptophan, serine, glutamine, and preferably H. 3.) - "LIQUID FERTILIZING COMPOSITIONS", characterized by having pH values ranging from 4 to 11 and preferably from 5 to more preferably from 6 to 9 and comprising water and at least one mineral chelate prepared with salts. L-aspartic acid or L-glutamic acid according to the formula: M is selected from zinc, iron, cobalt, nickel, manganese, calcium, magnesium or combinations thereof. R 1 and R 2 are equal to (CH 2) COO - Y + - or (CH 2) 2 COO - Y +, where Y + represents a cation selected from ammonium, sodium, potassium or primary, secondary or tertiary amines, and preferably ammonium or potassium. 4.) - "LIQUID FERTILIZING COMPOSITIONS", characterized by having pH values ranging from 4 to 11 and preferably from 5 to more preferably from 6 to 9 and comprising water and at least one amino acid prepared chelate containing basic functional groups and acids according to the formula: <formula> formula see original document page 22 </formula> M is selected from zinc, copper, iron, cobalt, nickel, manganese, calcium, magnesium or combinations thereof. R1 is equal to (CH2) COOH or (CH2) 2COOH R2 is equal to (CH2) 4NH2, (CH2) 3NH2 or (CH2) 3NHCNHNH2. 5.) - "LIQUID FERTILIZING COMPOSITIONS", characterized by having pH values ranging from 4 to 11 and preferably from 5 to e, more preferably from 6 to 9 and consisting of: ίο 2 to 15 parts of a mineral and preferably from 3 to 12 parts of mineral and more preferably from 5 to 10 parts of a mineral. to 42 parts of lysine salts and preferably 22 to 38 parts of lysine salts and more preferably 25 to 30 parts of lysine salts. 5 to 40 parts of a naturally occurring α-amino acid selected from glycine or lysine, alanine, phenylalanine, leucine, isoleucine, proline, hydroxyproline, arginine, methionine, valine, threonine, isotreonine, histidine, tryptophan, serine, glutamine in their forms L-, D- or D, L- enantiomers are preferably from 8 to 40 parts of the α-amino acid and more preferably from 10 to 40 parts of the α-amino acid or salts thereof. 9 to 90 parts water and preferably from 15 to 80 parts water and more preferably 40 to 75 parts water. 6.) - "LIQUID FERTILIZING COMPOSITIONS", characterized in that they have pH values ranging from 4 to 11 and preferably from 5 to 10 and more preferably from 6 to 9 and consisting of: 2 to 15 parts of a mineral and preferably from 3 to 12 parts of a mineral and more preferably from 5 to 10 parts of a mineral. 5 to 50 parts of arginine salts and preferably 20 to 40 parts of arginine salts and more preferably 25 to 40 parts of arginine salts or salts thereof. -5 to 25 parts of a naturally occurring α-amino acid selected from Glycine or Plant, alanine, phenylalanine, leucine, isoleucine, proline, hydroxyproline, arginine, methionine, valine, threonine, isotreonine, histidine, tryptophan, serine, glutamine enantiomeric forms L-, D- or D1L- and preferably from 6 to 25 parts of α-amino acid and more preferably from 8 to 25 parts of α-amino acid. 5 to 90 parts water and preferably 10 to 85 parts water and more preferably 35 to 70 parts water. 7.) - "LIQUID FERTILIZING COMPOSITIONS", characterized in that they have pH values ranging from 4 to 11 and preferably from 5 to -10 and more preferably from 6 to 9 and consisting of: -2 to 15 parts of a mineral and preferably from 3 to 12 parts of mineral and more preferably from 5 to 10 parts of a mineral. 10 to 65 parts of L-aspartic acid salts and preferably from 15 to 60 parts of L-aspartic acid salts and more preferably from 20 to 60 parts of L-aspartic acid salts. 9 to 90 parts of water and preferably 25 to 90 parts of water and more preferably 30 to 80 parts of water. 8.) - "LIQUID FERTILIZING COMPOSITIONS", characterized in that they have pH values ranging from 4 to 11 and preferably from 5 to -10 and more preferably from 6 to 9 and consisting of: -2 to 15 parts of a mineral and preferably from 3 to 12 parts of mineral and more preferably from 5 to 10 parts of a mineral. 10 to 60 parts of L-glutamic acid salts and preferably 15 to 60 parts of L-glutamic acid salts and more preferably 20 to 55 parts of L-glutamic acid salts. 9 to 90 parts of water and preferably 25 to 90 parts of water and more preferably 30 to 80 parts of water. 9.) - "LIQUID FERTILIZING COMPOSITIONS", characterized by having pH values ranging from 4 to 11 and preferably from 5 to -10, more preferably from 6 to 9 and consisting of: -2 to 15 parts of a mineral and preferably from 3 to 12 parts of mineral and more preferably from 5 to 10 parts of a mineral. 10 to 72 parts of L-aspartic acid salts and preferably from 10 to 60 parts of L-aspartic acid salts and more preferably from 20 to 50 parts of L-aspartic acid salts. -5 to 25 parts of a naturally occurring α-amino acid selected from glycine or alanine, phenylalanine, leucine, isoleucine, proline, hydroxyproline, methionine, valine, threonine, isotreonine, histidine, tryptophan, serine, glutamine in their enantiomeric forms. D- or D, L- is preferably from 5 to 20 parts of the α-amino acid and more preferably from 6 to 20 parts of the α-amino acid. 9 to 90 parts of water and preferably from 10 to 75 parts of water and more preferably 30 to 80 parts of water. 10.) - "LIQUID FERTILIZING COMPOSITIONS", characterized in that they have pH values ranging from 4 to 11 and preferably from 5 to -10 and more preferably from 6 to 9 and consisting of: -2 to 15 parts of a mineral and preferably from 3 to 12 parts of mineral and more preferably from 5 to 10 parts of a mineral. 10 to 72 parts of L-glutamic acid salts and preferably from 10 to 60 parts of L-glutamic acid salts and more preferably from 20 to 50 parts of L-glutamic acid salts. -5 to 25 parts of a naturally occurring α-amino acid selected from glycine or alanine, phenylalanine, leucine, isoleucine, proline, hydroxyproline, methionine, valine, threonine, isotreonine, histidine, tryptophan, serine, glutamine in their enantiomeric forms. D- or D, L- is preferably from 5 to 20 parts of the α-amino acid and more preferably from 6 to 20 parts of the α-amino acid. 5 to 90 parts water and preferably from 10 to 75 parts water and more preferably 30 to 80 parts water. 11.) - "LIQUID FERTILIZING COMPOSITIONS", characterized in that they have pH values ranging from 4 to 11 and preferably from 5 to -10 and more preferably from 6 to 9 and consisting of: -2 to 15 parts of a mineral and preferably from 3 to 12 parts of mineral and more preferably from 5 to 10 parts of a mineral. -5 to 49 parts of an amino acid and preferably 10 to 38 parts of an amino acid and more preferably 15 to 30 parts of an amino acid, the amino acid being selected from lysine, arginine or ornithine. -5 to 40 parts L-aspartic acid or L-glutamic acid and preferably 7 to 35 parts of L-aspartic acid or L-glutamic acid and more preferably 10 to 35 parts of L-aspartic acid or L-glutamic acid. 9 to 90 parts water and preferably 25 to 70 parts water and more preferably 30 to 60 parts water. 12.) "LIQUID FERTILIZING COMPOSITIONS" according to claims 5, 6, 9, 10 and 11, characterized by a mineral selected from zinc, copper, iron, cobalt, nickel, manganese, calcium, magnesium or combinations thereof . 13.) - "LIQUID FERTILIZING COMPOSITIONS" according to claims 7 and 8, characterized by a mineral selected from zinc, iron, cobalt, nickel, manganese, calcium, magnesium or combinations thereof. 14.) "LIQUID FERTILIZING COMPOSITIONS" according to claims 5 and 6, characterized by salts of lysine and arginine selected from hydrochloride, sulfate, acetate, formate, citrate, lactate, tartrate, gluconate, salicylate, fulvic acid salt and preferably lysine or arginine hydrochloride. 15.) "LIQUID FERTILIZING COMPOSITIONS" according to claims 7 to 10, characterized by salts of L-aspartic acid or L-glutamic acid selected from salts of ammonium, sodium, potassium or primary, secondary or tertiary amines. and preferably L-aspartic acid or L-glutamic acid ammonia. 16.) - "LIQUID FERTILIZING COMPOSITIONS", characterized by having pH values ranging from 4 to 11 and preferably from 5 to -10 and more preferably from 6 to 9 and consisting of: -2 to 15 parts of zinc and preferably from 3 to 12 parts of zinc and more preferably from 5 to 10 parts of zinc. From 10 to 42 parts of lysine hydrochloride and preferably from 20 to 40 parts of lysine hydrochloride and more preferably from 20 to 30 parts of lysine hydrochloride. -5 to 34 parts of a naturally occurring α-amino acid selected from glycine or others in its L-, D- or D1L- enantiomeric forms and preferably from 9 to 28 parts of the α-amino acid and more preferably from 10 to 25 parts of the α-amino acid. -9 to 90 parts water and preferably from 10 to 85 parts water and more preferably 30 to 60 parts water. 17.) "LIQUID FERTILIZING COMPOSITIONS" according to any one of claims 1 to 16, characterized in that they contain preservatives, surfactants, spreaders, adhesives, defoamers, anti-drift, wetting agents or combinations thereof. 18.) "PREPARATION PROCESS" according to any one of claims 1 to 17, characterized in that a chelate formed by the coordination of a mineral with at least two molar equivalents of amino acids or their salts with respect to the mineral is dissolved in water. 19.) "PREPARATION PROCESS" according to any one of claims 1 to 17, characterized in that the aqueous phase is reacted with a naturally occurring mineral source and amino acids or their salts in amounts not less than two molar equivalents of excess. relation to the mineral. 20.) "PREPARATION PROCESS" according to claims 18 and -19, characterized by a mineral source selected from oxides, hydroxides, carbonates, inorganic or organic salts of zinc, copper, iron, cobalt, nickel, manganese, calcium or magnesium. 21. "PREPARATION PROCESS" according to claims 18 and -19, characterized by amino acids selected from lysine, glycine, alanine, phenylalanine, yucine, isoleucine, proline, hydroxyproline, arginine, ornithine, methionine, aspartic acid, glutamic acid, valine, threonine, isotreonine, histidine, tryptophan, serine and glutamine. 22.) - "PLANT TREATMENT METHOD" according to any one of claims 1 to 17, characterized by application to the leaves of the plants in the soil or roots by means of processes selected from foliar application, fertigation and hydroponics. a liquid composition containing at least one mineral chelate prepared with amino acids. 23.) "Plant treatment method" according to Claim 22, characterized by the application of effective amounts of compositions corresponding to mineral contents ranging from 0,01 to -1,000 g per hectare of crops. 24.) "Plant treatment method" according to Claims 22 and 23, characterized in that the compositions are applied in combination with other nutrients selected from nitrogen, phosphorus, potassium, calcium, magnesium, sulfur, iron, manganese, copper, zinc, molybdenum, chlorine, boron or mixtures thereof in any proportion.