SK7859Y1 - The concentrates of plant nutrients and their use - Google Patents

Abstract

Described are plant nutrient concentrates containing trace and/or secondary biogenic elements bound in the form of 2-hydroxypropane-1,2,3-tricarboxylic acid complexes, so called Citric acid, wherein at least one of the amines or hydroxyamines is used in their preparation. Of the amines, ethanolamine is the most suitable. Liquid concentrates of biogenic elements are characterized by a significantly higher concentration of the biogenic elements contained therein, as well as their better chemical and phase stability and are useful for foliar - leaf - nutrition of plants as well as the source of the respective nutrients in the preparation of multicomponent fertilizers.

Description

The invention relates to plant nutrient concentrates containing trace and / or secondary biogenic elements bound in the form of 2-hydroxypropane-1,2,3-tricarboxylic acid complexes, so-called. citric acid, wherein at least one of the amines or hydroxyamines is used in their preparation. The concentrates are advantageously useful for foliar-nutrition of plants and also as a source of relevant nutrients in the preparation of multi-component fertilizers.

BACKGROUND OF THE INVENTION

Plants consist of the same elements as inanimate nature, while the formation of plant matter is the result of complex transformations of substances from the environment surrounding plants and energy. The chemical analysis currently used has made it possible to detect more than 75 elements in plants, not all of which are equally important for plant life.

In terms of their content and importance for plants are most often divided into basic, sometimes also referred to as macroelements, secondary elements, trace elements. microelements, ultra-microelements and useful elements. The secondary elements usually include calcium (Ca), magnesium (Mg) and sometimes also sulfur (S), which is now usually included among the basic, so-called. building macroelements. Although a number of microelements are not closed, the critical trace elements include: iron (Fe), boron (boron), manganese (Mn), zinc (Zn), copper (Cu), molybdenum (Mo) and cobalt (Co).

Plants consume approximately 1000 times less microelements compared to macroelements (nitrogen, phosphorus, potassium and sulfur).

Each biogenic element must be present in the plant nutrient medium at a certain minimum dose, none of which is substitutable by another biogenic element. It may happen that the intake of a certain plant nutrient from the soil is so severely hampered due to the antagonism of the elements that the plant suffers from its deficiency. Nutrient uptake from soil is also significantly influenced by the chemical reaction (pH) of the growing substrate (soil).

In the case of intensive crop cultivation, the lack of secondary and trace elements may be a limiting factor in the crop and quality of the plants.

In order to increase the availability of some plant elements, it is preferred that they are bound in a complex form. A special type of complexes are the so-called. chelates formed by complexing reactions. In these reactions, so-called. the central atom, the electron shell of which is capable of receiving electrons, merges with the so-called particles. ligands having at least one free electron pair. Ligands therefore provide a central atom, respectively. ion electrons, resulting in a dative bond. The central ions are most often cations, the ligands being anions or neutral molecules of a dipolar nature.

Examples of complexing reactions include, but are not limited to:

oral ion ligand complex (Hydrogen) Fe 2+ + 6CN- -> / Fe (CN) 6/4 Co 2+ + 6NH ₃ -> · / Co (NH ₃ ) 6/2 + H + + H2O -> / H ₃ O / + Ni + 4 CO -> / Ni (CO) 4 /

The above reaction schemes represent the simplest complexing reactions. Some ligands, especially complex organic molecules, are capable of occupying multiple central atom coordination sites as they have several groups with free electron pairs. Such substances are commonly referred to as polydonor ligands. Reactions of polydonoric ligands with one central particle (metal ion) give rise to cyclic complexes, which are referred to as chelates.

The name chelate is derived from the Greek word 'che' - claw, since the central atom is bound in the cyclic complex by two or more bonds to the complexing-chelating agent (ligand) molecule than claws.

Chelates are used to increase the efficiency of supplying certain plant nutrients to an environment in which these are unacceptable or poorly acceptable under normal plant conditions. The chelate bond provides effective protection of the biogenic element forming the central atom in the complex from adverse environmental influences, whereby the plant can accept the complex-chelate element. Some plant nutrients are found naturally bound in chelates, with amino acids, polysaccharides, sulfur-containing high molecular weight substances, saponins, organic acids, polyhydric alcohols and the like usually being used as natural complexing compounds in plants and microorganisms.

Chelates are used in building chemistry, in the production of detergents for industry and households, in the food industry, as additives in the production of feed, in the purification of natural gas, in leather processing processes, in the electrical industry, in metal separation, in petrochemistry, in photographic processes, in the manufacture of printing inks and inks, in the production of pulp and in the textile industry and also in relation to plant nutrition - in agriculture.

SK 7859 Yl

In order to ensure the highest possible efficiency of mainly trace nutrients - microelements, the use of a wide range of complex compounds has been extended in agriculture. In addition to a number of complexing agents of native origin, such as citrates, lignosulfonates, various polysaccharides and saponins, chelating agents formed by a combination of amines and carboxylic acids - so-called. aminopolycarboxylates, known in the art as "APC". These form stable complexes with metal ions, the resulting complexes - chelates, are characterized by good stability over a wide temperature and pH range and are also inert in most chemical environments. Solution concentrates of zinc, copper and manganese based on chelates EDTA, whose production was realized at the end of the last century in Slovakia (Istrochem, Bratislava) contained about 3 wt. % of the biogenic element.

It can be seen from the above that, in addition to aminopolycarboxylates and lignosulfonates, citrate complexes of secondary and, in particular, trace plant nutrients have been most used in the production and agricultural practice. Their preparation is based on the reaction of biogenic metal cations with 2-hydroxypropane-1,2,3-tricarboxylic acid, wherein the acidity of the reaction mixture is adjusted by ammonia or one of the alkali metal compounds, usually potassium or sodium. In the Czech Republic, the production of liquid citrate concentrates of trace plant nutrients was gradually introduced in the 1980s (Zincocit, Kuprocit and others). In order to maintain the desired phase stability and chemical reaction (pH) of solution concentrates of this type, the concentration of the biogenic element in the formulation could not usually significantly exceed the six weight percent limit.

The essence of the technical solution

It has now been found that disadvantages in the preparation and use of complex bound secondary and / or trace elements containing biogenic elements in the form of citrate complexes can be overcome by using this solution.

The plant nutrient concentrates of the solution are characterized by containing reaction products of at least one of cations including zinc, manganese, iron, copper, calcium and magnesium with 2-hydroxypropane-1,2,3-tricarboxylic acid (3-carboxylic acid). 3-hydroxypentanedioic acid, C ₃ H ₅ O. (COOH) ₃ , the so-called citric acid) and with at least one amine or hydroxyamine.

It has been shown experimentally that by using amines or hydroxyamines to neutralize the reaction mixture, significantly higher phase and chemical stability of the thus prepared citrate complexes can be achieved, which makes it possible to prepare liquid concentrates of true clear solutions. The concentration of biogenic elements in the thus obtained liquid concentrates of the secondary and / or trace elements is significantly higher than usual for liquid concentrates of a comparable type.

A great advantage of the liquid concentrates according to the solution is that they are obtained in a concentrated liquid form in their preparation according to the solution, and the reaction product, which can advantageously be carried out in one technological step, is characterized by high phase and chemical stability.

From the point of view of the practical use of liquid concentrates in the context of the solution, it has proved to be particularly important if they contain at least one of the following central atoms: manganese (Mn), zinc (Zn), iron (Fe), copper (Cu), cobalt (Co), calcium (Ca) and magnesium (Mg).

Similarly, it was shown that it is advantageous to neutralize the acidic reacting mixture used ethanolamine (2-aminoethanol, monoethanolamine, colamine) NH ₂ .CH ₂ .CH ₂ · OH, C ₂ H ₇ NO, ethylenediamine (1,2-ethanediamine ) NH ₂ .CH ₂ .CH ₂ .NH _2, C ₂ H ₈ N _2, triethanolamine (HO.CH ₂ .CH _{2) 3} N, ₅ C6Hj NC) _3, and triethylamine (C ₂ H _{5) 3} N, C ₆ H ₁₅ N, diethanolamine HN (CH ₂ CH ₂ OH) ₂ , methylamine (aminomethane) CH ₃ NH ₂ .

Experimentally it has been shown that it is particularly advantageous to neutralize the reaction mixture used ethanolamine (2-aminoethanol, 2-amino-ethyl alcohol, monoethanolamine, colamine) NH ₂ .CH ₂ .CH ₂ .OH (CAS-No: 141-43- 5).

The use of said strongly basic reacting compounds has a synergistic effect on the stability of the resulting complex biogenic element compounds and the properties of the liquid concentrates of the invention.

Liquid concentrates according to the invention can have a practically neutral chemical reaction and are freely miscible not only with water but also with virtually all liquid fertilizers and in the form of application solutions also with almost all plant protection products. It has also been shown that liquid concentrates of this type are, after appropriate dilution, very suitable for off-root - foliar plant nutrition in the form of both preventive and curative applications of secondary and trace plant nutrients.

It is also expedient to use them as liquid intermediates in the preparation of multicomponent fertilizers, while allowing the preparation of liquid fertilizers of different composition and destination.

SK 7859 Yl

EXAMPLES

The following examples illustrate, demonstrate and demonstrate the practical application of the solution. However, they do not in any way limit its protection.

Example 1

In order to prepare a complex-bound zinc solution concentrate according to the invention, 27.34 kg of tap water were introduced into a reactor equipped with a stirrer, and 13.67 kg of chemically pure zinc oxide (ZnO pa) were gradually added under stirring. 36.41 kg of citric acid monohydrate, C 3 H ₅ O. (COOH) ₃ .H ₂ O, of technical purity, was then added to the thus prepared white thick suspension. Due to the addition of crystalline acid, the reaction mixture first cooled slightly (endothermic dissolution), but after a short time the temperature of the mixture began to rise gradually and became more pronounced fluid. The mixture had a strongly acidic chemical reaction (pH: 0.33 / 52.6 ° C) and had the appearance of an off-white suspension. After stirring the reaction mixture for about 10 minutes, 22.58 kg of so-called monoethanolamine were gradually added. of technical quality collagen containing min. 99.5% of active substance (2-aminoethanol).

As a result of the neutralizing heat released, the reaction mixture was heated considerably and its temperature was close to 95 ° C. During the addition of the monoethanolamine, the reaction mixture gradually clarified, reaching a virtually neutral chemical reaction (6.97 / 76.8 ° C). The product was a light brown, clear solution, and after cooling and reacting (on the second day after preparation) the reaction was weakly basic - the pH of the undiluted concentrate was 8.21 / 21.2 ° C.

The solution of zinc prepared according to the process according to the invention contained almost 11 wt. % zinc (as Zn) and 5.15 wt. % amidic nitrogen (as N) and was used for foliar fertilization of the silage maize crop.

Example 2

In order to prepare a complex concentrate of complex bound zinc and copper, the solution was similar to Example 1, with the exception that crystallized copper sulphate - CuSO ₄ .5H ₂ O was added to the prepared aqueous zinc oxide suspension. it contained more than 98% active substance (25% Cu and 12.6% S).

After stirring, a light blue colored suspension was obtained, to which crystalline citric acid and monoethanolamine were further added. The chemicals used were of similar quality to Example 1.

The following quantities of substances were used:

tap water ................................................ .. 22,51 kg, zinc oxide, ZnO ....................................... ..... 11.46 kg, crystalline copper sulfate. Blue vitriol .... 2.49 kg, crystalline citric acid ............................ 31.50 kg, monoethanolamine .. ............................................... 32.04 kg.

Approximately 100 kg of a zinc-copper solution complex was prepared as described above, having the character of a blue, viscous but free-flowing, clear basic reaction solution (pH after preparation 8.46 / 76 ° C). The prepared product contained 9.2 wt. % zinc (as Zn), 0.62 wt. % copper (as Cu) and 7.3 wt. % amide nitrogen (as N).

Example 3

The preparation of the complex-bound iron concentrate according to the invention was carried out analogously to Example 1, using water, citric acid and monoethanolamine of the same quality as described above. As the source of iron is used the technical ferrous sulfate heptahydrate, FeSO4.7H ₂ O (S Melstar - Melchem Holland), containing 94.6% of active ingredient (19 wt.% Fe, and 10.9 wt.% S).

When preparing about 100 kg of the concentrate in question:

26.04 kg of tap water,

22.38 kg of crystalline ferrous sulphate,

24.75 kg of crystalline citric acid and 26.83 kg of monoethanolamine.

After the addition of ferrous sulphate and citric acid, the reaction mixture had the appearance of an off-brown suspension, and by adding the first portions of monoethanolamine, the suspension began to clear until it finally became brown and of a solution nature. The mixture was allowed to cool gradually with stirring (from the original temperature of about 85 ° C), having a practically neutral chemical reaction at 28 ° C (pH: 7.28).

The iron concentrate prepared in this manner was used for the foliar treatment of fruit trees as a prevention against chlorotic manifestations due to iron deficiency.

SK 7859 Yl

Example 4

In order to prepare a complex bound zinc and manganese concentrate, according to the solution, intended primarily for curative but also preventive treatment of corn crop, the procedure was similar to the previous examples. 32 wt. % manganese (as Mn). In the preparation, manganese sulfate was added to the reaction mixture only after thoroughly homogenizing the mixture containing the aqueous suspension of zinc oxide with citric acid.

In the preparation of this liquid concentrate:

18.42 kg of tap water,

12.05 kg of zinc oxide,

35.95 kg of crystalline citric acid,

6.54 kg of manganese sulfate monohydrate and 27.04 kg of monoethanolamine.

As a result of the addition of monoethanolamine, the initially pale pink suspension, a strongly acidic chemical reaction (pH: 0.35 / 41 ° C), gradually changed its appearance and, after complete clarification, had the appearance of a light brown, relatively viscous, clear solution. The undiluted product prepared had a weakly basic chemical reaction (pH: 8.01 / 21.7 ° C).

The liquid concentrate thus prepared contained 9.7 wt. % zinc (as Zn) and more than 2 wt. % manganese (as Mn).

Example 5

The preparation of the liquid zinc-copper complex concentrate of the present invention was similar to that of the previous example, except that crystalline copper sulfate was used instead of manganese sulfate in the form of its pentahydrate.

The following amounts of reactants were used to prepare approximately 100 kg of concentrate:

24.73 kg of tap water,

13.57 kg of zinc oxide,

36.08 kg of crystalline citric acid,

2.26 kg of copper sulfate pentahydrate and 23.36 kg of monoethanolamine.

The liquid concentrate was blue-green in color and was a viscous, clear solution. It contained 10.9 wt. % zinc (as Zn), 0.56 wt. % copper (as Cu) and 5.3 wt. % amide nitrogen (as N).

Example 6

The preparation of the liquid complexed magnesium concentrate according to the invention was carried out by initially feeding an appropriate amount of crystalline citric acid into the aqueous suspension of MgO, MgO, while stirring. The acidic reaction mixture was then neutralized with triethanolamine (HO.CH ₂ .CH ₂ ) 3 N until a neutral reaction was obtained.

Example 7

The preparation of the liquid complex calcium complex concentrate according to this solution was similar to the previous example 6, except that calcium oxide in the form of so-called calcium oxide was used instead of magnesium oxide. Hydraulic lime for neutralization of acidic reacting the reaction mixture was used ethylenediamine (1,2-ethanediamine) NH ₂ .CH ₂ .CH ₂ .NH _second

PROTECTION REQUIREMENTS

Claims (4)

Crop nutrient concentrates containing trace and / or secondary biogenic elements bound in the form of 2-hydroxypropane-1,2,3-tricarboxylic acid complexes, characterized in that they contain reaction products of at least one of cations including zinc, manganese, iron, copper , calcium and magnesium with 2-hydroxypropane-1,2,3-tricarboxylic acid and at least one amine or hydroxyamine. Plant nutrient concentrates comprising trace and / or secondary biogenic elements bound in the form of 2-hydroxypropane-1,2,3-tricarboxylic acid complexes according to claim 1, characterized in that the hydroxyamine is ethanolamine. Use of plant nutrient concentrates according to claim 1 for foliar plant nutrition. Use of plant nutrient concentrates according to claim 1 as a source of biogenic elements in the preparation of multi-component fertilizers. End of document