SK1172016U1 - The liquid fertilizers containing trace biogenic elements and the use of them - Google Patents

Abstract

Described are liquid fertilizers which contain the products of the reactions of at least one of the cations including zinc, manganese, copper, and iron with sulfurates. Of the biogenic cations, zinc and ammonium sulphate (NH4) 2S2O3 have proved to be particularly suitable. The liquid concentrates of the biogenic elements are characterized by a significantly higher concentration of trace plant nutrients contained therein, as well as the presence of sulfur in plants in a particularly well-acceptable form. Liquid fertilizers can be used for fertilization into the soil, but are particularly suitable for foliar plant nutrition.

Description

Technical field

The present invention relates to liquid fertilizers containing trace biogenic elements containing reaction products of at least one of the cations including zinc, manganese, copper and iron with sulphates, the so-called " tisíranmi. For the preparation of liquid fertilizers according to the solution, it is particularly advantageous to use ammonium and / or potassium sulphate. Liquid fertilizers in the sense of the solution can be used for fertilization to the soil, but are particularly suitable for foliar - leaf nutrition of plants.

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 many 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 100 times less microelements compared to macroelements (nitrogen, phosphorus, potassium and sulfur).

Each biogenic element must be present in the culture medium of the plant 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 as a result of which a dative bond is formed. The central ions are most often cations, the ligands being anions or neutral molecules of a dipolar nature.

Sulfates, also referred to as thiosulfates or hyposulfites, are salts of thiosulphuric acid, H2S2O3, which is unstable in the pure state and has so far been prepared only in a weak solution. It can be considered as a derivative of sulfuric acid, derived by the fact that one oxygen in its molecule is replaced by sulfur and is therefore called thiosulphuric acid ("sulfuric sulfuric acid") and its salts as thiosulphates i.e. thiosulfates.

Sulfates are usually produced by:

• by combining sulfites with elemental sulfur, • by oxidizing polysulphides - polysulfides in aqueous solution, • by reacting sulfur dioxide into a solution of the respective sulfide.

The combination of sulphites with sulfur is similar to the oxidation of sulphites with oxygen, which binds to the free electron pair of sulfur. Sulfates are decomposed by the action of acids, releasing sulfur dioxide and sulfur in the form of so-called. of sulfur milk. Sulfates have significant reducing effects - they are easily oxidized (used for example as "antichlorine" - to remove chlorine, eg when bleaching textiles). In addition to the alkaline thiosulfates are highly water-soluble also hyposulphite, ammonium - (NH 4) 2 S ₂ O _3rd Especially the high solubility of potassium sulphite - K2S2O3 and the already mentioned ammonium sulphate are the basic prerequisites for the preparation of liquid type fertilizers, which are sources of assimilable sulfur plants.

Sulfur is currently considered to be the fourth essential plant nutrient, since the effect of sulfur on plants is significant and irreplaceable in plant physiology. Among the many sulfur functions we can mention:

• Sulfur is irreplaceable in achieving cereal quality parameters • Increases oil content in oilseeds • Increases chlorophyll content in green parts of plants • Provides better assimilation and storage of sugar • Promotes cereal branching and rape branching • Like phosphorus affects the generation of generative organs, • positively affects nitrogen metabolism, • acts to reduce nitrate content, which is particularly important in vegetable cultivation, • positively affects phosphorus uptake.

In the 1970s, sulphites, when applied to soil, have been shown to inhibit processes that cause unwanted changes in nitrogen forms (soil urease and nitrification). The efficacy of this inhibitory action of sulphites has recently been demonstrated and confirmed by Italian agrochemists (Agrcultural Sciences, 2015, 6, 1502 1512).

From the viewpoint of agrochemistry, the ability of sulphites-thiosulphates to form complex salts from some metal cations is also important. This property was used a few years ago, for example, in the classical process of photography based on the use of silver halides - removing unreduced silver - undecomposed halide salt from a photographic plate, film or paper. When dissolving the silver halide in a sulphate solution, initially, only a slightly soluble silver sodium sulphate (thiosulphate) is formed, according to the scheme:

AgBr + Na ₂ S ₂ O ₃ - + NaBr + NaAgS ₂ O ₃ .

Subsequently, however, the sulphate reacts to a well-soluble complex salt of silver-thiosulfate, or complex tritiosulfathioiones of the - (Ag (S ₂ O ₃ ) ₃ ) type, according to the considerably simplified reaction scheme:

NaAgS ₂ O ₃ + In ₂ S2O ₃ -> Na 4 / Ag 2 (S ₂ O _{3) 3} /.

It is noteworthy that only normal salts are known from thiosulphuric acid, i. salts in which both hydrogen atoms are replaced by cations, and also the fact that, unlike the highly volatile acid, most of its salts are substantially stable in aqueous solution.

The essence of the technical solution

It has now been found that the production of reaction products of at least one of the cations of trace biogenic elements, including zinc, manganese, copper and iron with sulphates, can be utilized in the preparation of liquid fertilizers characterized by a high content of assimilable sulfur plants.

The ability of sulphites-thiosulphates to form complex compounds with heavy metals is used in the preparation of liquid fertilizers of this type. The formation of complex compounds with cations of trace biogenic elements is a prerequisite for achieving higher plant utilization. The advantage is that the complexing anion is also a source of a significant biogenic element - sulfur, and the use of sulfur sulphate in connection with the cultivation of plants brings many other advantages.

It has been shown experimentally that the products of the chemical reactions of the sulphate anion with iron, zinc, manganese and copper cations are characterized by the necessary stability while allowing the preparation of liquid fertilizers with an unusually high concentration of trace plant nutrients. It has been confirmed that liquid-type liquid fertilizers with sufficient phase stability at temperatures below 0 ° C can also be prepared on this basis. Remarkably, the mixed solutions containing the reaction products of the sulphate anion with the cations of the biogenic micronutrients in question are stable even in a neutral to weakly acidic environment (at pH £ 7), where simple salts of most sulphites usually already undergo decomposition associated with elemental sulfur release. colloidal sulfur solutions, so-called sulfur milk).

In this context, the stability of the products of the reactions of the sulfonate (thiosulfate) anion with zinc cations is particularly noteworthy.

For production and economic reasons, it seems to be particularly advantageous to use as a source of sulphate anion or ammonium sulphate (NH4) 2S2O3 or potassium sulphate - K2S2O3 in the preparation of liquid fertilizers in terms of solution. Both of these thiosulphates are characterized by very good solubility in water (they allow the preparation of aqueous solutions containing more than 50% by weight of salt in solution, while maintaining sufficient phase stability even at temperatures below 0 ° C), plants in a well acceptable form - nitrogen, respectively. potassium.

The advantage of liquid fertilizers in the sense of the solution is also the fact that they enable the preparation of multi-component mixtures even without the use of more difficult and especially economically demanding complex sources of micronutrients. In their preparation, conventional inorganic salts of iron, zinc, manganese and copper, such as their nitrates or sulphates, can advantageously be used.

Liquid fertilizers in the sense of the solution can be used for fertilization into the soil, but it is particularly advantageous to use them for foliar - leaf nutrition of plants.

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 verify the possibility of preparing a liquid fertilizer of the solution fertilizer according to a solution that would be a source of chloride-free potassium, sulfur and zinc, the following was done.

902.2 kg of a concentrated aqueous solution of potassium sulphite (thiosulphate) containing 50.5 wt. % K2S2O3.

While stirring, 97.8 kg of zinc sulfate monohydrate, ZnSO 4 .H 2 O, containing min. 35 masses. % zinc (as Zn). Due to the gradual dissolution of the zinc salt, the pH gradually decreased from the initial value of 10.26 / 23.7 ° C to a virtually neutral pH; 6.57 / 30.3 ° C.

The prepared liquid fertilizer, which had the character of a practically clear solution, contained 22.6 wt. % potassium (as K 2 O) in chlorine free form, 15.3 wt. % sulfur (as S) and more than 3.4 wt. % zinc (as Zn).

The liquid fertilizer thus prepared, according to the solution, was used for basic fertilization of the soil under corn.

Example 2

In order to prepare a liquid fertilizer - concentrate, intended for foliar fertilization of the maize plant containing nitrogen, sulfur and zinc, the procedure was as follows.

838.3 kg of a concentrated aqueous solution of ammonium sulphate (thousand) containing about 60 wt. % (NH ₄₎ 2S2O _third The aqueous sulphate solution used only smelled slightly of ammonia, was clear, had only a weakly basic chemical reaction (pH: 8.16 / 24.0 ° C) and contained about 12 masses. % nitrogen (as N) and about 26 wt. % sulfur (as S).

Next, while stirring gradually added a total of 161.7 kg of zinc sulfate monohydrate, _ZnSO4 .H2O. During the addition and dissolution of the sulphate, the pH of the mixed mixture gradually decreased, with the undiluted liquid fertilizer prepared having a weakly acidic chemical reaction (pH: 4.52 / 28.8 ° C). The prepared liquid type fertilizer contained more than 10 wt. % nitrogen (as N), 21.8 wt. % sulfur (as S) and 5.66 wt. % zinc (as Zn).

The prepared liquid fertilizer, according to the solution, after dilution with water in the ratio of 1:20 was applied in a dose of 6 liters of concentrate per hectare foliar applied to the maize crop.

Example 3

In order to prepare a liquid fertilizer, according to the solution, containing nitrogen, sulfur, manganese and copper, intended for off-root cereal nutrition, the procedure was analogous to Example 2. 960 kg of concentrated aqueous ammonium sulphate solution containing about 60 wt. % Of salt was gradually added with stirring 30 kg of manganese sulfate monohydrate, MnSO ₄ .H2O containing about 32 materials. % manganese (as Mn) and 10 kg of a concentrated aqueous solution of copper nitrate containing about 41 wt. % Cu (NO 3) 2.

In this way, about 1000 kg of liquid fertilizer was prepared in the sense of a solution containing more than 12 wt. % of total nitrogen in ammoniacal and nitrate forms, about 25 wt. % sulfur (as S), about 1 wt. % manganese (as Mn) and 0.14 wt. % copper (as Cu). The prepared liquid fertilizer after dilution with water in a volume ratio of 1:20 was in doses of 5 and 5, respectively. 3 liters applied by spraying on cereal leaves. The first application was carried out at the end of the harvesting at a dose of 5 liters. The second application of the liquid fertilizer according to the solution, at a rate of 3 liters / ha, was carried out in the metering phase. While the first application was mainly to influence the formation of ears, the second was primarily to improve the baking properties of grain.

Example 4

In order to prepare a liquid fertilizer, according to the solution, containing potassium, sulfur and iron, intended for the preventive and curative treatment of small fruit, the procedure was similar to that of Example 1. To a concentrated aqueous solution of potassium sulphite (thousand) containing about 50 wt. % of the salt was added with stirring, ferrous sulfate heptahydrate, so-called. green vitriol, FeSO ₄ .7H2O.

The prepared concentrated liquid fertilizer was diluted in a volume ratio of 1: 100 to 150 before spraying on the leaves of currants. In particular, the preventive protection of the currants against the manifestations of iron and sulfur deficiency was monitored.

Example 5

In the preparation of the liquid fertilizer for foliar fertilization of cereals, according to the solution, a mixed aqueous solution of ammonium sulphate with potassium sulphate was first prepared in a tank equipped with a stirrer. The blend solution consisted of 65 parts by volume of an aqueous ammonium sulphate solution containing about 60 wt. % (NH ₄ ) ₂ S ₂ O ₃ and 40 parts by volume of an aqueous potassium sulfite solution containing about 50 wt. % K2S2O3.

To 835 of the mixed sulphite solution thus prepared was further added with stirring 100 kg of urea and after dissolution of 40 kg of concentrated aqueous manganese nitrate solution containing about 200 g of manganese (as Mn) per liter, 15 kg of concentrated aqueous zinc nitrate solution containing approx. 200 g of zinc (as Zn) per liter and 10 kg of a concentrated aqueous solution of copper nitrate containing about 170 g of copper (as Cu) per liter. By thoroughly mixing the mixture, about 1000 kg of liquid fertilizer containing nitrogen, potassium, sulfur, manganese, zinc and honey were obtained. The fertilizer was applied by spraying, after dilution with water (approx. 1:50), to the barley in the seedling phase.

Claims (5)

PROTECTION REQUIREMENTS Liquid fertilizers containing trace biogenic elements, characterized in that they contain the products of the reactions of at least one of cations including zinc, manganese, honey and iron with silanes. Liquid fertilizers containing trace biogenic elements according to claim 1, characterized in that the cation source is sulphate and / or nitrate. Liquid fertilizers containing trace biogenic elements according to claim 1, characterized in that they contain zinc. Liquid fertilizers containing trace biogenic elements according to claim 1, characterized in that the sulphate is ammonium sulphate. Use of liquid fertilizers containing trace biogenic elements according to claim 1 for foliar plant nutrition.