SK7055Y1 - Nutrition preparations for plants - Google Patents

Abstract

Preparations intended for plant nutrition containing calcium and/or magnesium contain at least one of calcium and/or magnesium salts of carboxylic acids of type R-COOH, wherein R is hydrogen cation or methyl group, where at least 0,1 and maximum 55 parts of weights of the mentioned salts is in 100 parts by weight of the preparation. The preparation contain 45 to 99,9 parts by weight at least one of the components involving water, carboxylic acid, inorganic compounds containing calcium and/or magnesium, urea, an additive regulating rheological properties and stability of the liquid preparation. In addition to calcium and/or magnesium the preparations can contain also basic nutrients, next nutrients from secondary plant nutrients, trace elements, growth stimulators or pesticides.

Description

The present invention relates to liquid plant nutrients containing calcium and / or magnesium which are intended to preventively and curatively eliminate the deficiency of these secondary plant nutrients, in particular in the form of extracorporeal foliar nutrition, but also in connection with the use of certain special plant nutrition methods.

BACKGROUND OF THE INVENTION

Calcium (Ca) is one of the elements without which the life of plants is not possible. Calcium in the Earth's crust (to a depth of about 16 km) is the highest of all plant nutrients. Calcium is a constituent of many minerals, particularly aluminosilicates, carbonates and phosphates.

Mineral weathering releases mainly in the form of bicarbonate - Ca (HCO ₃ ) ₂ , where the rate of weathering depends on the level of precipitation and also on the formation of hydrogen cations and carbon dioxide content in the atmosphere and soil. The hydrogen cations formed by dissociation can release calcium cations in the weathering process, with two hydrogen cations being replaced by one divalent calcium cation. The decomposition of organic materials increases the formation of carbon dioxide in the soil solution, forming carbonic acid. In this way, it is possible to explain why due to the fertilization with organic materials, the weathering of calcium minerals in the soil increases. Nitrogen compounds contained in the soil solution also play an important role in these weathering processes, since hydrogen cations are also formed during nitrification processes to a greater extent than in the case of dissociation of the already mentioned carbonic acid. Similarly, sulfur compounds, such as emissions from the combustion of fossil fuels, also contribute to the weathering of calcium minerals. The calcium content of the plant dry matter is usually in the range of 5 to 30 mg Ca per gram (Mengel, K.-Kirkby, EA: Principles of Plant Nutrition, Intemational Potash Institute, Bern, Switzerland 1987). Although the proportion of calcium in the soil solution is usually up to 10 times higher than that of potassium, the amount of calcium taken up by plants is often lower than that of potassium. This may also be related to the fact that the plants only absorb calcium through young root peaks, and its uptake is also inhibited by the presence of other ions in the soil solution.

In the absence of calcium there are symptoms of disorders that weaken the whole plant. The need for calcium in higher plants begins to manifest itself already in the earliest stages of development - in the period of seed germination. In a severe calcium deficiency, the germinating plants begin to wither before the seeds are depleted and the plants die. Calcium is of great importance in balancing the physiological equilibrium of the soil solution, especially when various other cations predominate unilaterally. It dampens the harmful effects of elements that increase the acidity of the environment and allows plants to take better nutrients. The presence of sufficient calcium in the soil solution is also indispensable for the normal development of the root system - especially in an acidic environment. In plant life, calcium also plays an important role in detoxifying physiological conversion products, especially oxalic acid. In the absence of calcium, oxalic acid is bound exclusively to potassium, accumulates in the form of potassium oxalate and acts poisonously to the plants.

One symptom of calcium deficiency is the typical fading of plant tops and young leaves. Newly formed sheets are small, coiled and often also have irregular edges. Spots of dead tissue appear on these sheets. With a strong and long-lasting lack of calcium, the growth peak dies completely. After its death, new young shoots are formed, which later also die. In cereals, the young leaves gently twist and then dry. Later, we observe a gradual drying of the leaves from the top, even older leaves.

In sunflowers, flax, peas and some other plants, we observe the tops of the stems and leaf stalks breaking. Lupins and corn in the calcium deficit have frayed leaf edges. The roots are short and very ragged, later die, turning brown to dark brown. In plants that produce oxalate-rich and pectin-rich fruits, symptoms of calcium deficiency usually also manifest themselves in the fruit during periods of intense growth, e.g. tomato top rot or bitter apple spotting. It has also been found that the occurrence of potato scab is correlated with the tuber calcium concentration, which depends on the amount of calcium exchanged in the soil solution.

Sufficient content of available calcium has been shown to significantly affect the apple fruits and especially the quality and shelf life of fruits (Lánský M .: AGRO 8,2006, pp. 37-38).

Plants particularly sensitive to calcium deficiency in soil solution include cauliflower and apple tree.

Calcium salts of mineral acids, in particular nitrate, carbonate, phosphate and sulphate, are most commonly used as calcium sources in the context of plant nutrition. Especially in connection with the development of production and use of liquid fertilizers, the use of calcium nitrate - Ca (NO ₃ ) ₂ in the form of so-called. Calcium. In the calcium additive, in addition to the ammonium nitrate content, calcium nitrate constitutes its essential component.

Calcium is one of the basic types of fertilizers with the possibility of use in all forms of nutrition

SK 7055 Υ1 plants. Among its great advantages is that, unlike most other nitrogen fertilizers, it reacts physiologically alkaline (the alkalinity equivalent of calcium lime is 231.5 kg CaCO ₃ per ton of lime). It therefore has a very positive effect on acid soils. It is suitable for all cultures except those plant species which require an acidic soil reaction (eg conifers, grasses, azaleas, juniper) for their full growth and physiological development.

Calcium is especially suitable for basic fertilization in soil, and it is recommended to apply it to 10 m ² during the growing season as follows:

root and deep-fried vegetables 180 - 360 g fruit vegetables 180 - 240 g leafy vegetables, bulbs and potatoes up to 180 g legumes up to 140 g stone fruits and small fruits 180 - 300 g strawberries up to 360 g vines 50-100 g

Calcium is one of the fast-acting fertilizers with extra-root fertilization. leaf nutrition. When applied to plant leaves, it is recommended to use calcium salt in the form of a 0.1 to 0.2% solution. The foliar application of the calcium lime has also proved successful against the bitter spot of pome fruits, especially apples. It is advisable to spray the apple leaves with preventive solutions until the second half of July. It is recommended to take 5-6 preventive sprays of apple trees at 10 - 14 day intervals, while it is recommended to use a 0.5 - 1% calcium salt solution.

The use of calcium lime is also widespread in relation to hydroponic cultivation of plants and is also used in various types of fertilizer irrigation (drip irrigation, watering plants). Calcium lime is also suitable for the treatment of used growing substrates. The disadvantage of calcium lime is related to the nitrogen that this calcium fertilizer contains. In agricultural practice, there are relatively frequent cases where it is necessary to provide plants with readily available calcium and often magnesium, but it is not desirable to supply nitrogen.

Of the calcium fertilizers whose use is widespread in current agricultural practice, calcium salt is the most widely used source of water-soluble potassium. To a lesser extent, calcium chloride - CaCl ₂ is also used as a source of soluble calcium, especially when it is not appropriate to provide plants with nitrogen, which in turn is a source of undesirable chlorine.

Magnesium is one of the most important secondary plant nutrients and its presence in sufficient quantities is important for healthy and full-fledged development of plants, animals and humans.

In addition to several solid magnesium fertilizers, of which in particular magnesium sulphate, magnesium nitrate, magnesium chloride and magnesium carbonate - magnesite or magnesium-calcium carbonate - dolomite, in particular in relation to extracorporeal foliar nutrition, also liquid nutrients are used. magnesium fertilizers.

As in the case of the above mentioned solid industrial fertilizers, their base is usually the sulphate and nitrate forms of magnesium.

In the past, considerable attention has been paid to the study of the theoretical foundations of the production of liquid fertilizers based on magnesium nitrate (AGROCHEMIA 16, 12 - 1976, pp. 344 - 348). The results of this research work were later applied in production practice of several companies producing liquid fertilizers both in Slovakia and in the Czech Republic. Although the use of the Mg (NO ₃ ) ₂ - H ₂ O binary system allowed the production of phase-stable liquid fertilizers of the solution type, their disadvantage was the relatively low concentration of the magnesium component in the product (usually up to 8 wt.% MgO). along with the magnesium application, the plants always had to be supplied with approximately the same amount of nitrogen in nitrate form - which was not always desirable.

In the case of magnesium sulphate, the study of the thematic system of magnesium sulphate - urea - water has been the focus of attention in the past period. The results of measurements in this area resulted in the production of special foliar fertilizers (AO 200 677, 218 087). Although the above mentioned liquid magnesium fertilizers have been well applied in agricultural practice, the best evidence of this is their continued production.

In the previous period, attention was also paid to the production of magnesium liquid fertilizers based on magnesium chloride and / or magnesium nitrate (AO 221 002).

In the 1990s, in our agricultural practice, we started to use suspension, respectively in the cultivation of special agricultural crops (grape vine, fruit trees, vegetables). paste-like magnesium product based on an aqueous suspension of magnesium hydroxide (PV CR Nos. 1965-97, UV CR Nos. 6478 and 8920).

Although very good agronomic results have been achieved in practice with this type of magnesium suspension (gradual - long-acting form of magnesium, alkaline physiological reaction of fertilizer), the disadvantage of these suspension fertilizers is their high cost, mainly due to the price of the magnesium material used.

SK 7055 Υ1 low suspension stability, exclusively long-lasting form of magnesium and also less suitable rheological properties of the product - pasty and after long storage very difficult to resuspend consistency of magnesium concentrate.

Although several of these disadvantages were successfully eliminated by some other solutions (AO 232 216, AO No. 257 125, PV SR No. 2022 - 2000, PV CR No. 2001 - 4666, PV SR No. 1588 - 2001, ÚV SR No. 2849), the application of an exclusively slow-acting form of magnesium often led to an unbearable increase in application costs, and the effect of the magnesium fertilization was only slow.

Several liquid fertilizers, mainly for foliar application, which are a source of calcium and / or magnesium, are produced abroad and also in our country. However, these are almost exclusively mixed calcium and magnesium nitrate solutions, which in some cases still contain calcium chloride, boric acid, urea or some microelements.

Among the liquid concentrates of this type, for example, CAMPOFORT Ultra Ca leaf fertilizer containing 90 g of CaO (64 g of Ca), 24 g of MgO (14.5 g of Mg) and 1 g of boron per liter are particularly successful. Similarly, CALiMAGic solution concentrate containing 5 wt. Is currently available on the market for hydroponic plant cultivation, especially abroad. % Ca, 1.5 wt. % Mg, 1 wt. % nitrogen (as N) in nitrate form as well as 0.1 wt. % iron (as Fe) in chelated form (DTPA).

The essence of the technical solution

In an effort to eliminate the shortcomings in the preparation and use of liquid formulations for the nutrition of plants containing calcium and / or magnesium, it has now been found that many of the above problems make it possible to solve the formulations of this solution.

Liquid plant nutrient compositions containing calcium and / or magnesium according to the present invention are characterized in that they contain, in 100 parts by weight of the composition, 0.1 to 55 parts by weight of a calcium and / or magnesium salt of at least one of the carboxylic acids of the formula R - COOH wherein R is H and / or CH ₃ .

Calcium and / or magnesium salts of carboxylic acids in the present invention thus include methanoic acid - HCOOH (so-called formic) and / or ethanoic - CH ₃ COOH (so-called acetic). The carboxylic acids used in connection with the solution are commercially available, and they also have suitable handling and storage properties - they are all liquid at room temperature, allowing for a better handling mechanism (solidification temperature of formic acid, HCOOH is +8.4 ° C, temperature solidification of pure acetic acid, CH ₃ COOH is +16.6 ° C).

It has been experimentally confirmed that the magnesium and calcium salts of the subject carboxylic acids are characterized by their good water solubility, which allows the preparation of solution concentrates characterized by a high nutrient content in their chloride-free and nitrogen-free form, characterized by good handling and storage properties. It has now surprisingly been found that several of the beneficial properties of the present calcium and / or magnesium salts of said carboxylic acids can be utilized in connection with plant nutrition with these important secondary nutrients, based on which it is possible to prepare phase-stable liquid fertilizers and concentrates magnesium and / or calcium of the solution type.

The use of ethanoic acid, the so-called ethanoic acid, has proven to be particularly suitable in the preparation of liquid formulations. acetic - CH ₃ COOH, so that the liquid formulations contain a magnesium and / or calcium salt of ethanoic acid, the so-called. acetic - (CH ₃ COO) ₂ Mg and / or (CH ₃ COO) ₂ Ca.

It has also been shown that mixtures of carboxylic acids containing at least some of the said carboxylic acids can also be used in the preparation of calcium and / or magnesium concentrates according to the invention. The liquid formulations according to the invention may furthermore contain water and / or methanoic acid and / or ethanoic acid and / or an inorganic calcium-containing and / or magnesium-containing and / or urea-containing compound, depending on the reaction conditions chosen - in particular the reactant ratios. , and / or one of the additives adjusting the rheology and stability of the final formulation. The preparations in addition to calcium and / or magnesium may also contain basic nutrients, another of the secondary plant nutrients, trace elements, growth promoters or pesticides. In practice, it has also been confirmed that available raw materials can be used in the preparation of calcium and / or magnesium salts of carboxylic acids characterized by the formula R-COOH, wherein R is hydrogen and / or CH ₃ . Suitable sources of calcium and / or magnesium raw materials are especially oxides, hydrated oxides and hydroxides. The use of calcium and / or magnesium carbonates and bicarbonates is, for practical reasons, only less suitable due to the strong foaming of the reaction mixture caused by the release of carbon dioxide upon decomposition.

Multi-year agricultural practice has also confirmed the high plant tolerance of the subject group of substances, which is probably directly related to the related carboxylic acids' relationship to biosystems and the plant kingdom. At the same time, the use of organic forms of calcium and / or magnesium salts of the type in question has completely eliminated the influence of inorganic anions, which is usually a source of certain limitations both in manufacturing but mainly in application practice. The importance of the concentrates according to the solution is particularly great when needed

The plants can only be supplied in a rapidly acceptable form with magnesium and / or calcium, and fertilization with one of the other plant nutrients is not desirable.

Especially in cases where it is not suitable or possible to completely or only partially separate the solids from the reaction mixture after decomposition of the calcium and / or magnesium raw materials with carboxylic acids, it has proven advantageous to prevent sedimentation of the solid particles by appropriately adjusting the theological properties of the mixture. To this end, the efficacy of some of the high molecular weight polysaccharides of natural origin has been practically demonstrated. For example, xanthan gum and / or one of the carrageenans has been shown to be suitable as additives of this kind.

Liquid formulations of the type also satisfy the requirements for the application of calcium and / or magnesium in connection with the cultivation of submerged (e.g., aquaristic plants) or in various forms of soilless (e.g., hydroponic or aeroponic) plant cultivation.

Liquid products containing calcium and / or magnesium according to the invention are suitable for the preparation of complex liquid concentrates intended for plant nutrition after their previous dilution with water or can be used as a source of the subject secondary plant nutrients in the preparation of tank mix fertilizer sprayers. They are suitable for both preventive and curative treatment of plants.

The advantage of the solution is that it enables the preparation of very efficient sources of calcium and / or magnesium in their chloride-free form, while their use does not need to introduce another biogenic or in the worst case ballast element (chlorine, sodium etc.). In addition, formulations of the type in question are a source of usable carbon plants. Application solutions prepared using liquid concentrates according to the invention have a virtually neutral chemical reaction and are characterized by a low necrotizing effect on the treated plants.

The organic form, in which the secondary plant nutrients are bound in the compositions according to the invention, is not foreign to the plants, is rapidly and with high efficiency accepted by the plants, favorably affecting in particular their full-value physiological development, their quality and shelf life. The advantage of the compositions according to the invention is that they allow the supply of calcium and / or magnesium in a readily accessible form even without the need to introduce an additional plant nutrient or ballast element. The possibility of preparing liquid concentrates of magnesium and / or calcium in solution form characterized by a relatively high secondary nutrient content is also of considerable importance. The formulations of the present invention are also a source of organically bound carbon, the source of which is a biodegradable and commonly occurring carboxylic acid naturally occurring in the natural environment.

Liquid preparations according to the solution fully meet the criteria for growing organic food, their production can be waste-free and their use is not a source of environmental pollution - the products are self-contained.

EXAMPLES

The examples given illustrate and explain the substance of the solution in greater detail, but do not limit the claims for protection.

Example 1

In the laboratory verification of the preparation of the liquid calcium preparation according to the solution, the calcium component hydrate supplied under the commercial designation Hasit was used as the source of the calcium component. The procedure was carried out by adding 101 g of distilled water to the flask equipped with stirring and gradually adding 12.35 g of calcium hydrate with stirring. 15.3 g of glacial acetic acid, containing 99.8% CH3COOH, were added successively via an addition funnel to the calcium slurry thus prepared, with stirring. Due to neutralization heat, the reaction mixture was heated from the original 24.9 ° C to 48.2 ° C. This procedure yielded a practically clear colorless calcium acetate solution of weakly acidic reaction (pH: 5.78), having a specific gravity-density at room temperature of 1.078 g / cm ³ . It was determined by chelatometric titration that the prepared liquid product contained 4.12 wt. % Ca, corresponding to 16.3 wt. % of calcium acetate in the needles crystal solution, which concludes that the solution does not exhibit the necessary phase stability.

Example 3

In order to prepare a product that is sufficiently phase stable during storage, an aqueous solution of calcium acetate was prepared using the same quality as in the previous two examples and by a similar procedure: 13.1% by weight. % calcium hydrate Hasit, 69.9 wt. % distilled water and 17.0 wt. % glacial acetic acid (99.8 wt.% CH 3 COOH).

The density - density of the prepared liquid product was 1.1285 g / cm ³ . The product showed a virtually neutral chemical reaction (pH: 7.17). Calcium content was determined by complexometric titration

SK 7055 Υ1

6.05 wt. % Ca (23.9 wt.% Calcium acetate). The prepared product showed sufficient phase stability even after long-term storage at room temperature.

Further laboratory experiments using the same raw materials have shown that products containing 6.67 wt. % Ca (26.3 wt.% Calcium acetate), characterized by a weakly acidic chemical reaction (pH 5.2, d = 1.044 g / cm ³ ) and 6.6 wt. % Ca (26 wt.% Calcium acetate), characterized by a pH of 6.38, were phase stable even after prolonged storage at room temperature.

Example 4

In the laboratory preparation of calcium preparation based on the calcium salt of methane acid, the so-called calcium salt. Calcium formate was followed by a chemical reaction:

CaCO ₃ + 2 HCOOH - Ca (COOH) ₂ + CO ₂ + H ₂ O

Under stirring in a sulphonation flask, 127.95 g of 85% methanoic acid, so-called calcium carbonate (precipitated), was gradually added to the aqueous suspension prepared by homogenizing 880 g of distilled water with 115.65 g of calcium carbonate in the sense of Cs 4. formic acid.

In this way, 1076 g of a finely milky-cloudy colloidal solution were obtained, which contained 6 wt. % CaO, whose pH was 4.42 / 22.6 ° C.

The prepared calcium formate solution contained min. 65 g CaO per liter and was used after dilution with water for foliar fertilization of tomatoes in the form of 0.5% (v / v). The application solution thus prepared had a virtually neutral chemical reaction (pH 7.2) and its electrical conductivity was EC = 1.26 mS / cm.

Example 5

In order to prepare a liquid product of the solution type containing organically bound calcium and amide nitrogen, an aqueous solution characterized by the composition: 76.0 wt. % distilled water, 13.34 wt. % calcium formate (Calciumformiat - Bayer AG) and 10.66 wt. % urea adhered.

The aqueous solution thus prepared contained 4.11 wt.%, Ca (5.75 wt.% CaO) and 4.9 wt.%. % amide nitrogen (as N). The solution was a virtually neutral chemical reaction (pH 6.9).

Example 6

In order to prepare a magnesium preparation for plant nutrition in the sense of a solution based on the magnesium salt of methane, so-called. form, the following procedure was performed under laboratory conditions.

781.3 g of distilled water were charged to the sulfonation flask and 77.25 g of finely powdered Duhor N-PL magnesium hydroxide was added with stirring. To the aqueous Mg (OH) ₂ slurry thus prepared was then added 143.95 85% methanoic acid, a so-called " formic acid. During the acid addition, the temperature of the reaction mixture rose from 22 ° C to 52 ° C. Only a very slightly cloudy solution was obtained and completely clarified into the second dfta. The prepared product had a weakly acidic chemical reaction (pH 4.16) and its specific gravity-density at room temperature was 1.103 g / cm ³ . The clear product obtained was phase stable even after long-term storage.

Example 7-9

In order to determine the properties of the preparations in terms of the solution containing a higher proportion of magnesium acetate - (CH ₃ CO ₂ ) ₂ Mg in the form of genuine aqueous solutions, the chemical scheme was followed:

Mg (OH) ₂ + 2 CH ₃ COOH -> (CH ₃ COO) ₂ Mg + 2 H ₂ O

In the preparation of the solutions, the technical, finely dispersed magnesium hydroxide type Duhor N-PL, 80% ethanoic acid, so-called " acetic and tap water. In total, three laboratory experiments were carried out in which the following amounts of raw materials were used:

Experiment-example: 7 8 9

Amount of the reactant in grams

Tap water 706.8 633.5 5,560.2 Magnesium hydroxide type Duhor N-PL 82.3 102.9 123.5 Acetic acid 80% CH3COOH 210.9 263.6 316.3.

SK 7055 Υ1

In all three laboratory experiments, practically clear, colorless solutions were obtained which were characterized as follows:

Experiment - Example #

8 9

Calculated concentration of magnesium acetate in the mass solution. % (CH ₃ COO) ₂ Mg 20 25 30 Magnesium content of the solution (wt% Mg) 3.41 4.27 5.12 pH of the undiluted product 5.59 5.57 5.74 Specific gravity - density at room temperature (g / cm ³ ) 1,115 1,146 1,176

The liquid products prepared during experiments 7-9 showed very good phase stability.

Examples 10-14

In this series of laboratory experiments, the possibility of preparing liquid magnesium concentrates, according to a solution based on magnesium acetate, was investigated. In all experiments, technical magnesium oxide - MgO was used as the source of the magnesium component.

Work was carried out according to the reaction scheme:

MgO + 2 CH ₃ COOH - (CH ₃ COO) ₂ Mg + H ₂ O

5 experiments were carried out using the following amounts of raw materials:

Experiment - Example No .; 10 11 12 13 14

Amount of the reactant in grams

Tap water 589.35 520.9 452.5 384.1 315.6 Magnesium oxide technical, MgO 94.35 110.1 125.8 141.5 157.2 Acetic acid 80% CH 3 COOH 316.3 369.0 421.7 474.4 527.2.

To prepare the liquid magnesium concentrates, the required amount of technical magnesium oxide and tap water was introduced into a sulphonation flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, and a homogeneous suspension of MgO was prepared by mixing. Acetic acid was then added to the suspension thus prepared. During the experiments, the conditions summarized in the following overview were achieved:

Experiment - Example #

11

13 14

MgO suspension temperature before the start of acid dosing (° C) 22.0 22.0 21.8 24.5 25.0 Maximum reaction temperature reached. mixtures (° C) 64.0 78.0 80.0 85.0 82.0 Duration of acid dosing (min) 61 83 95 104 155

SK 7055 Υ1

The pH of the reaction mixture after completion of the acid addition 4.30 4.32 4.30 4.06 4.14 The pH of the reaction mixture after 24 hours 4.68 4.65 4.76 4.68 4.61 Clear product specific weight (g / cm ³ ) 1,147 1,172 1,198 1,221 1,246

Sensory properties of the product: brownish-red solution, slightly odorous in acetic acid.

Example 15

In order to assess the effect of different calcium salt anions on the electrical conductivity (EC) value of their aqueous solutions, their aqueous solutions were characterized by the same molarity.

For solutions of calcium salts of methane, ethanoic, hydrochloric and nitric acids, characterized by concentrations of 0,01 M, 0,05 M and 0,1 M using distilled water (EC = 3,5 pS), the following electrical conductivity values were measured:

Concentration - molarity of aqueous solution: Type of calcium salt (HCOa) ₂ Ca (CH ₃ CO ₂ ) ₂ Ca CaCl ₂ Ca (NO ₃ ) ₂

Electrical conductivity (EC) (pS / cm)

0.01 M 1584 / 25.0 ° C 1317 / 25.0 ° C 1263 / 25.0 ° C 1875 / 25.0 ° C 0.05 M 7240 / 25.0 ° C 5890 / 25.0 ° C 6300 / 25.0 ° C 8980 / 25.0 ° C 0.1 M 12595 / 25.0 ° C 10020 / 25.0 ° C 11600 / 25.0 ° C 16080 / 25.0 ° C

Examples 16 and 17

In these laboratory experiments, the possibility of preparing liquid concentrates containing the calcium and magnesium salts of ethanoic acid, the so-called. acetic acid in the form of a true solution. Both calcium and magnesium sources were oxides and decomposed using 80% acetic acid.

The following quantities of raw materials were used during two experiments:

Experiment - Example #

17

Amount of the reactant in grams

Tap water 601.7 522.1 Calcium Oxide 71.6 85.9 Magnesium oxide technical, MgO 31.4 37.7 Acetic acid 80% CH ₃ COOH 295.3 354.3.

The preparation of calcium-magnesium acetate-containing products was carried out in a similar manner to that described in the examples. 10 to 14.

The parameters describing the preparation conditions as well as the basic properties of the products are given in the following overview:

SK 7055 Υ1

Experiment - Example # 16 17 MgO suspension temperature before the start of acid dosing (° C) 24.5 23.0 Maximum reaction temperature reached. mixtures (° C) 64.0 69.5 Duration of acid dosing (min) 19 25 The pH of the reaction mixture after completion of the acid addition 4.19 / 39.2 ° C 4.22 / 47.2 ° C The pH of the reaction mixture after 24 hours 4.68 / 24.7 ° C - Clear product specific weight (g / cm ³ ) 1,138 Sensory product properties: brownish-red solution, slightly odorous in acetic acid viscous gel. Example 9

In order to adjust the theological properties of the product obtained by decomposing the oxides of calcium and magnesium with acetic acid, the preparation conditions of which are given in Example 17, and having the character of a relatively strong viscous gel, 136 g of tap water were added gradually and under stirring. water and 490.7 g of urea added.

Upon dissolution of the urea, a brown solution was obtained, having a pH of 5.65 / 25.1 ° C.

Example 19

The product obtained by the decomposition of technical magnesium oxide under acetic acid under the conditions of Example 14 contained about 50 wt. % magnesium acetate.

Due to the high concentration, the solid unreacted residue formed, although only a thin but rather stable suspension, with the fine sludge only settling slowly.

For this reason, after 24 hours, the layer of the finely cloudy brown product was separated from the tiny fraction of settled coarse sludge deposited at the bottom by squeezing. The separation was stabilized by addition of 1.2 wt. % polysaccharide of natural origin - powdered xanthan gum. The stabilizing additive was added with effective mixing of the mixture, and the mixture was stirred for about 10 minutes after the addition of the gelling agent was complete.

Thus a magnesium concentrate was obtained in the sense of the solution, which contained approximately 14 masses. % MgO in the form of a stable suspension.

Example 20

In order to prepare a liquid product containing plants readily accessible to calcium, magnesium and boron, in accordance with the invention, 597 parts by weight of calcium-magnesium acetate containing 5 wt. % Ca and 1.5 wt. % Mg (product obtained under the conditions of Example 16) with 403 parts by weight of a monoethanolamine-type liquid boron concentrate containing 9.5% by weight. % B.

Homogenization of the mixture yielded a brown-orange clear solution, slightly acidic chemical reaction (pH: 5.61 / 21.3 ° C), containing almost 3.0 wt. % calcium (as Ca), 0.9 wt. % magnesium (as Mg) and 3.8 wt. % of boron (as B). The product obtained was freely miscible with water.

Example 21

By mixing, 860 parts by weight of a 15% aqueous solution of magnesium formate containing 5.3% by weight were homogenized. % MgO with 140 parts by weight of a citrate type microelement concentrate used in the production of Floralesad liquid fertilizer. Thus a magnesium concentrate was obtained, which ob

SK 7055 Υ1 reached more than 4.5 masses. % MgO, 0.028 wt. % copper (as Cu), 0.056 wt. % zinc (as Zn), 0.056 wt. % manganese (as Mn), 0.017 wt. % molybdenum (as Mo) and 0.225 wt. % of boron (as B).

The prepared magnesium liquid product, enriched with trace plant nutrients, had a light green-blue color, was clear and had a pH of 4.24 / 22.4 ° C.

Example 10

In order to prepare a potassium concentrate enriched with an effective source of calcium and magnesium for the preventive treatment of woody plants, 552 parts by weight, parts of an aqueous solution of calcium acetate containing 5 parts, were mixed. % calcium (as Ca) and 1.5 wt. % magnesium (as Mg) with 448 parts by weight of an aqueous solution of potassium formate containing 35% by weight. % K ₂ O (Liquid Potassium Concentrate Cukrostimul K 500). Homogenization of the mixture yielded a clear light brown-orange weak acid solution (pH 6.01 / 23.5 ° C) containing 15.7 wt. % potassium in chlorine free form (such as K ₂ O), almost 2.8 wt. % calcium (as Ca) and more than 0.8 wt. % magnesium (as Mg).

Industrial usability

The present invention relates to plant nutrients containing calcium and / or magnesium. The compositions according to the invention are characterized by containing at least one of the calcium and / or magnesium salts of carboxylic acids of the R-COOH type, wherein R is a hydrogen cation or a methyl group, with 100 parts by weight of the composition having a minimum of 0.1 and a maximum of 55 parts of said salts.

The organic form, in which the secondary plant nutrients are bound in the compositions according to the invention, is not foreign to the plants, is rapidly and with high efficiency accepted by the plants, favorably affecting in particular their full-value physiological development, their quality and shelf life. The advantage of the compositions according to the invention is that they allow the supply of calcium and / or magnesium in a readily accessible form even without the need to introduce an additional plant nutrient or ballast element. The possibility of preparing liquid concentrates of magnesium and / or calcium in solution form characterized by a relatively high secondary nutrient content is also of considerable importance. The formulations of the present invention are also a source of organically bound carbon, the source of which is a biodegradable and commonly occurring carboxylic acid naturally occurring in the natural environment.

The production of liquid concentrates in terms of the solution is technologically and materially undemanding.

Liquid concentrates of potassium in the sense of solution by their nature are among the products usable in organic farming systems.

Claims (6)

Liquid plant nutrition preparations containing calcium and / or magnesium, characterized in that, in 100 parts by weight of the preparation, they contain 0.1 to 55 parts by weight of a calcium and / or magnesium salt of at least one of the carboxylic acids of the general formula: R - COOH wherein R is H and / or CH ₃ by containing a magnesium salt, as a carboxylic acid, as an inorganic compound and 45 to 99.9 parts by weight of at least one of water, a carboxylic acid, an inorganic compound comprising calcium and / or magnesium, urea, an additive to adjust the rheological properties and stability of the liquid formulation. Liquid preparations according to claim 1, characterized by seletium ethane. acetic - (CH ₃ CO ₂ ) ₂ Mg. Liquid preparations according to claim 1, characterized in that they comprise methane and / or ethanoic acid. Liquid preparations according to claim 1, characterized by containing calcium and / or magnesium comprising at least one of calcium and / or magnesium compounds including their oxide, hydrated oxide, hydroxide and carbonate. Liquid formulations according to claim 1, characterized in that they contain at least one of high molecular weight polysaccharides of natural origin as an additive regulating the rheological properties and stability of the liquid formulation. Liquid preparations according to claim 5, characterized in that they contain xanthan gum and / or one of the carrageenans as high molecular weight polysaccharide of natural origin.