CS211287B1 - Method of preparation of the trace elements concentrates and/or secondary plant nutrients suitable for nutrition and/or treating the plants - Google Patents

Abstract

A method of preparing trace concentrates and / or secondary plant nutrients suitable for nutrition and / or plant \ t containing one or a combination of several trace elements and / or secondary plant sulphite leachate nutrients and / or sulphite stillage, the so-called. "felts" falling in the production of fodder yeast in the form of calcium salt containing 5 to 60, preferably 10 to 30, weight % dry matter, at. 10 ° C to 105 ° C, preferably at 50 to 85 ° C, chemical by reaction with magnesium sulfate and / or ferrous and / or zinc and / or cupric and / or manganese and / or cobalt and / or titanium and / or titanium dioxide titanium dioxide called. titanyl sulphate with na every 100 parts by weight of sulfite solids and / or sugar-free sugars of sulphite stillage in the reaction mixture 2 to 35 parts by weight of sulphates of said metal cations contemplated as anhydrous salts, with the reaction being excluded the precipitate of the sulphate precipitated from the reaction separation of the mixtures.

Description

(54) Method for the preparation of trace element concentrates and / or secondary plant nutrients suitable for nutrition and / or plant treatment

A process for the preparation of nutrient and / or plant nutrient concentrates of trace and / or secondary plant nutrients comprising one or a combination of several trace elements and / or secondary plant nutrients from sulphite leaches and / or sulphate-free sugar soils. shells falling off in the manufacture of feed yeast in the form of a calcium salt containing 5 to 60, preferably 10 to 30% by weight of dry matter, at. a temperature of 10 to 105 ° C, preferably at a temperature of 50 to 85 ° C, by chemical reaction with magnesium and / or ferrous and / or zinc and / or copper and / or manganese and / or cobalt and / or titanium and / or oxisulphane titaničítýra tzv. titanyl sulphate, wherein for each 100 parts by weight of the sulphite extract liquor and / or the sulphite-free sugar in the reaction mixture there are 2 to 35 parts by weight of sulphates of said metal cations, considered anhydrous, the precipitate of calcium sulfate being separated by reaction. .

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SUMMARY OF THE INVENTION The present invention provides a process for the preparation of concentrates of trace and / or secondary plant nutrients suitable for nutrition and / or treatment of plants containing one or a combination of several trace and / or secondary plant nutrients.

It is generally known that for plant nutrition in addition to the basic so-called. macronutrients / N, P, K /, also use secondary nutrients, which most often include calcium, magnesium, sulfur and usually also iron and micro-nutrients - trace elements / CU, Μη, Zn, B, Mo, Co, Ti and many other/. Secondary nutrients (calcium, magnesium, iron), as well as trace elements, are usually applied in the forrae of different organometallic compounds.

Organometallic compounds containing at least trace elements are used for preventive and / or curative relief of the symptoms present in plants as a result of their deficiency.

Recently, the composition of cultivated crops has largely changed, especially in terms of species and variety. Growing high-performance cultivars using modern agro-technology ensures their high yields. The specialization and intensive production of agricultural crops of the same kind for several consecutive years, in some farms, results in unilaterally draining nutrients from the pod. Also, fertilization with high doses of essential nutrients (Ν, Ρ, Κ) at low levels of secondary nutrients and trace elements can under certain conditions lead to the induction of various symptoms associated with their deficiency, often compounded by various antagonistic effects.

In order to avoid these negative phenomena, it is necessary to maintain the level of secondary nutrients and trace elements at the necessary height. For this purpose, both in terms of prevention and the possibilities of curative intervention, these elements are applied in various forms such as commonly technical inorganic salts, frits, chelates, organo-complex compounds or also as various industrial wastes, mainly from chemical, mining and metallurgical industry.

Frits are essentially finely ground trace elements containing silicate, phosphor or borate glasses, which, due to the gradual release of trace elements, are particularly suitable for the storage of trace elements, particularly on acidic sandy soils in areas with a relatively high level of rainfall.

Inorganic salts of trace elements and secondary plant nutrients are usually used in the form of aqueous solutions or suspensions! both for pod fertilization and foliar plant nutrition.

Recently, the use of secondary plant nutrients and trace elements in the form of aqueous solutions of their chelates or in the form of various organometallic complexes has been extensively developed.

In particular, derivatives derived from various aliphatic amines and diamines are usually used as the compounding agents for the preparation of this type of compounds.

In the current agricultural practice, the use of complexes based on ethylenediaminotetraacetic acid (EDTA), nitriloacetic acid (NTTA), diethylenetriaminopentaacetic acid (DTPA), hydroxyethylenediarainotetraacetic acid (HEDTA), dihydroxyDiethylenediamino (some other DA) is widely used.

Of these complexing agents, which are used in connection with the application of secondary and especially trace plant nutrients, the most widespread is the use of EDTA and DTPA, which is related to their relatively good efficacy.

Despite the fact that the use of trace elements and secondary plant nutrient elements in the form of the aforementioned complexes achieves very good results, in particular at rapid

1287, the expansion of their use in large-scale agricultural production encounters considerable difficulties, mainly due to the high price of the raw materials and hence the final products, their limited availability, the considerable difficulty of their production, and the ecological reasons associated with their slow biodegradability. v pode.

It has now been found that most of these disadvantages, in particular with the availability of the necessary raw materials, their cost, as well as their biodegradability and agronomic efficiency, can be eliminated by the process of producing trace element concentrates and / or secondary plant nutrient concentrates according to the invention.

The essence of the invention is that sulphite leaches and / or sugars free of sulphite stillage, so-called " the pellets resulting from the production of feed yeast in the form of a calcium salt containing 5 to 60% by weight of dry matter, preferably 10 to 30% by weight of dry matter, are subjected to a reaction at 10 to 105 ° C, preferably at 50 to 85 ° C with magnesium sulphate and / or ferrous and / or ferric and / or zinc, and / or copper and / or manganese and / or cobalt and / or titanium and / or titanium dioxide sulphate. titanyl sulfate.

At the same time for every 100 weight. In the reaction mixture, 2 to 35 parts by weight, preferably 12 to 22 parts by weight, of the sulphates of said metal cations, considered to be anhydrous salts, are precipitated from the reaction mixture by precipitating calcium sulphate from the reaction mixture. separated.

The preparation of trace element concentrates and / or secondary plant nutrients according to the invention is based on a double decomposition which is subject to the formation of a sparingly soluble calcium sulphate, which can be illustrated, with considerable simplification, by the scheme:

CaSV + MeSO. »MeSV + CaSO.

4 wherein CaSV is a sulphite liquor and / or a sugar-free sulphate stillage. The calcium salt and MeSO4 is a trace element and / or secondary plant nutrient sulphate characterized by a higher solubility in the reaction system than at the same temperature is the calcium sulphate solubility.

Desired reaction - double decomposition begins in the system when the concentration of calcium sulfate in the solution corresponds to its product of solubility in the reaction system. The water solubility of calcium sulfate at 25 ° C is Κ _β = 6.2.10 \

In order to achieve the necessary precipitation rate of calcium sulfate, and in particular to obtain this in good form, it is preferred to carry out the reaction at elevated temperature, and it has also been found that the concentration of sulfite leaches and / or stillage is particularly preferred 30% by weight of dry matter.

The sulphates of the biogenic elements which form the species' principal reactant may also be added to the reaction mixture in solid-crystalline form, but for the formation of a good processable gypsum sludge it is preferred to incorporate these into the reaction in the form of aqueous solutions or suspensions.

The calcium sulfate sludge formed by the reaction can be separated from the reaction mixture by sedimentation, filtration or centrifugation. Combination of sedimentation with subsequent filtration or centrifugation of the concentrated gypsum sludge is particularly preferred.

The liquid phase after gypsum separation can be adjusted to the desired concentration by evaporating water at atmospheric or reduced pressure, or it can be treated by completely evaporating the water to form a water-soluble powder concentrate. For this purpose it is advantageous to use one of the so-called types. spray driers.

Organometallic compounds-concentrates of trace elements and / or secondary plant nutrient elements prepared according to the invention have a number of advantages over the currently used forms. In the bottom they are completely biodegradable. They are suitable both for incorporation into the podium and for foliar application. Their use in extracorporeal-foil application improves the wettability of the leaves of the plants, resulting in a substantially higher adhesion of the biologically active ingredients to the leaf surface. The starting material for their preparation is the by-product - waste from cellulose production or fermentation processes, by which this waste is partially recovered, the use of which significantly reduces pollution of public recipients and more comprehensive use of wood mass. Due to the low production costs and the sufficiency of the basic raw material, which is still the most unpleasant waste of the pulp industry today, opportunities for the use of trace elements and / or secondary plant nutrients in the form of concentrates in a large-scale agricultural production are opening up.

By using the preparations according to the invention, organic substances which significantly improve the structure of the soil as well as substances important in terms of humus formation are introduced into the soil. The addition of most of the formulations of the present invention to suspension and some solution liquid fertilizers improves their physicochemical and especially rheological properties. Concentrates of trace elements and / or secondary plant nutrients prepared on the basis of the substances and in accordance with the present invention are compared to chelating agents of the EDTA, DTPA, HEDTA, DHEDDA type as well as on the basis of most organometallic compounds used today are also very economically advantageous.

The utility of biogenic elements from the concentrates prepared by the process of the invention is many times greater than that of commonly used inorganic salts. The application of trace element concentrates and / or secondary plant nutrients to the soil reduces the possibility of retrogradation of the applied soil. Most of the concentrates prepared by the process of the invention act to inhibit corrosion. * the essence of aqueous solutions of some inorganic salts to commonly used metal construction materials (for example in the environment of nitrogenous liquid fertilizers prepared on the basis of ammonium nitrate and urea).

• F - -. ·

The following examples illustrate but do not limit the invention in any way.

Examples 1 to 5

Under laboratory conditions, individual liquid concentrates of the following biogenic elements have been prepared for subsequent bioassays: magnesium, media, zinc, iron and manganese.

In the tests, the extract used was sulphite cooking of the cellulose, after its treatment by fermentation and fermentation, after distilling off the alcohol and concentrating. The sulphite stillage thus obtained contained 47.46 weight percent dry matter and 2.10 weight percent calcium.

For the preparation of the individual samples, the batch of distilled water was added to 100.00 g of the sulphite stillage and also the calculated amount of crystalline biogenic sulfate was calculated.

Thereafter, the reaction mixture was kept under reflux with stirring at 75-85 ° C for 1 hour.

After cooling the reaction mixture to about 50 ° C, the cured calcium sulfate precipitate was filtered off.

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The weights of the basic components and also the concentration of the relevant biogenic element in each prepared sample are given in the table below:

Example Weights of the reactants in g Concentration of biogenic element in the product in fcinot. % Sulphite Shapes / 47,46 2 / Distilled water Quantity and type of sulphate used I 100.0 368.0 _A 12.92 g MgS0 7H ₂ 0 0.27 2 100.0 369.0 13.08 g CuS0 ₄ .5H ₂ 0 0.70 3 100.0 368.0 15.06 g ZnSO ₄ .7H ₂ 0 0.71 4 100.0 368.0 14.57 g EeSO ₄ .7H ₂ O 0.61 5 100.0 370.8 11.69 g of MnSO 4 H 4 0.60

The allocation vápanetého sulfate formed in the reaction is, on average, 460 g of a liquid concentrate with about 9 g dry weight of calcium in the form of CaSO ^ 2H ₂ O.

Example 6

Weigh 4.2 g of titanium dioxide (TiO ₂ ) in the form of a so-called beaker. titanium dioxide, 5.4 g of concentrated sulfuric acid containing 95 Z of MH - H ₂ SO 4 was added and the mixture was heated on an asbestos mesh cooker with occasional vigorous stirring of the bar. After concentration, the reaction mixture was moistened with a small amount of distilled water and allowed to cool freely after about 2 hours of heating and almost complete re-evaporation. After cooling, the reaction mixture was evaporated in 1 250 ml of cold distilled water. Due to the complete decomposition of the oxide with concentrated sulfuric acid, a nearly clear titanium dioxide solution was obtained by dissolution.

3

A second beaker of about 600 cm was charged with 100.0 g of concentrated sulfite stillage of the same composition as in Examples 1-5. 125.0 cm @ 3 of cold distilled water (about 25 DEG C.) was added to the weight of the sulfite stillage. After homogenization of the stillage with water, the entire volume of an aqueous solution of titanyl sulfate, prepared by reaction of TiO ₂ with sulfuric acid, was added to the dark brown solution. The mixture was stirred for about an hour and then the gypsum sludge was collected by filtration.

Approximately 450 g of a solution containing about 0.52% by weight of titanium were prepared as described above. Washing and drying of the filter cake to afford 8.4 g CaSO ^, 2H ₂ O.

Example 7

Pironette plants of the Pironette variety were grown in a greenhouse in a manganese deficient pod, to which, before planting the seeds, NPK nutrient solution was added and in one case manganese in the form of Mn-concentrate prepared according to the invention at a dose corresponding to 15 kg Mn.ha. were maintained in a greenhouse with a combined watering and 32 days after the experiment was established, the post-mortem plant length and dry weight of the aboveground mass were determined.

variant pos tmor t, . The length weight 1 growth in cm v Z in g v Z NPK 16.4 100 0,580 100 NPK + Mn 17.1 104.3 0,653 112.6

Example 8

Diadem oat plants were grown in a honey-deficient pod, to which NPK nutrient solution was added prior to planting the seeds and, in one case, honey in the form of

The plants were kept in a greenhouse with controlled watering and 32 days after the start of the experiment, the post-mortem plant length and the weight of the dry aerial mass were obtained.

Variant postmort. length in cm% weight in g / container

NPK 2, 7.06 100 0,890 NPK + Cu 29.80 110.1 '0,971

100 109, 1

Example 9

Balanced growth of oz. wheat of the Grana variety in the posting phase was foliar fertilized with a nitrogen solution of DAM-390 at a dose corresponding to 30 kg N. ha and on the other hand a mixture of nitrogen solution and test magnesium concentrate prepared according to the invention from MgSO4 and thickened sulphite stillage, at a dose corresponding to (30 kg N + 6 kg Mg). ha \ The increase in grain yield was 117.5, resp. up to 141.5 Z.

Variant úrodazrna

t.ha ¹ FROM k o n t r c l a 3.77 100 30 kg N 4.44 117.5 30 kg N + 6 kg Mg 5.34 141.6

Example 10

Sugar beet variety Dobrovická A ”on the pod. with a magnesium deficiency, the foliar fertilized 22.6, on the one hand by using a magnesium-containing concentrate of magnesium sulphate and thickened sulphite liquor according to the invention at a dose corresponding to 6 kg Mg.ha and on the other hand by keserite. \ Harvesting of the seed, performance was recorded. ·) 'Qualitatively analyzed for sugar content and calculated raffinate yield / tab. /. Seed crops ·; in both cases fertilization increased by more than 4 Z compared to the control, the raffinate yield increased by 14,4% after the tested fertilizer, by 3,4 Z after kieserite.

variant harvest of the bulbs refinery yield t.ha FROM t. ha 7th inspection 5.41 100 5.85 100 Try. fertilizer 6 kg Mg.ha ¹ 5.67 104.8 7.05 119.6 kieserite 30 kg 5.66 104.5 6.36 108.7

Example 11

Maize plants, TO-510 hybrid, were grown on a zinc-deficient floor to which NPK nutrient solution was added prior to seed seed and, in one case, zinc in the form of a Zn-concentrate prepared according to the invention at a dose of 17 kg Zn ha. were maintained in a greenhouse by a controlled watering and the dry matter masses were found 3 days after the start of the experiment.

Variant Dry mass in g / container

NPK

NPK + Zn

1.63

1.72

100

105.5

Example 12

Equilibrium of oz, wheat variety Slavia were fertilized with Mg-concentrate by the MgSO4 reaction and concentrated sulphite stillage according to the invention in a dose corresponding to 6 kg Mg.ha. The indication of effect was the grain yield in comparison with the non-fertilized control.

Variant of grain harvest

t.ha ¹ 7.

control 5.15

Mg-concentrate 5.61

100 109, 1

Example 13

Apple tree culture, Starking variety, year 1980, locality Dunajská Středa - Búšlak. By a single application of the Fe-concentrate prepared according to the invention at a dose of 500 g to the barley tree and 4-fold. by application of spraying at a concentration of 0.4 7 we found a curative effect (gradual greening of vegetative organs) and subsequently apple crop increments per 1 ha.

variant

Podium app foliar application Harvest 7 crop 7 v t.ha v t. ha 1

Untreated control 17.76

Fe-concentrate 31.63

Example 14

100.00 17.76 100.00

178.12 27.75 156.25

Culture - grapevine, year 1979, variety Muller Thurgau, locality Vištuk, okr. Bratislava-countryside and Vrbové, okr. Trnava, with the application of 200 g of Fe - concentrate according to the invention per 1 kilogram of vine, we found a curative effect and an increase in the yield of grapes.

variant crop t. ha Vištuk 7 1 willow Harvest - 1 t.ha 7 inspection 6,280 100.00 7,400 100.00 Fe Concentrate 6,580 104.77 10,440% 141, 08 EXAMPLE 15 Culture - vine, r. 1980 Muller variety Thurgau, locality Vištuk, okr. Bratislava

the countryside.

Vine with visually diagnosed Fe deficiency / typical chlorosis - the physiological yellowing of vegetative organs from Fe deficiency in growing. tissues /. After a 4-fold application of the Fe-concentrate produced according to the invention at a concentration of 0.4% per leaf need together with pesticidal formulations, the curative effect / gradual greening increased. 7. The increase in yield was 18.8 7. against untreated control, and we did not find any deterioration in the quality parameters.

Claims (1)

OBJECT OF THE INVENTION A method for preparing concentrates of trace elements or secondary plant nutrients suitable for the maintenance and / or for the treatment of plants, comprising a combination of one or more trace elements and / or second _row of plant nutrients, characterized in that the waste liquors and / or sugar-free sulphite residues, so called. the sclerapate which is produced in the manufacture of feed yeast in the form of a calcium salt containing 5 to 60% by weight of dry matter, preferably 10 to 30% by weight of dry matter, is subjected to a chemical treatment at a temperature of 10-105 ° C, preferably 50-85 ° C. reactions with magnesium sulphate and / or ferrous and / or zinc and / or copper and / or manganese and / or cobalt and / or titanium and / or titanium dioxide sulphate. titanyl sulphate, wherein for each 100 parts by weight of the sulphite extract liquor and / or the sulphate-free sugar in the reaction mixture there are 2 to 35 parts by weight, preferably 12 to 22 parts by weight, of said metal cation sulphates, considered anhydrous, the calcium sulfate precipitate is separated from the reaction mixture.