CS211287B1 - A method of preparing trace element concentrates and / or secondary plant nutrients suitable for nutrition and / or plant dressing - Google Patents

Abstract

Method for preparing concentrates of trace and/or secondary plant nutrients suitable for nutrition and/or treatment of plants, containing one or a combination of several trace elements and/or secondary plant nutrients from sulfite leachates and/or sugars freed from sulfite distillates, so-called "sludge", which is discarded during the production of feed yeast in the form of 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 sulfate and/or iron sulfate and/or zinc sulfate and/or copper sulfate and/or manganese sulfate and/or cobalt sulfate and/or titanium sulfate and/or titanium oxysulfate, so-called titanyl sulfate, whereby for every 100 parts by weight of dry matter of sulfite leachates and/or sugars freed from sulfite calcinations in the reaction mixture there are 2 to 35 parts by weight of sulfates of the above metal cations, considered as anhydrous salts, whereby the precipitate of calcium sulfate formed by the reaction is separated from the reaction mixture.

Description

(54) Method for preparing concentrates of trace elements and/or secondary plant nutrients suitable for plant nutrition and/or treatment

Method for preparing concentrates of trace and/or secondary plant nutrients suitable for nutrition and/or treatment of plants, containing one or a combination of several trace elements and/or secondary plant nutrients from sulfite leachates and/or sugars freed from sulfite distillates, so-called slops, waste during the production of feed yeast in the form of 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 sulfate and/or iron sulfate and/or zinc sulfate and/or copper sulfate and/or manganese sulfate and/or cobalt sulfate and/or titanium sulfate and/or titanium oxysulfate, so-called titanyl sulfate, whereby for every 100 parts by weight of dry matter of sulfite leachates and/or sugars freed from sulfite calcinations in the reaction mixture there are 2 to 35 parts by weight of sulfates of the above metal cations, considered as anhydrous salts, whereby the precipitate of calcium sulfate formed by the reaction is separated from the reaction mixture.

1287

The subject of the invention is a method for preparing concentrates of trace and/or secondary plant nutrients suitable for plant nutrition and/or treatment, containing one or a combination of several trace and/or secondary plant nutrients.

It is generally known that, in addition to the basic so-called macronutrients /N, P, K/, secondary nutrients are also used for plant nutrition, which most often include calcium, magnesium, sulfur and usually iron, as well as micronutrients - trace elements /Cu, Mn, Zn, B, Mo, Co, Ti and many others/. Secondary nutrients /calcium, magnesium, iron/, but also especially trace elements are usually applied in the form of various organometallic compounds.

Organometallic compounds containing mainly trace elements are used for the preventive and/or curative elimination of symptoms manifested in plants as a result of their deficiency.

In recent times, the composition of cultivated agricultural crops has changed to a great extent, especially in terms of species and varieties. The cultivation of high-yielding cultivars using modern agricultural technology ensures their high yields. Specialization and intensive production of agricultural crops of the same type, even for several years in a row, has in some agricultural enterprises the result of a one-sided depletion of nutrients from the soil. Similarly, fertilization with high doses of basic nutrients /Ν,Ρ,Κ/ at low levels of secondary nutrients and trace elements can, under certain conditions, lead to the induction of various symptoms related to their deficiency, often multiplied by various antagonistic effects.

In order to prevent this negative phenomenon, it is necessary to maintain the level of secondary nutrients and trace elements at the required level. For this purpose, both from the point of view of prevention and from the point of view of the possibilities of curative intervention, these elements are applied in various forms such as common technical inorganic salts, frits, chelates, organocomplex compounds or also as various industrial wastes, mainly from the chemical, forging and metallurgical industries.

Frits are essentially finely ground trace element containing silicate, phosphate or borate glasses, which, due to the gradual release of trace elements, are mainly suitable for stock fertilization with trace elements, especially on acidic sandy soils in areas with relatively high levels of rainfall.

Inorganic salts of trace elements and secondary plant nutrients are usually used in the form of aqueous solutions or suspensions, both for soil fertilization and for 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 developed to a large extent.

For the preparation of this type of compounds, derivatives derived from various aliphatic amines and diamines are usually used as complexing agents.

In current agricultural practice, the use of complexes based on ethylenediaminetetraacetic acid (EDTA), nitrile acetic acid (NTTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediaminetetraacetic acid (HEDTA), dihydroxyethylenediamineacetic acid (DAEDDA) and some others is quite widespread.

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

Despite the fact that the use of trace elements and secondary plant nutrient elements in the form of the above-mentioned complexes achieves very good results, especially with rapid

1287 rative interventions, the expansion of their use in large-scale agricultural production encounters significant difficulties associated mainly with the high price of starting materials and therefore also of final preparations, with their limited availability, the considerably difficult technology of their production, as well as ecological reasons related to their slow biodegradability in the soil.

It has now been found that most of the above disadvantages, related in particular to the availability of the necessary raw materials, their price and also to their biodegradability and agronomic efficiency, can be eliminated by the method of producing trace element concentrates and/or secondary plant nutrient concentrates according to the invention.

The essence of the invention lies in the fact that sulfite liquors and/or sugar-free sulfite distillates, so-called slush, remaining after the production of feed yeast in the form of calcium salt, containing 5 to 60 percent by weight of dry matter, preferably 10 to 30 percent by weight of dry matter, are subjected to a reaction at a temperature of 10 to 105 °C, preferably at a temperature of 50 to 85 °C, with magnesium sulfate and/or ferrous sulfate and/or ferric sulfate and/or zinc sulfate and/or copper sulfate and/or manganese sulfate and/or cobalt sulfate and/or titanium sulfate and/or titanium oxysulfate, so-called titanyl sulfate.

For every 100 parts by weight of dry matter of sulphite liquors and/or sugars freed from sulphite stillages in the reaction mixture, there are 2 to 35 parts by weight, preferably 12 to 22 parts by weight, of sulphates of the said metal cations, considered as anhydrous salts, whereby the precipitate of calcium sulphate formed by the reaction is separated from the reaction mixture.

The basis for the preparation of concentrates of trace elements and/or secondary plant nutrients by the method according to the invention is a double decomposition, which is accompanied by the formation of poorly soluble calcium sulfate, which can be represented, with considerable simplification, by the following scheme:

CaSV + MeSO. » MeSV + CaSO.

4 where CaSV is sulfite leachate and/or sugar-free sulfite distillates, so-called "sludge in the form of calcium salt, and MeSO^ is a sulfate of a trace element and/or a secondary plant nutrient characterized by a higher solubility in the reaction system than the solubility of calcium sulfate at the same temperature.

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

In the interest of achieving the required rate of precipitation of calcium sulfate and especially in an effort to obtain it in a good filterable form, it is advantageous to carry out the reaction at an elevated temperature, and it has also been found that the concentration of the sulfite leachates and/or calcinations is particularly advantageous to choose in the range of 10 to 30 percent by weight of dry matter.

Sulphates of biogenic elements, which form the second basic reaction component, can be added to the reaction mixture in solid-crystalline form, however, from the point of view of the formation of a well-processable gypsum slurry, it is preferable to introduce them into the reaction in the form of aqueous solutions or in the form of suspensions.

The calcium sulfate sludge formed by the reaction can be separated from the reaction mixture by sedimentation, filtration or centrifugation. It is particularly advantageous to combine sedimentation with subsequent filtration or centrifugation of the thickened gypsum sludge.

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

Organometallic compounds-concentrates of trace elements and/or elements of secondary plant nutrients prepared by the method according to the invention have a number of advantages in comparison with the forms commonly used today. They are completely biodegradable in the soil. They are suitable for both incorporation into the soil and for foliar application. When they are used in the form of foliar-foliar application, the wettability of plant leaves is improved, as a result of which a significantly higher adhesion of biologically active components to the surface of the leaf surface is achieved. The starting materials for their preparation are by-products-waste from cellulose production or from fermentation processes, by which this waste is partially recovered, the use of which significantly reduces the pollution of public recipients and makes more comprehensive use of wood material. Due to low production costs and the abundance of basic raw materials, which are still in most cases unpleasant waste products of the cellulose industry, opportunities are opening up for the use of trace elements and/or secondary plant nutrients in the form of concentrates in large-scale agricultural production.

By using the preparations produced by the method according to the invention, organic substances are introduced into the soil, significantly improving the structure of the soil, as well as substances important in terms of humus formation. By adding most of the preparations produced by the method according to the invention to suspension and some solution liquid fertilizers, their physicochemical and especially rheological properties are improved. Concentrates of trace elements and/or elements of secondary plant nutrients prepared on the basis of the substances and method according to the invention are also economically very advantageous in comparison with preparations produced on the basis of chelating substances of the type EDTA, DTPA, HEDTA, DHEDDA, as well as on the basis of most of the organometallic compounds used today.

The utilization of biogenic elements from concentrates prepared by the method according to the invention is many times higher than from commonly used inorganic salts. When applying concentrates of trace elements and/or secondary plant nutrients to the soil, the possibility of retrogradation of the applied p i is reduced. Most of the concentrates prepared by the method according to the invention have an inhibitory effect on the corrosion. * esivitu aqueous solutions of some inorganic salts on commonly used metal construction materials /for example, in the environment of nitrogenous liquid fertilizers prepared on the basis of ammonium nitrate and urea/.

•F ž - .·

The following examples illustrate, but do not limit, the subject matter of the invention.

Example 1 to 5

In laboratory conditions, individual liquid concentrates of these biogenic elements were prepared for the purpose of conducting follow-up biological tests: magnesium, copper, zinc, iron and manganese.

The tests used the liquor resulting from the sulphite cooking of cellulose, after its treatment by the fermentation process, after the distillation of alcohol and concentration. The sulphite stills thus obtained contained 47.46% by weight of dry matter and 2.10% by weight of calcium.

When preparing individual samples, the procedure was as follows: to 100.00 g of sulfite calcinations, a weight of distilled water was added, as well as the calculated amount of crystalline sulfate of the biogenic element.

The reaction mixture was then kept under reflux with stirring for 1 hour at a temperature of 75-85°C.

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

1 1287

The weights of the basic components and also the concentration of the respective biogenic element in the individual prepared samples are given in the table:

Example Weights of reactants in g Concentration of the biogenic element in the product in % Sulphites shots /47.46 2/ Distilled water Amount and type of sulfate used I 100.0 368.0 12.92 g MgSO ₄ .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 ZnS0 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 MnSO ,4H 0 0.60

By separating the calcium sulfate formed during the reaction, an average of 460 g of liquid concentrate and approximately 9 g of dry calcium in the form of CaSO4.2H ₂ O were obtained.

Example 6

Into a tall beaker with a volume of about 300 cm was weighed 4.2 g of titanium dioxide /TiO ₂ / in the form of so-called titanium white, 5.4 g of concentrated sulfuric acid containing 95% MH - H ₂ SO^ was added and the mixture was heated on a stove equipped with an asbestos mesh with occasional thorough stirring. After thickening, the reaction mixture was moistened with a small amount of distilled water and after about 2 hours of heating and almost complete evaporation, it was allowed to cool freely. After cooling, the reaction mixture - the residue - was evaporated under 11 250 cm of cold distilled water. As a result of the complete decomposition of the oxide with concentrated sulfuric acid, an almost clear solution of titanium oxysulfate was obtained by dissolution.

3

Into a second beaker with a volume of about 600 cm was placed 100.0 g of concentrated sulfite calcinations of the same composition as in examples 1 to 5. 125.0 cm^ of cold distilled water (temperature approx. 25 °C) was added to the weighed sulfite calcinations. After homogenizing the calcinations with water, the entire volume of an aqueous solution of titanyl sulfate, prepared by reacting Ti0 ₂ with sulfuric acid, was added to the prepared dark brown solution. The mixture was stirred for about an hour and then the precipitated gypsum sludge was separated from it by filtration.

Approximately 450 g of a solution containing about 0.52 wt% titanium was prepared by the above method. Washing and drying the filter cake yielded 8.4 g of CaSO4.2H ₂ O.

Example7

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

variant after dark, . length weight 1 growth in cm in Z in g in Z NPK 16.4 100 0.580 100 NPK +Mn 17.1 104.3 0.653 112.6

Example 8

Oat plants of the Diadem variety were grown in soil deficient in honey, to which a nutrient solution of NPK and, in one case, honey in the form of a pripra5 preparation was added before planting the seeds.

1 1287 applied by the method according to the invention in a dose corresponding to 18 kg Cu-ha. The plants were kept in a greenhouse with controlled watering and 32 days after the start of the experiment, the postmortem length of the plants and the weight of the dry aboveground mass were determined.

Variant postmortem. length in cm % weight in g/container Z

NPK 2 7.06 100 0.890 NPK + Cu 29.80 110.1 '0.971

100 109, 1

Example 9

A leveled stand of wheat of the Grana variety in the tillering phase was foliarly fertilized with a nitrogen solution DAM-390 at a dose corresponding to 30 kg N per ha and with a mixture of a nitrogen solution and a tested magnesium concentrate prepared by the method according to the invention from MgSO^ and concentrated sulphite calcinations, at a dose corresponding to /30 kg N + 6 kg Mg/ per ha. The increase in grain yield reached 117.5, respectively. up to 141.5 Z.

Grain variant

t.ha ¹ From c 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 of the Dobrovicka A variety on soil with magnesium deficiency was foliarly fertilized 22.6, both by using a concentrate containing magnesium from magnesium sulfate and concentrated sulfite leachate according to the method according to the invention in a dose corresponding to 6 kg Mg.ha and secondly by kieserite, by spreading solid fertilizer in a dose corresponding to 30 kg Mg.ha. The yield of tubers was recorded at harvest, the performance of qualitative analysis for sugar content and the yield of raffinate was calculated /tab. /. The yield of tubers in both cases of fertilization increased compared to the control by more than 4%, the yield of raffinate decreased compared to the control after the tested fertilizer by 14.4%, after kieserite by 3.4%.

Variant bulb harvest refined product yield t.ha From t. ha 7. control 5.41 100 5.85 100 test 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

Corn plants, hybrid TO-510, were grown on soil deficient in zinc, to which a nutrient solution of NPK was added before sowing the seeds and in one case also zinc in the form of a Zn concentrate prepared by the method according to the invention in a dose corresponding to 17 kg Zn ha. The plants were maintained in a greenhouse with controlled watering and the weight of the dry aboveground mass was determined 3 days after the start of the experiment.

Variant Dry matter weight in g/container Z

NPK

NPK + Zn

1.63

1.72

100

105.5

Example 12

A leveled stand of wheat of the Slavia variety was foliarly fertilized in the early tillering phase with a Mg concentrate prepared by the reaction of MgSO4 and concentrated sulfite sludge according to the method according to the invention in a dose corresponding to 6 kg Mg.ha. The effect was indicated by the grain yield in comparison with the unfertilized control.

Grain harvest variant

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 secondary application of Fe-concentrate prepared by the method according to the invention in a dose of 500 g to the barley tree and 4-fold. by spraying in a concentration of 0.4 7 we found a curative effect /gradual greening of vegetative organs/ and subsequent increases in apple yield per 1 ha.

Variant

Soil application Foliar plant application Harvest 7 Harvest 7 in t.ha in 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, localities Vištuk, district Bratislava-vidiek and Vrbové, district Trnava, with the soil application of 200 g of Fe - concentrate according to the invention per 1 bush of vine, we found a curative effect and an increase in grape yield.

Variant Harvest t. ha Vistuk 7 1 Willow Harvest - 1 t.ha 7 Control 6,280 100.00 7,400 100.00 Fe-concentrate 6,580 104.77 10.440% 141 .08 positive 15 Culture - grapevine, r. 1980, Muller variety Thurgau, Vištuk locality, Bratislava district

countryside.

Grapevine with visually diagnosed Fe deficiency /typical chlorosis - physiological yellowing of vegetative organs due to lack of Fe in plant tissues/. After 4-fold application of Fe-concentrate produced by the method according to the invention in a concentration of 0.4% by spraying on the leaf together with pesticide preparations, we found a curative effect /gradual greening of plant tissues/ and an increase in grape yield by 18.8% compared to the untreated control, while we did not find any deterioration in 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.