RU2054404C1 - Organomineral fertilizer - Google Patents

Abstract

FIELD: fertilizers. SUBSTANCE: organomineral fertilizer has organic component, mineral component (N, P, K, Mg) and trace elements (Mo, Mn) and, additionally, calcium, elemental sulfur, chlorocholine chloride, dimethylsulfoxide and binder. Organic component - modified hydrolyzed lignin where humic carbon content is 25-46 wt.-% of total carbon at the following ratio of active substances in fertilizer, wt.-%: nitrogen 8-14; phosphorus 6-9; potassium 6-9; calcium 20-28; magnesium 2.3-3.2; elemental sulfur 2.7-4.0; molybdenum 0.04-0.06; manganese 0.13-0.20; chlorocholine chloride 0.43-0.54; dimethylsulfoxide 1.4-2.0; modified hydrolyzed lignin 32-47, and binder 1-3. EFFECT: enhanced quality of fertilizer proposed. 4 tbl

Description

 The invention relates to the production of organomineral fertilizer, namely, a complex slow-acting organomineral fertilizer intended for growing crops, in particular wheat.

 A long-acting complex granular mineral fertilizer is known [1] containing a core of nutrients (nitroammophosk, urea, calcium carbonate, magnesium oxide, elemental sulfur, ammonium molybdate, manganese chlorate) bonded with cationic polyurethanesemicarbazide with a number of ion centers of 0.8-1.1 meq / g of polymer. The core of the granule is covered with a fertilizer layer containing foundationazole, 2.4-D-butyl ether, hexachlorocyclohexane, chlorocholine chloride and nutrients. Such a granule is coated with a two-layer shell, the first layer of which is located on a fertilizer layer containing foundationazole and other substances, contains a mixture of polyurethanesemicarbazide with dimethyl sulfoxide, and the integumentary, second layer is cationic polyurethanesemicarbazide.

 The structure of this fertilizer allows you to release the necessary agrochemical substances in the phases of plant development. The disadvantage of this fertilizer is the use of a fairly significant amount of polymer in its composition (8-10 wt.% Of the mass of agrochemical substances), which increases the price of fertilizer, and with prolonged use in the soil, the decomposition products of this polymer can accumulate.

 In order to slow down the process of nutrient release from fertilizers, it is most advisable to use hydrolysis lignin and its processed products in the form of composts with mineral fertilizers, in this case, the sorption properties of hydrolysis lignin are used. It retains mineral components, protects them from rapid washing out by atmospheric precipitation and creates the conditions for their constant presence in the soil layer and, therefore, gradual assimilation by plants.

 It is known to use various mineral fertilizers (phosphorite flour, ammonium nitrate, potassium chloride and many others) for composting hydrolytic lignin, and their ratios are determined by the needs of the soil and cultivated agricultural crop.

 Known fertilizer based on lignin [2] containing the degradation product of hydrolytic lignin, one or more alkaline earth metal compounds (hydroxides or salts of Ca, Mg, Ba), one or more compounds of transition elements of the III-YIII groups of the periodic system (salts or oxides of Mo, Mn , B, Zn, Co, Cu, Fe) and phosphorus-containing compounds.

 Such a fertilizer is highly effective when applied to humus-poor soils, since it contains humus-like substances from the degradation product of hydrolytic lignin.

 However, this fertilizer does not contain all the necessary complex of nutrients and other substances that optimally ensures the development of cereal plants, which affects their growth, resistance to adverse conditions and productivity.

 It is known organic-mineral fertilizer based on lignin [3] obtained by nitration oxidation of lignin with nitric acid at the moment of its formation, released during the interaction of a mixture of powdered lignin and potassium nitrate in a ratio of 1: (1-1.5) with phosphoric acid with a ratio of the amount of lignin mixture and potassium nitrate and phosphoric acid 1: (1.7-2.0) for 30-60 minutes, followed by neutralization with carbon ammonium salts.

 The chemical composition of the final product, wt. total phosphorus 32.7-33.2; total nitrogen 12.8-16.8; organic nitrogen 3.6-3.8; potassium 7.6-8.4; organic matter 15.1-18.1; carboxyl groups 12.7-12.9; the amount of nutrients 70.2-73.5.

The fertilizer contains a set of nutrients consisting only of phosphorus (P), nitrogen (N), potassium (K), as well as organic matter, the content of which, including and C _gum. increased compared to the original after the modification of hydrolytic lignin.

 However, this composition of the fertilizer does not provide activation of metabolic processes in plants and does not significantly affect the soil absorption complex, since calcium and magnesium are not included in its composition. It is the joint content of Ca, Mg and organic matter that creates the conditions under which the physicochemical processes improve.

The closest in technical essence to the invention is a universal organomineral fertilizer biostimulator [4]
The fertilizer contains an organic component (not less than 70 wt.) Based on humic acids contained in a selected of a number of substances: lignin, brown coal, a mixture of brown coal with manure, peat or cellulose-based materials; 0.2-0.5 wt. biostimulants per dry matter and the rest up to 100 wt. mineral component and trace elements.

The mineral component contains N, P ₂ O ₅ , K ₂ O, and trace elements Cu, Fe, Mg, Mo, Co, B, Zn, etc.

 Biostimulants are selected from the groups: riboflavin, allantoin, tryptophan, glutamic acid, allantoic acid and others.

 This fertilizer contains a set of substances to increase yield. Due to the presence of an organic component based on humic acids, this fertilizer structures the soil and resists the process of leaching nutrients into deep layers and groundwater due to the sorption properties of the organic component.

 However, the organic part of this fertilizer (peat, manure, cellulose, wood waste, as well as hydrolytic lignin without its modification) is poor in humic acids. The latter are formed as a result of humification of these substances in the soil under the influence of soil microorganisms and this process has been going on for several years.

 It is known about the inhibitory effect on the growth of plants using only one hydrolysis lignin as a fertilizer, therefore, the use of hydrolysis lignin as an organic part of the fertilizer in an amount of 70-80 wt. will lead to inhibition of plant growth.

 The mineral part of the fertilizer contains the composition of macroelements: nitrogen (N), phosphorus (P), potassium (K), magnesium (Mg), as well as a large set of trace elements, which is not always advisable. In the soil, some trace elements may already be present in significant quantities, so the introduction of an additional amount of them, especially in the case of iron (Fe) and especially zinc (Zn), will cause pollution of the soil, and then plants with heavy metals.

 At the same time, calcium (Ca) is not included in the fertilizer, which may adversely affect the soil-absorbing complex, the essential components of which are magnesium (Mg), calcium (Ca) together with organic substances.

 The soil-absorbing complex is an important component of soil enrichment with nutrients, as it regulates the physicochemical processes in the soil, creating its lumpy structure and preventing nutrients from migrating into deep layers inaccessible to plants.

 The objective of the invention is to create such an organomineral fertilizer that would allow, by selecting certain ratios of agrochemical substances in it, to improve soil fertility and its structure, as well as to enhance the metabolic processes of cereal plants.

The problem is solved in that in an organomineral fertilizer containing as an organic component a material containing humic acids, as a mineral component nitrogen, phosphorus, potassium, magnesium, and as trace elements molybdenum, manganese, calcium, elemental sulfur, chlorocholine chloride are introduced according to the invention , dimethyl sulfoxide and a binder, and as a material containing humic acids, a modified hydrolysis lignin in which humic carbon is 25-46 wt. from C _total in the following ratio of active substances (AI) in fertilizer, wt. Nitrogen 8-14 Phosphorus 6-9 Potassium 6-9 Calcium 20-28 Magnesium 2.3-3.2 Elemental sulfur 2.7-4.0 Molybdenum 0.04-0.06 Manganese 0.13-0, 20 Chlorocholin chloride 0.43-0.54 Dimethyl sulfoxide 1.4-2.0 Modified
hydrolysis lignin 32-47 Binder 1-3
In the proposed composition of organomineral fertilizer, hydrolytic lignin is introduced after its chemical modification and in a certain ratio with other agrochemical substances. In the process of chemical modification, mono- and oligomeric derivatives containing functional groups are formed from the macromolecule of hydrolysis lignin, which determine the reactivity of the modified hydrolysis lignin. The most important of them, as in the components of humus-humic and fulvic acids, are carboxyl and phenol-hydroxyl groups. When interacting with the mineral elements of the soil, the products of the modification of hydrolytic lignin form heteropolar salts and complex complex organomineral compounds that fix easily moving elements in the soil, which prevents their migration into deep layers and leaching. Subsequently, these compounds are fully used by plants and soil microflora as organomineral nutrients.

 The ability to complexation allows the modified hydrolytic lignin, when combined with the mineral elements of both the fertilizer and soil, to exhibit the properties of a complex slow-acting organomineral fertilizer that uniformly provides plants with mineral and organic nutrients during the growing season.

 Mono- and oligomeric derivatives of modified hydrolysis lignin are similar in chemical nature to soil humic substances. Consequently, the modification of hydrolytic lignin leads to an accelerated conversion of hydrolytic lignin macromolecules to soil humic substances, bypassing the processes of their long-term transformation by microorganisms.

 Virulent microflora of the soil when fertilizing based on modified hydrolysis lignin is inhibited to a greater extent than other groups of microorganisms. This is due to the fact that it has a powerful destructive enzyme system and uses modified lignin as an energy material. Mono- and oligomeric derivatives formed upon modification of hydrolysis lignin exhibit fungicidal properties. As a result of this, they inhibit the development of virulent microflora of the soil and thereby contribute to the protection of the plant root system from diseases. Inhibition of virulent microflora vital activity leads to a shift in soil microbocenosis towards the development of beneficial microflora, soil improvement due to a decrease in the number of toxic metabolites of virulent microflora vital activity, and consequently, ecology.

 When a modified hydrolysis lignin is combined in a fertilizer with the main nutrients (nitrogen, phosphorus, potassium, etc.), complex organomineral compounds are formed. The latter, under the influence of plant root excretions of organic acids, are destroyed into ions, absorbed by the plant roots and assimilated by them. The conversion rate of these complexes is regulated by the physiological state of plants and their need for nutrients at a specific development phase, as well as by the state of the soil-absorbing complex, which is beneficially affected by the combined presence of calcium, magnesium and the organic component (modified hydrolysis lignin) of the fertilizer.

 The physiological status of the plant increases due to both the presence of the growth regulator of chlorcholine chloride and the membrane-active substance dimethyl sulfoxide in the organomineral acquisition, and the presence and entry into the plants of growth regulators and quinone groups of the most modified hydrolytic lignin exhibiting physiological activity. Such a joint content of the organomineral part with growth regulators and a membrane active substance allows, firstly, due to the formation of complex compounds between the organic and mineral parts of the fertilizer, to ensure the slow release of nutrients from these complexes, and, secondly, due to the action of the membrane active substance and regulators growth enhance the activity of absorption of nutrients by the root system. It is thanks to the formation of these complexes and their slow destruction that the plants are provided with nutrients during their growing season, which avoids multiple nitrogen top dressing of grain crops during their cultivation using intensive technologies.

 Increasing the efficiency of use of each component contained in the granule, which is regulated by the physiological state of the plant and the need for nutrients at each phase of its development, as well as strengthening the assimilation of nutrients entering the tissue, leads to an increase in yield and an improvement in its quality.

 The ratio of agrochemical substances of the proposed organic fertilizer were selected experimentally, based on the need for them cereal plants, in particular wheat. A smaller number of them than represented by the minimum limit of the claims does not satisfy the physiological needs of plants, a larger number of them leads to a saturation of the soil with these compounds.

 This is due to the fact that only the physiological norm of nutrient elements is assimilated by plants in each specific development phase and exceeding it leads to their inefficient expenditure.

The degree of modification of hydrolytic lignin was also determined experimentally. It is characterized by the content of humus carbon (C _hum. ) After modification in the range of 25-46 wt. from C _total

The indicated degree C _gum. is achieved by any of the known methods for modifying hydrolytic lignin with nitric acid formed at the moment of its isolation, for example, by the interaction of sulfuric acid with ammonium nitrate, and depends on the quantitative ratio of the substances involved in the reaction and on the type of feedstock for producing hydrolytic lignin.

 An increase in the amount of sulfuric acid involved in the reaction does not lead to a significant increase in the degree of modification of hydrolytic lignin, but only to an increase in the free acidity of a product that requires neutralization. An increase in the amount of ammonium nitrate involved in the reaction slightly increases the degree of modification of hydrolytic lignin, while at the same time leads to an increase in nitrate nitrogen in the product, which reduces its environmental value.

 To bind agrochemicals into the granule, a binder is introduced into the fertilizer, in the form of a 10% aqueous solution of any of the polymers or other substances (for example, sapropel), which are widely recommended for use in the production of organic fertilizers. The amount of active substance (d.v.) was determined experimentally for the following binders: cationic polyurethanesemicarbazide with the number of ion centers of 0.8-1.1 meq / g of polymer; polyacrylamide; carboxymethyl cellulose; sapropel and amounted to 1-3 wt. to the weight of the fertilizer. A smaller amount of binder does not allow to obtain durable, resistant granules. A further increase in the amount of binder is not economically justified.

This fertilizer in laboratory conditions is obtained as follows. Powdered hydrolysis lignin and ammonium nitrate (NH ₄ NO ₃ ) are placed in a reactor, 50% sulfuric acid (H ₂ SO ₄ ) is added to them and the mixture is stirred vigorously for 30-60 minutes at room temperature. Then, the obtained modified hydrolysis lignin is added with preliminarily powdered and thoroughly mixed nutrients (nitroammophoska, urea, calcium carbonate, magnesium oxide, elemental sulfur, ammonium molybdate, manganese chloride) and the growth regulator chlorocholine chloride taken in the amounts shown in the examples in the tables. one.

 The mixture is thoroughly mixed until a homogeneous mass. The moist crumbling mass is transferred to a granulator and, with constant rotation at a speed of 100-120 rpm, a 10% aqueous binder solution in the amount of 2/3 parts of the initial volume is added in small portions (5-10 ml) using a spray gun. Types of binder, the amount of its preparative form, as well as the amount of active substances in them, etc. are presented in table. 12.

Formed fertilizer granules are classified on sieves. The optimal granule size is from 2 to 3 mm. Fertilizers Granules of this size are dried in an oven at 40-45 ^{° C} for 10-12 hours. The granules smaller than 2 mm and more than 3 mm are ground and recycled to granulator to obtain a new portion of the desired size granules.

 Dry granules of the required size are poured into the granulator and treated at a speed of 100-120 rpm with a pre-prepared mixture of an aqueous binder solution (1/3 remaining from the pre-prepared solution) with dimethyl sulfoxide (DMSO) (see tables 1 and 2) .

Then the fertilizer granules with DMSO applied to their surface are removed from the granulator, dried in a thermostat at a temperature of 40-45 ^о С for 6-8 hours or in the open air for 10-12 hours.

The result is a granular organomineral acquisition containing macro- (N, P, S, K, Ca, Mg), microelements (Mo, Mn), a growth regulator chlorocholine chloride, a membrane-active compound dimethyl sulfoxide, which simultaneously serves as a cryoprotectant and the organic component of the modified hydrolytic lignin, With _gum. which 25-46 wt. from C _total

The study of the effect of organic fertilizer on the vegetation cycle of the development of cereal plants was carried out under physiologically accurate vegetation experiments. Vegetation experiments in a 20-fold repetition were carried out in Wagner vessels with a capacity of 8 kg of soil. For stuffing the vessels, meadow chernozem podzolic soil was used. Organomineral fertilizer was introduced into the soil of the experimental vessels, characterized by the composition shown in examples 4-8 of the table. 1, in the amounts indicated in the table. 3, examples 4 and 8. These amounts of fertilizer in terms of basic nutrients correspond to the amount of active substance N _{1.2 g} ; P _{0.8 g} ; To _{0.8 g} .

For comparison, similar experiments were carried out when growing cereal plants in vessels, in the soil of which they introduced:
And an equivalent amount of only one modified hydrolysis lignin (example 2, table 1);
An equivalent amount of agrochemical substances was used, and instead of the modified hydrolysis lignin, hydrolysis lignin was taken (Example 3 of Table 1).

Fertilizer was introduced into the soil of the control vessels in the form of a mixture of 4.7 g of nitroammophos and 0.8 g of urea, which corresponds to the amount of the active substance N _{1.2 g} ; P _{0.8 g} ; To _{0.8 g} (example 1 of table. 1).

 In more detail, the invention is illustrated by the examples 4-17 table. 1, in each of which for the preparation of organic fertilizer agrochemical substances are taken in the following ratio (see table. 1).

 The content of basic (NPK) nutrients in the composition of the fertilizer and its quantity introduced into the vessel with the soil according to a laboratory experiment comparing the effects of different quantitative (within the active substances protected by the claims) and qualitative (composition of organic fertilizers protected by the claims; composition organic fertilizer with hydrolytic lignin; composition of the fertilizer containing only nutrients; composition of the fertilizer containing only one anny lignin) it is shown in Table. 3.

 The results of the analysis of the influence of organic fertilizer on the vegetation cycle of plant development according to the laboratory experiment and similar results of comparative experiments are statistically processed and are given in table. 4.

Plants were grown to full ripeness without further feeding. Soil moisture was maintained constant during the growing season at 60 or 70% of the total moisture capacity. During the vegetation of plants, the passage of the phases of growth and development, the degree of damage to their diseases, in particular root rot, the formation of the root system and its functional activity were monitored. The phases of plant development in leaves, stems, roots, and ears determined the activity of the key enzyme of nitrogen metabolism of nitrate reductase, the content of nitrates and various forms of nitrogen, as well as other elements. At the end of plant vegetation, the morphological structure of the stem, the structural elements of the crop, the content of protein nitrogen and protein, dry and crude gluten, and the amino acid composition of acid hydrolysates of grain flour were studied. The results were obtained from 5-7 parallel determinations, were processed on a SM 1 computer. The determination error in each case did not exceed 5-7%
As can be seen from the analysis of the data presented in table. 1-4 when using organomineral fertilizer (examples 4-8, Tables 1, 3), a manifestation of synergism was observed in the effect on cereal plants of all components of the fertilizer: physiologically active substances of the growth regulator of chlorocholine chloride and the membrane-active substance of dimethyl sulfoxide; minerals containing nitrogen, phosphorus, potassium, calcium, magnesium, elemental sulfur, molybdenum, manganese, and the organic component of the modified hydrolysis lignin containing C _gum. 25-46 wt. from C _total

 Thus, the proposed organomineral fertilizer, due to the selection of a certain ratio of agrochemical substances, improves the structure of the soil and increases its fertility, as well as accelerates the metabolic processes of cereal plants, as a result of which it increases the grain yield of plants by 35-48 wt. compared with comparative experiments (examples 2, 3 of the table. 1, 3, 4) and control (example 1 of the table. 1, 3, 4).

 The content of protein, gluten and amino acids in the hydrolysates of grain flour of experimental plants for examples 4 and 8 (experiments with fertilizer according to the invention) was also higher by 30-40 wt. compared to control.

 The manifestation of synergism was also confirmed by a sharp increase in nitrate reductase activity and photosynthesis intensity, which can be explained both by the favorable effect of fertilizers according to the invention on the soil-absorbing complex, soil structure, humification and accumulation of nutrients in the soil in the form of organomineral complexes, and the slow intake of nutrients into plants according to physiological needs at each phase of development during the growing season.

 As a result of the enrichment of plant tissues with mineral elements, in particular nitrogen, and also the enhancement of the physiological status of plants due to the introduction of the membrane-active substance dimethyl sulfoxide and the growth regulator of chlorocholine chloride, as well as growth regulators present in the modified hydrolysis lignin, the processes of biosynthesis and storage of transporting substances to the kernels are enhanced, their accumulation, which leads to increased yield and improved grain quality.

Claims (1)

ORGANOMINERAL FERTILIZER, comprising an organic component based on humic acids, nitrogen, phosphorus, potassium, magnesium, containing components, as well as salts of trace elements molybdenum and manganese, characterized in that it additionally contains calcium, elemental sulfur, chlorocholinchloride, dimethyl sulfoxide and a binder, and in the quality of the organic component is a modified hydrolysis lignin with a humic carbon content of 25 - 46 wt.% of the total carbon in the following ratio of active ingredients in fertilizer, wt.%:
Nitrogen - 8.00 - 14.00
Phosphorus - 6.00 - 9.00
Potassium - 6.00 - 9.00
Magnesium - 2.30 - 3.20
Calcium - 20.00 - 28.00
Elemental Sulfur - 2.70 - 4.00
Molybdenum - 0.04 - 0.06
Manganese - 0.13 - 0.20
Chlorocholin chloride - 0.43 - 0.54
Dimethyl sulfoxide - 1.40 - 2.00
Modified hydrolysis lignin - 32.00 - 47.00
Binder - 1.00 - 3.00

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