RU2826766C1 - Method of producing chelate complexes based on bioactive salts of lignosulphonic acids and biogenic metals - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a method for synthesis of chelate complexes based on lignosulphonates and biogenic metals used in agriculture as microfertilizers, in animal breeding as a fodder additive, as well as in production of food microelement additives. Method of producing chelate complexes is characterized by that nitration of lignosulphonates is carried out by adding 15–20 wt.% aqueous solution of lignosulphonates of nitric acid solution with concentration of 30.0–55.0 wt.% with constant stirring and maintaining temperature in range of 25–35 °C. Salts of inorganic biogenic metals are added with constant stirring and while maintaining temperature within 35 to 50 °C not earlier than 30 minutes after completion of addition of nitric acid. After dissolution of all components, the solution is stabilized step-by-step by adding KOH or NH₃⋅H₂O to achieve pH 3.0–3.5 for 30 minutes, after which the solution is finally stabilized by adding potassium hydroxide or ammonium hydroxide to achieve pH 4.5–5.5 for 60 minutes.

EFFECT: providing long-term stability of the liquid target complex with high concentration of retained biogenic metals.

4 cl, 2 tbl, 5 ex

Description

The invention relates to a method for producing chelate complexes based on organic complexones and biogenic metals. The use of chelate complexes ensures much greater availability of microelements when used in agriculture, as microfertilizers, in livestock farming for cattle and poultry, as a feed additive, and also in the production of food microelement additives.

Complexones based on EDTA and Glycine perform only the transport function of delivering biogenic metals, but in themselves are ballast compounds for soil, plants or animals. At the same time, EDTA salts are not permitted in Russia and the EU for the production of feed additives. Unlike EDTA complexones, chelate complexes according to the proposed technology, obtained on the basis of lignosulfonic acids transformed by nitration, in addition to the chelating and transport functions, contain natural components that are valuable for plant and animal nutrition: a wide range of amino acids and vitamins, fulvic-humic acids, high-molecular carbohydrates in the form of mono- and polysaccharides [1], [2].

An important feature of the proposed technology is the ability for the manufacturer to refuse importing expensive EDTA and Glycine complexones and to implement its own production of complexones in one technological chain with the production of chelate complexes. At the same time, the initial raw material, Technical Lignosulfonate (LST), is a relatively cheap and accessible raw material that is used to produce organomineral fertilizers, growth stimulants, for the production of feed and food additives and even pharmaceuticals. This raw material is produced and sold in Russia in large volumes, both for the domestic market and for export.

The prior art includes patent for invention of the Russian Federation 2165936 dated 27.04.2001.

The invention concerns a method for producing a lignosulfonate iron chelate, which can be used in agriculture and veterinary medicine. The essence of the invention consists in mixing a chelating agent with a salt of di- or trivalent iron, wherein nitrosated lignosulfonic acids formed at the stage of preparing the chelate are used as the chelating agent, and iron salts are introduced in two stages.

To achieve maximum iron chelate capacity, the remaining amount of iron salt is added to the chelate solution after completion of the nitrosation reaction.

The Russian Federation patent 2660929 of 11.07.2018 declares an ORGANIC COMPONENT OF A NUTRIENT MIXTURE FOR PLANTS, LST modified by nitration is used, using concentrated nitric acid, the nutrient mixture is synthesized as follows. 1 ml of concentrated nitric acid (concentration 63.6%) was added to 100 ml of a 10% LST solution. The nitration duration was 60 min. After completion of nitration, the following nutrients were dissolved in the reaction mixture with stirring (in % of the mass of the initial LST: FeSO ₄ ⋅7H ₂ O - 80; H ₃ BO ₃ - 7.4; ZnSO ₄ ⋅7H ₂ O - 14.2; CoCl ₂ ⋅6H ₂ O - 3.9; (NH ₄ ) ₆ Mo ₇ O ₂₄ ⋅H ₂ O - 28.9; MnCl ₂ ⋅4H ₂ O - 11.6; MgSO ₄ ⋅7H ₂ O - 32.6; CuSO ₄ ⋅5H ₂ O - 12.6; urea - 100; K ₂ HPO ₄ ⋅3H ₂ O - 1.5). Wheat germination was monitored. Germination was carried out for 7 days, monitoring the height of the sprouts and the length of the roots. The average height of the plants was 16.0 cm, the weight of all plants was 6.6 g (on absolutely dry matter).

The specified method according to Russian patent 2660929 is the closest in technical essence and is taken as a prototype.

The technical task, the solution of which is aimed at creating the developed method, is the development of a continuous technological cycle for obtaining liquid chelate complexes with high chelate capacity, based on a complexone, which is transformed by nitration of LST in a mixture with cations of biogenic metals.

The technical result of the method consists in ensuring long-term stability of the liquid chelate complex at a high concentration of retained biogenic metals.

The peculiarity of the proposed method and production of chelate complexes is that a continuous technological cycle is proposed based on an improved method of nitration of technical LST, providing a high effect of chelation and retention of the cation with minimal foaming and emission of nitrogen oxides.

The technology of nitration is carried out under the developed conditions of the process (time, temperature, sequence of actions, kinetics) and the selected optimal balance of active components in the reaction mixture. This allowed to ensure effective complex formation and to retain ions of biogenic metals in concentrations not inferior or even exceeding the results of other technologies for the production of chelate complexes.

The essence of the method for obtaining chelate complexes includes nitration of an aqueous solution of technical lignosulfonates (TLS) using nitric acid, followed by the addition of inorganic salts of biogenic metals.

The key parameters of the method (technology) are the balance and concentration of the components, the nitration time, the temperature of the reaction mixture, the rate and sequence of dissolution of the salts of biogenic metals, as well as the time and method of stabilizing the solution until the finished liquid chelate complex is obtained. Thus, in the course of research it was determined that the maximum reactivity of chelation was observed when adding salts of biogenic metals no earlier than 30 minutes after adding nitric acid.

The transformation of LST is carried out by nitration with the addition of diluted nitric acid with a concentration of 30.0 ÷ 55.0% by weight to a 15 ÷ 20 wt.% aqueous solution of LST with constant stirring and maintaining temperatures within the range of +25.0 to +35.0 °C, and salts of inorganic biogenic metals are added with constant stirring and maintaining the temperature within the range of +35.0 to +50.0 °C, not earlier than 30 minutes after the completion of the addition of nitric acid. After dissolving all components, the solution is gradually stabilized by adding potassium hydroxide or ammonium hydroxide until a pH of 3.0 ÷ 3.5 is reached within 30 min. After dissolving all components, the solution is finally stabilized by adding potassium hydroxide or ammonium hydroxide until a pH of 4.5 ÷ 5.5 is reached within 60 min.

Inorganic salts of biogenic metals copper, zinc, manganese, iron, calcium, magnesium, cobalt are added to their individual or total content in the chelate complex up to 16% in terms of absolutely dry matter.

To increase biological activity, when pH reaches 5.0÷5.5, fulvohumic acid salts are added to the solution with constant stirring, with a content of up to 15% in terms of absolutely dry matter.

To increase biological activity, when pH 5.0÷5.5 is reached, melamine salt of bis(oxymethyl)phosphinic acid is added to the solution with constant stirring until its content in the solution reaches ^10-6 % to ^10-7 %.

Example #1

Preparation of sample No. 1 of a multi-component composition based on sodium lignosulfonate, to test the biological effectiveness in pre-sowing treatment of winter wheat seeds.

The preparation of the multicomponent microelement composition was carried out in a laboratory equipped with a fume hood.

A 2-liter glass reactor with heating and an adjustable magnetic stirrer was used.

30 ml of nitric acid (55.0% concentration) were added to a 19% aqueous solution of technical sodium lignosulfonate (850 ml).

The nitration duration was 30 min at a set temperature of +25.0°C.

After completion of nitration, the temperature in the reactor is increased and maintained in the range of +35.0÷45.0°C

With constant stirring, inorganic salts of biogenic metals “chemically pure” and boric acid are added in the following quantities: CoSO ₄ ⋅7H ₂ O - 4.0 g, CuSO ₄ ⋅5H ₂ O - 10.0 g, MnSO ₄ ⋅H ₂ O - 25.0 g, ZnSO ₄ ⋅H ₂ O - 25.0 g, FeSO ₄ ⋅7H ₂ O - 50.0 g, MgSO ₄ ⋅7H ₂ O - 25.0 g, H ₃ BO ₃ - 10.0 g, (NH ₄ ) ₆ Mo ₇ O ₂₄ ⋅4H ₂ O - 1.0 g.

Each subsequent ingredient is added to the reaction mixture after the previous one has completely dissolved.

After all components of the mixture had completely dissolved, the reactor heating was turned off in order to reduce foaming, and the mixing intensity was reduced.

Stabilization of chelation at the final stage was achieved by the stepwise addition of ammonium hydroxide (concentration 25.0%) to the reaction mixture.

The first stage of stabilization was carried out by adding 20 ml of ammonium hydroxide until the solution pH reached 3.0÷3.5, the stirring time was about 30 minutes.

The second stage of stabilization was carried out after completion of the first, by adding the required amount of ammonium hydroxide to achieve the solution pH = 4.8÷5.2, the mixing time was about 60 minutes.

The pH values of the aqueous solution were determined using a laboratory pH meter throughout the stabilization stage.

As a result of the reactions, multicomponent chelate complexes of transformed LSTs were obtained with the following calculated values of the components:

- sulfur content - up to 2.0%

- total nitrogen content in solution - up to 0.75%

- total dry matter content - 26.1%.

- total content of biogenic microelements - 11.95% on an admixture basis.

- Boron content - 0.57% on an absolutely dry basis.

- Molybdenum content - 0.17% on an absolutely dry basis.

Of these, chelated:

- Cobalt content - 0.27% on an absolutely dry basis.

- Copper content - 0.82% on an absolutely dry basis.

- Manganese content - 2.63% on an absolutely dry basis.

- Zinc content - 2.94% on an absolutely dry basis.

- Iron content - 3.73% on an absolutely dry basis.

- Magnesium content - 0.81% on an absolutely dry basis.

- total content of organic matter - 56.3% on an absolutely dry basis.

The obtained sample No. 1 is divided into two parts.

The first part was collected and placed in a plastic bottle and hermetically sealed for arbitration storage. The shelf life was 4 years. During the entire storage period of sample No. 1, no sedimentation, stratification, color change or gas formation were observed.

The second part of the obtained sample was sent for biological activity studies and laboratory testing.

The biological efficiency test was carried out on winter wheat seeds, variety “Adel” at the Kuban State Agrarian University named after I.T. Tribulin. Field tests [5]. Pre-sowing seed treatment, at the rate of 1 liter of sample per 1 ton of seeds. The test results are presented for two key indicators - yield and grain quality [6], [7].

1. Productivity exceeded the control variant, from 42.2 to 45.9 c/ha, in the control - 39.6 c/ha. NSR ₀₅ - 2.0 c/ha.

2. The content of crude gluten in the grain was 18.5%, in the control 17.0%. - the protein content in the grain was 14.8%, in the control 14.0%.

Example #2

Preparation of sample #2 based on magnesium lignosulfonate with chelated iron for testing biological efficiency in germination of barley hydroponic cattle feed.

The preparation of the chelated iron(II) sample was carried out in a laboratory equipped with a fume hood.

A 2-liter glass reactor with heating and an adjustable magnetic stirrer was used.

In a 18.5% aqueous solution of technical magnesium lignosulfonate, volume 800 ml, 32 ml of nitric acid (concentration 52.5%) were added.

The nitration duration was 45 min at a set temperature of +28.0°C.

After completion of nitration, the temperature in the reactor is increased and maintained in the range of +40.0÷45.0°C.

With constant stirring, FeSO ₄ ∙7H ₂ O “chemically pure” - 300.0 g is added in 50 g portions.

Each subsequent sample is added to the reaction mixture after the previous one has completely dissolved.

After the entire volume of iron sulfate had completely dissolved, the reactor heating was turned off in order to reduce foaming, and the mixing intensity was reduced.

Stabilization of chelation at the final stage was achieved by the stepwise addition of ammonium hydroxide (concentration 25.0%) to the reaction mixture.

The first stage of stabilization was carried out by adding 25 ml of ammonium hydroxide until the solution pH reached 3.0÷3.5, the stirring time was about 35 minutes.

The second stage of stabilization was carried out after the completion of the first, by adding the required amount of ammonium hydroxide to achieve the solution pH = 5.2, the mixing time was 60 min.

The pH values of the aqueous solution were determined using a laboratory pH meter throughout the stabilization stage.

As a result of the reactions, a chelate iron complex was obtained with the following calculated values of the components:

- sulfur content - up to 2.0%

- total nitrogen content in solution - up to 0.7%

- total dry matter content - 30.6%.

- Iron content - 15.4% on an absolutely dry basis.

- total content of organic matter - 44.5% on an absolutely dry basis.

The resulting sample is divided into two parts.

The first part was collected and placed in a plastic bottle and hermetically sealed for arbitration storage. The shelf life was 3 years. During the entire storage period of sample No. 2, no sedimentation, stratification, color change or gas formation were observed.

The second part of the obtained sample was sent for biological activity studies and laboratory testing.

The biological efficiency of sample No. 2 of the transformed LST with chelated iron was tested on barley seeds, variety "Borisfen" intended for winter feeding of cattle. Germination time on a hydroponic installation is 7 days. The application rate of the sample with chelated iron is 1 liter per 500-800 liters of working solution.

The qualitative characteristics of the feed additive sprouted barley were carried out in the laboratory of the Leningrad MVL, St. Petersburg.

The following results were obtained:

1. Increase in content, vitamin B _c - 2.2 mg/kg (+13.0% to control), carotene 3.9 mg/kg (+17.0% to control), ppm crude protein - 1.86% on n.v. (+4.5% to control), Iron - 6.4 mg/kg on n.v. (+22.2% to control)

2. Improving the quality characteristics of the feed additive resulted in an increase in milk yield by 5÷7%, improved cattle health and digestibility of other feeds.

Example #3

Preparation of sample No. 3 of a multicomponent composition based on calcium lignosulfonate to test the biological effectiveness in feeding egg-laying hens.

The preparation of the multicomponent microelement composition was carried out in a laboratory equipped with a fume hood.

A 2-liter glass reactor with heating and an adjustable magnetic stirrer was used.

30 ml of nitric acid (concentration 30.0%) were added to a 17% aqueous solution of technical calcium lignosulfonate (volume 900 ml).

The duration of nitration was 55 min at a set temperature of +25.0°C.

After completion of nitration, the temperature in the reactor increases and is maintained in the range of +40.0÷45.0°C

With constant stirring, inorganic salts of biogenic metals “chemically pure” are added in the following quantities: MnSO ₄ ⋅H ₂ O - 50.0 g, ZnSO ₄ ⋅H ₂ O - 40.0 g, FeSO ₄ ⋅7H ₂ O - 50.0 g, MgSO ₄ ⋅7H ₂ O - 50.0 g.

Each subsequent ingredient is added to the reaction mixture after the previous one has completely dissolved.

After all components of the mixture had completely dissolved, the reactor heating was turned off in order to reduce foaming, and the mixing intensity was reduced.

Stabilization of chelation at the final stage was achieved by stepwise addition of potassium hydroxide (concentration 37.0%) to the reaction mixture.

The first stage of stabilization was carried out by adding 10 ml of potassium hydroxide until the solution pH = 3.0÷3.5 was reached, the stirring time was about 30 minutes.

The second stage of stabilization was carried out after the completion of the first, by adding the required amount of potassium hydroxide to achieve the pH of the solution = 4.9 ÷ 5.3, the mixing time was about 60 minutes.

The pH values of the aqueous solution were determined using a laboratory pH meter throughout the stabilization stage.

As a result of the reactions, multicomponent chelate complexes of transformed LSTs were obtained with the following calculated values of the components:

- sulfur content - up to 2.0%

- total nitrogen content in solution - up to 0.4%

- total dry matter content - 29.1%.

- total content of biogenic microelements - 15.0% on an admissible dry matter basis.

- Manganese content - 4.8% on an absolutely dry basis.

- Zinc content - 4.3% on an absolutely dry basis.

- Iron content - 3.4% on an absolutely dry basis.

- Magnesium content - 1.5% on an absolutely dry basis.

- Calcium content - 1.0% on an absolutely dry basis.

- total content of organic matter - 52.0% on an absolutely dry basis.

The resulting sample No. 3 is divided into two parts.

The first part was collected and placed in a plastic bottle and hermetically sealed for arbitration storage. The shelf life was 3 years. During the entire storage period of sample No. 3, no sedimentation, stratification, color change or gas formation were observed.

The second part of the obtained sample was sent for biological activity studies and laboratory testing.

The biological efficiency test was conducted in a poultry farm in the Leningrad Region, on hens slaughtered and with no or significant reduction in egg production. A 5% aqueous solution was prepared from the sample and given to the animals for drinking for 6 days.

The results of the tests were an increase or restoration of egg production.

Example #4

Preparation of sample No. 4 with a multicomponent composition based on calcium lignosulfonate, to assess the effect of transformed salts of lignosulfonic acids with biologically active microelements in chelate form on soil desalination.

The preparation of the multicomponent microelement composition was carried out in a laboratory equipped with a fume hood.

A 2-liter glass reactor with heating and an adjustable magnetic stirrer was used.

35 ml of nitric acid (concentration 55.0%) were added to a 15% aqueous solution of technical calcium lignosulfonate (volume 900 ml).

The duration of nitration was 35 minutes at a set temperature of +30.0°C.

After completion of nitration, the temperature in the reactor is increased and maintained in the range of +40.0÷50.0°C

With constant stirring, inorganic salts of biogenic metals “chemically pure” are fed in the following quantities: CoSO ₄ ⋅7H ₂ O - 5.0 g, CuSO ₄ ⋅5H ₂ O - 15.0 g, MnSO ₄ ⋅H ₂ O - 25.0 g, ZnSO ₄ ⋅H ₂ O - 25.0 g, FeSO ₄ ⋅7H ₂ O - 30.0 g, MgSO ₄ ⋅7H ₂ O - 50.0 g, H ₃ BO ₃ - 15.0 g, (NH ₄ ) ₆ Mo ₇ O ₂₄ ⋅4H ₂ O - 2.0 g.

Each subsequent ingredient is added to the reaction mixture after the previous one has completely dissolved.

After all components of the mixture had completely dissolved, the reactor heating was turned off in order to reduce foaming, and the mixing intensity was reduced.

Stabilization of chelation at the final stage was achieved by the stepwise addition of ammonium hydroxide (concentration 25.0%) to the reaction mixture.

The first stage of stabilization was carried out by adding 30 ml of potassium hydroxide until the solution pH = 3.0÷3.5 was reached, the stirring time was about 40 minutes.

The second stage of stabilization was carried out after the first stage was completed, by adding the required amount of ammonium hydroxide to achieve the solution pH = 5.0÷5.2, the mixing time was about 60 min.

After stabilization is complete and the solution pH reaches 5.0÷5.2 with constant stirring, add 100 ml of 15% aqueous solution of fulvic-humic acid salts until the component is completely dissolved.

The pH values of the aqueous solution were determined using a laboratory pH meter throughout the stabilization stage.

As a result of the reactions, multicomponent chelate complexes of transformed LST with the addition of a fulvic-humic composition with the following calculated values of the components were obtained:

- sulfur content - up to 2.2%

- total nitrogen content in solution - up to 0.8%

- total dry matter content - 27.5%.

- total content of biogenic microelements - 13.1% on an absolutely dry basis.

- Boron content - 0.8% on an absolutely dry basis.

- Molybdenum content - 0.3% on an absolutely dry basis.

Of these, chelated:

- Manganese content - 2.5% on an absolutely dry basis.

- Zinc content - 2.8% on an absolutely dry basis.

- Iron content - 2.2% on an absolutely dry basis.

- Magnesium content - 1.5% on an absolutely dry basis.

- Calcium content - 1.5% on an absolutely dry basis.

- Cobalt content - 0.3% on an absolutely dry basis.

- Copper content - 1.2% on an absolutely dry basis.

- content of fulvic-humic acid salts - 14.8% on an absolutely dry basis.

- total organic matter content - 54.0% on an admixture basis.

- The obtained sample No. 4 is divided into two parts.

- The first part was collected and placed in a plastic bottle and hermetically sealed for arbitration storage. The shelf life was 3 years. During the entire storage period of sample No. 4, no sedimentation, stratification, color change or gas formation were observed.

- The second part of the obtained sample was sent for biological activity studies and laboratory testing.

The impact of the sample on soil desalination was assessed at the Branch of the Federal State Budgetary Institution “Russian Agricultural Center” in the Astrakhan Region.

The experiments were conducted on soils with different levels of salinity: medium, slightly and strongly saline, with low humus content. The application rate and sample processing regulations are 4 treatments per vegetation season, with a consumption rate equivalent to 5 l/ha.

The results are shown in Table No. 1.

Table No. 1

Experimental variant Highly saline area Salinity assessment pH of aqueous extract Soil humus level before making a contribution after 4 treatments before making a contribution after 4 treatments before making a contribution after 4 treatments Sample No. 4 0.089 0.032 7.5 6.4 0.8 1.3 Moderately saline area Salinity assessment pH of aqueous extract Soil humus level before making a contribution after 4 treatments before making a contribution after 4 treatments before making a contribution after 4 treatments 0.048 0.028 7.3 5.6 0.7 1,2 Lightly salted Salinity assessment pH of aqueous extract Soil humus level before making a contribution after 4 treatments before making a contribution after 4 treatments before making a contribution after 4 treatments 0,041 0.026 7.4 6.1 0.7 1,2

An increase in the level of soil humus supply was noted in all three sites, with an average increase of 63%.

The soil reaction level decreased on average from 7.5 to 6.2 (approximately 17%), which changed the soil acidity level from neutral and slightly alkaline to slightly acidic.

A decrease in soil salinity was observed in all three sites.

Example #5

Preparation of sample No. 5 of a multicomponent composition based on sodium lignosulfonate to test the biological effectiveness of pre-sowing treatment of corn seeds.

Sample No. 5 was prepared according to the recipe for sample No. 1 with the addition of melamine salt of bis(oxymethyl)phosphinic acid to the finished liquid multi-component microelement composition.

- In a ready-made liquid microelement chelate composition at a temperature of +25.0° With a volume of 980 ml, with constant stirring, 20 ml of an aqueous solution of melamine salt of bis(oxymethyl)phosphinic acid with a concentration of 10 were added^-4%.

- Complete and uniform mixing was ensured after 30 minutes of magnetic stirrer operation, the content of melamine salt of bis(oxymethyl)phosphinic acid in the aqueous solution was 0.5*10 ^-7 %.

A comparative test of biological efficiency according to the recipe of example No. 5 was carried out on the basis of a comparative biotest on corn seeds at the Kuban State Agrarian University named after I.T. Tribulin.

The biotest was carried out by germinating seeds in a 0.05% solution of samples No. 1 and No. 5. The result of the test on distilled water and sample No. 1 without adding melamine salt of bis(oxymethyl)phosphinic acid was used as a control. Confirmation of the increase in biological activity of samples No. 1 and No. 5 was the increase in the mass of corn sprouts, the results are given in Table No. 2.

Table No. 2. Effect of samples based on a multi-component microelement composition on the efficiency of corn seed treatment

Option WITH _mass. samples, %, C _m Germination energy, % Germination,
% Weight, g/100 pcs. sprouts Roots/change in % Sprouts/change in % raw dry %, S.V raw dry %, S.V. Control 0 94.5 96.5 6,084 0,900 14.8 7,200 1,289 17.9 Sample No. 1 0.05 98.5 99.5 8,866
45% 1,356
50.6% 15.3
3.4% 8,950
24% 1,701
32% 19.0
6% Sample #5 0.05 100,0 100,0 9,050
48.7% 1,403
55.8% 15.5
4.7% 9,450
31.2% 1,843
43% 19.5
8.9%

The examples given indicate that the process of step-by-step stabilization of the resulting solution results in the absence of sediment, stratification, color change, and gas formation during storage for 3-4 years.

The method ensures a reduction in emissions of volatile nitrogen compounds by reducing the concentration of nitric acid and the volume of ammonium hydroxide or completely replacing the latter with potassium hydroxide, as well as reducing the nitration time, which is an important environmental aspect when implementing the technology on an industrial scale.

In the method according to patent RF2660929, taken as a prototype, there are no stages of stabilization of the obtained nutrient mixture. One-time addition of ammonia water to pH 4÷6 is not enough to obtain a completely homogeneous solution, which can lead to precipitation during storage, i.e. insufficient stability.

An important feature of the developed technology for obtaining chelate complexes is the ability to create our own production of complexones using a single technological process, the ability to abandon expensive imported EDTA and Glycine complexones without losing production capacity, since the concentration of chelate biogenic metals reaches 16% in terms of absolutely dry matter.

Literature:

1) F.E. Browns and D.A. Browns, "Lignin Chemistry", "Forest Industry", Moscow, 1964. UDC 668.474:54.

2) K.V. Sarkanen and K.H. Ludwig, “Lignins”, “Forest Industry”, Moscow, 1975. UDC 634.0.813.11.

3) N.I. Afanasyev, S.E. Teltevskaya, N.A. Makarevich, L.N. Parfenova, “Structure and physicochemical properties of lignosulfonates” Ural Branch of the Russian Academy of Sciences, Ekaterinburg, 2005. UDC 541.183:634.0.864.

4) M.I. Chudakov, “Industrial use of lignin”, “Forest industry”, Moscow, 1972. UDC 634.0.864.

5) Dospekhov B.A. Methodology of field experiment / B.A. Dospekhov. - M.: Kolos, 1985.

6) Barchukova A.Ya. Efficiency of application of growth regulators in technology of winter wheat cultivation / A.Ya. Barchukova, Ya.K. Tosunov, N.V. Chernysheva, S.G. Fat. Proceedings of the Kuban Agrarian University, 2009.

7) Kodanev I.V. Improving the quality of grain / I.V. Kodanev. - M.: Kolos, 1976.

Claims (4)

1. A method for producing chelate complexes comprising the transformation of technical lignosulfonates by nitration with nitric acid followed by the addition of inorganic salts of biogenic metals, characterized in that the nitration of lignosulfonates is carried out by adding diluted nitric acid with a concentration of 30.0-55.0% by weight to a 15-20 wt.% aqueous solution of lignosulfonates with constant stirring and while maintaining the temperature within the range of 25.0 to 35.0 °C, and the salts of inorganic biogenic metals are added with constant stirring and while maintaining the temperature within the range of 35.0 to 50.0 °C no earlier than 30 minutes after the completion of the addition of nitric acid, after dissolving all components, the solution is gradually stabilized by adding potassium hydroxide or ammonium hydroxide until a pH of 3.0-3.5 is reached within 30 minutes, after dissolving all components, the solution is finally stabilized by adding potassium hydroxide or ammonium hydroxide until pH 4.5-5.5 is reached within 60 minutes. 2. The method according to paragraph 1, characterized in that inorganic salts of biogenic metals copper, zinc, manganese, iron, calcium, magnesium, cobalt are added up to their individual or total content of up to 16% in terms of absolutely dry matter. 3. The method according to item 1, characterized in that, in order to increase biological activity, upon reaching a pH of 5.0-5.5, salts of fulvic-humic acids are added to the solution with constant stirring, with a content of up to 15% in terms of absolutely dry matter. 4. The method according to item 1, characterized in that, in order to increase biological activity, upon reaching a pH of 5.0-5.5, melamine salt of bis(oxymethyl)phosphinic acid is added to the solution with constant stirring until its content in the solution is from ^10-6 % to ^10-7 %.