Method for producing chelate complexes of lignosulfonates

Abstract

The method for obtaining chelate complexes is earned out by nitrating aqueous solutions of lignosulfonates in 30-55.0 wt.% nitric acid, while maintaining the temperature within the range of 25-35°C. Salts of biogenic metals are added with constant stirring, while maintaining the temperature from 35 to 50°C not earlier than 30 minutes after the completion of the addition of nitric acid. After dissolving all the components, the solution is gradually stabilized by adding KOH or ammonia water, initially for 30 minutes until a pH of 3.0-3.5 is reached, after which for 60 minutes until a pH of 4.5-5.5 is reached. The technical result of the invention consists in ensuring long-term stability of the solution form of the target complex at a high concentration of retained biogenic metals.

Description

[0001] METHOD FOR PRODUCING CHELATE COMPLEXES OF LIGNOSULFONATES

[0002] TECHNICAL FIELD

[0003] This invention relates to the method for obtaining chelated complexes based on organic Complexones and biogenic metals. The use of chelated complexes provides a much greater availability of microelements when using in agriculture, as microfertilizers, in animal husbandry for cattle and poultry, as a feed additive, as well as in the production of food micronutrient additives.

[0004] BACKGROUND OF THE INVENTION

[0005] Complexones based on EDTA and Glycine perform only the transport function of delivering nutrient metals, but themselves are ballast compounds for soil, plants or animals. At the same time, EDTA salts are not allowed in Russia and the EU for the production of feed additives. In contrast to EDTA Complexones, chelated complexes by proposed technology, obtained on the basis of lignosulfonic acids transformed by nitration, in addition to the chelating and transport functions, contain natural and valuable components for plant and animal nutrition: a wide range of amino acids and vitamins, fulvi-humic acids, high-molecular carbohydrates in the form of mono and polysaccharides [1], [2],

[0006] An important feature of the proposed technology is the ability for the manufacturer to abandon the import of expensive EDTA and Glycine Complexones and implement its own production of Complexones in the same technological chain with the production of chelated complexes. At the same time, the raw material Lignosulfonate Technical (LST) is a relatively cheap and accessible raw material, which is used for the production of organo-mineral fertilizers, growth stimulants, for production of feed and food additives and even pharmaceuticals. These raw materials are produced and sold in Russia in large volumes, both for the domestic market and for export.

[0007] The method for producing of Iron lignosulfonate chelate, which can be used in agriculture and veterinary medicine is known according to Patent RU 2165936 published 27.04.2004, in which mix it up a chelating agent with a salt of bi- or ferric iron, wherein nitrosated lignosulfonic acids formed at the stage of preparation of chelate are used as a chelating agent, and iron salts are administered in two stages.

[0008] In order to achieve the maximum Iron chelate capacity, the remaining amount of Iron salt is added to the chelate solution after the nitrosation reaction is completed.

[0009] In the Patent RU 2660929 published 11.07.2018, the ORGANIC COMPONENT OF THE NUTRIENT MIXTURE FOR PLANTS is known that LST modified by nitration is used with the help of 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 duration of nitration was 60 minutes. After the nitration was completed, the following nutrients were dissolved in the reaction mixture with stirring (in % of the weight of the initial LST: FeSO4-7H2O - 80; H3BO3- 7,4; ZnSO4-7H2O - 14,2; CoCI2-6H2O - 3,9; (NH4)6MO7O24H2O - 28,9; MnCI2-4H2O - 11 ,6; MgSO4-7H2O - 32,6; CuSO4-5H2O - 12,6; Urea - 100; K2HPO4-3H2O - 1 ,5). It was controlled by germination of wheat. Germination was carried out for 7 days, controlling 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 a completely dry matter).

[0010] SUMMARY OF THE INVENTION

[0011] The technological problem is to develop a continuous technological cycle for the production of liquid chelated complexes with a high chelated capacity, based on complexone, which is used as a nitration-transformed LST mixed with cations biogenic metals.

[0012] The technical result of the method is to ensure long-term stability of the liquid chelated complex with a high concentration of retained biogenic metals.

[0013] A feature of the proposed method and production of chelated complexes is that a continuous technological cycle is proposed based on an improved method of nitration of technical LST, which provides a high effect of chelation and cation retention with minimal foaming and separation of nitrogen oxides.

[0014] The nitration technology is carried out under the proven conditions of the process (time, temperature, sequence of actions, kinetics) and the selected optimal balance of the active components in the reaction mixture. This made it possible to ensure effective complex formation and retain biogenic metal ions in concentrations that are not inferior or even exceed the results of other technologies for the production of chelated complexes.

[0015] The essence of the method for obtaining chelated complexes includes nitration of an aqueous solution of technical lignosulfonates (LST) with the help of nitric acid with the subsequent addition of inorganic salts of biogenic metals.

[0016] The key parameters of the method (technology) are the balance and concentration of components, nitration time, temperature of the reaction mixture, the rate and sequence of dissolution of biogenic metal salts, as well as the time and method of stabilization of the solution until the finished liquid chelated complex is obtained. Thus, in the process of research, it was determined that the maximum reactivity of chelation was observed with the addition of biogenic metal salts not earlier than 30 minutes after the addition of nitric acid.

[0017] LST transformation is carried out by nitration with the addition of dilute nitric acid with a concentration of 30.0-5-55.0% into 15-5-20% aqueous solution of LST with constant mixing and maintaining temperatures in the range from +25.0 to +35.0°C, and salts of inorganic biogenic metals are added with constant mixing and maintaining the temperature in the range from +35.0 to +50.0°C, not earlier than 30 minutes after the addition of nitric acid. After dissolving of 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 the components, the solution is finally stabilized by adding potassium hydroxide or ammonium hydroxide for 60 minutes until a pH is reached of 4.5-5.5.

[0018] Inorganic salts of biogenic metals Copper, Zinc, Manganese, Iron, Calcium, Magnesium, Cobalt are added to their individual or total content in the chelated complex up to 16% in terms of a.d.m.

[0019] To increase biological activity when the pH reaches 5.0+5.5, salts of fulvohumic acids are added to the solution with constant stirring, with a content of up to 15% in terms of a.d.m. To increase biological activity when the pH reaches 5.05.5, the melamine salt of bis(oxymethyl) phosphic acid is added to the solution with constant stirring - until its content in the solution is from 10’6to 10'7%.

[0020] Example 1

[0021] Preparation of sample 1 with a multicomponent composition based on Sodium lignosulfonate to test biological efficacy during pre-sowing treatment of winter wheat seeds.

[0022] • The preparation of the multicomponent microelement composition was carried out in a laboratory equipped with a fume hood.

[0023] • A 2-liter glass reactor with a heated capacity and an adjustable magnetic stirrer was used.

[0024] • In a 19% aqueous solution of technical sodium lignosulfonate with a volume of 850 ml, 30 ml of nitric acid (concentration of 55.0%) was added.

[0025] • The duration of nitration was 30 minutes at a given temperature of +25.0°C.

[0026] • After the nitration is completed, the temperature in the reactor rises and is maintained in the range of +35.0^-45.0°C

[0027] • With constant mixing, inorganic salts of biogenic metals "CP" and boric acid are supplied in the following quantities: CoSO4.7H2O - 4.0 g, CUSO4-5H2O - 10.0 g, MnSO4H2O - 25.0 g, ZnSO4H2O - 25.0 g, FeSO4-7H2O - 50.0 g, MgSO4-7H2O - 25.0 g, H3BO3 - 10.0 g, (NH4)6Mo7O24-4H2O - 1.0 g.

[0028] • Each subsequent ingredient is added to the reaction mixture after the previous one has been completely dissolved.

[0029] • After the complete dissolution of all components of the mixture, the heating of the reactor was turned off in order to reduce foaming, the intensity of mixing decreased.

[0030] • Stabilization of chelation at the final stage was achieved by step- by-step 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 pH of the solution 3.0+3.5 was reached, the mixing time is about 30 minutes.

[0031] • The second stage of stabilization was carried out after the completion of the first by adding the necessary amount of Ammonium hydroxide to achieve the pH of the solution 4.8+5.2, the mixing time was about 60 minutes

[0032] • The pH values of the aqueous solution were determined by laboratory pH- meter throughout the stabilization phase.

[0033] As a result of the reactions, multicomponent chelated complexes of transformed

[0034] LST with the following design values of components were obtained:

[0035] - Sulfur content - up to 2.0%

[0036] - Total Nitrogen content in solution - up to 0.75%

[0037] - Total dry matter content - 26,1%.

[0038] - Total content of biogenic m / e - 11.95% a.d.m

[0039] - Boron content - 0.57% a.d.m.

[0040] - Molybdenum content - 0.17% a.d.m.

[0041] Of these, chelated:

[0042] - Cobalt content - 0.27% a.d.m.

[0043] - Copper content - 0.82% a.d.m.

[0044] - Manganese content - 2.63% a.d.m.

[0045] - Zinc content - 2.94% a.d.m.

[0046] - Iron content - 3.73% a.d.m.

[0047] - Magnesium content - 0.81% a.d.m.

[0048] - The total content of the organic substances - 56.3% on a.d.m.

[0049] • The resulting sample 1 is divided into two parts.

[0050] • The first part was selected, placed in a plastic bottle and hermetically packed for arbitration storage. The shelf life was 4 years. During the entire storage time of sample N?l, sedimentation, delamination, discoloration and gas formation were not observed. • The second part of the obtained sample was sent for biological activity studies and laboratory tests.

[0051] Biological efficiency was tested on seeds of winter wheat, variety "Adel", at the Kuban State Agrarian University named after I.T. Tribulin. Field tests- [5], Presowing seed treatment, at the rate of 1 liter of sample per 1 ton of seeds.

[0052] The test results are given for two key indicators - yield and grain quality [6], [7],

[0053] 1. The yield exceeded the control variant from 42.2 to 45.9 c / ha, in the control - 39.6 c / ha. HCP05- 2.0 c / ha.

[0054] 2. The content of raw 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%.

[0055] Example 2

[0056] Preparation of sample 2 based on Magnesium lignosulfonate with chelated Iron to test biological efficacy in germination of barley hydroponic feed for cattle

[0057] • The preparation of the sample with chelated Iron (II) was carried out in a laboratory equipped with a fume hood.

[0058] • A 2-liter glass reactor with a heated capacity and an adjustable magnetic stirrer was used.

[0059] • In 18.5% aqueous solution of Magnesium lignosulfonate with a volume of 800 ml, 32 ml of nitric acid (concentration of 52.5%) was added.

[0060] • The duration of nitration was 45 minutes at a given temperature of +28.0°C.

[0061] • After the nitration is completed, the temperature in the reactor rises and is maintained in the range of +40.0 45.0°C

[0062] • With constant stirring, weights of 50 g of FeSO4-7H2O "CP" are added - 300.0 g.

[0063] • Each subsequent weight is added to the reaction mixture after the previous one has been completely dissolved.

[0064] • After the complete dissolution of the entire volume of Iron sulfate, the heating of the reactor was turned off in order to reduce foaming, the intensity of mixing decreased. • Stabilization of chelation at the final stage was achieved by step-by-step addition of Ammonium hydroxide (concentration 25.0%) to the reaction mixture.

[0065] • The first stage of stabilization was carried out by adding 25 ml of Ammonium hydroxide until the pH of the solution 3.03.5 was reached, the mixing time is about 35 minutes.

[0066] • The second stage of stabilization was carried out after the completion of the first, by adding the necessary amount of Ammonium hydroxide to achieve the pH of the solution = 5.2, the mixing time was 60 minutes

[0067] • The pH values of the aqueous solution were determined by laboratory pH- meter throughout the stabilization phase.

[0068] As a result of the reactions, a chelated Iron complex was obtained with the following calculated values of components:

[0069] - Sulfur content - up to 2.0%

[0070] - Total Nitrogen content in solution - up to 0.7%

[0071] - Total dry matter content - 30,6%

[0072] - Iron content - 15.4% a.d.m.

[0073] - The total content of the organic substances - 44.5% a.d.m.

[0074] • The resulting sample is divided into two parts.

[0075] • The first part was selected, placed in a plastic bottle and hermetically packed for arbitration storage. The shelf life was 3 years. During the entire storage time of sample 2, sedimentation, delamination, discoloration and gas formation were not observed.

[0076] • The second part of the obtained sample was sent for biological activity studies and laboratory tests.

[0077] Testing of the biological efficiency of sample 2 of transformed LST with chelated Iron was carried out on barley seeds, variety "Borisfen" intended for winter feeding of cattle. Germination time on a hydroponic unit is 7 days. The norm for using a sample with chelated Iron is 1 liter per 500800 liters of working solution.

[0078] Qualitative characteristics of the feed additive of sprouted barley were carried out in the veterinary laboratory, St. Petersburg. The following results were obtained:

[0079] 1. Increase in: Vitamin Bc- 2.2 mg / kg (+13.0% to control), carotene 3.9 mg / kg (+17.0% to control), crude protein - 1.86% (+4.5% to control), Iron - 6.4 mg / kg (+22.2% to control)

[0080] 2. Improvement of the quality characteristics of the feed additive led to an increase in milk yield by 5-7%, to an improvement in the health of cattle and the digestibility of other feeds.

[0081] Example 3

[0082] Preparation of sample 3 with a multicomponent composition based on Calcium lignosulfonate to test biological efficacy in feeding of egg-laying hens.

[0083] The preparation of the multicomponent microelement composition was carried out in a laboratory equipped with a fume hood.

[0084] A 2-liter glass reactor with a heated capacity and an adjustable magnetic stirrer was used.

[0085] In a 17% aqueous solution of technical Calcium lignosulfonate with a volume of 900 ml, 30 ml of Nitric acid (concentration of 30.0%) was added.

[0086] The duration of nitration was 55 minutes at a given temperature of +25.00C.

[0087] After the nitration is completed, the temperature in the reactor rises and is maintained in the range of +40.0-45.00C

[0088] With constant mixing, inorganic salts of biogenic metals "CP" are supplied in the following quantities: MnSO4 H2O - 50.0 g, ZnSO4 H2O - 40.0 g, FeSO4-7H2O - 50.0 g, MgSO4-7H2O - 50.0 g.

[0089] Each subsequent ingredient is added to the reaction mixture after the previous one has been completely dissolved.

[0090] After the complete dissolution of all components of the mixture the heating of the reactor was turned off in order to reduce foaming, the intensity of mixing decreased.

[0091] Stabilization of chelation at the final stage was achieved by step-by-step addition of Potassium hydroxide (concentration 37.0%) to the reaction mixture.

[0092] The first stage of stabilization was carried out by adding 10 ml of Potassium hydroxide until the pH of the solution 3.0-3.5 was reached, the mixing time was about 30 minutes. • The second stage of stabilization was carried out after the completion of the first by adding the necessary amount of Potassium hydroxide to achieve the pH of the solution 4.9-^-5.3, the mixing time was about 60 minutes

[0093] • The pH values of the aqueous solution were determined by laboratory pH- meter throughout the stabilization phase.

[0094] As a result of the reactions, multicomponent chelated complexes of transformed LST with the following design values of components were obtained:

[0095] - Sulfur content - up to 2.0%

[0096] - Total Nitrogen content in solution - up to 0.4%

[0097] - Total dry matter content - 29,1%

[0098] - Total content of biogenic m / e - 15.0% a.d.m

[0099] - Manganese content - 4.8% a.d.m.

[0100] - Zinc content - 4.3% a.d.m.

[0101] - Iron content - 3.4% a.d.m.

[0102] - Magnesium content - 1.5% a.d.m.

[0103] - Calcium content - 1.0% a.d.m.

[0104] - The total content of the org. substances - 52.0% a.d.m.

[0105] • The resulting sample 3 is divided into two parts.

[0106] • The first part was selected, placed in a plastic bottle and hermetically packed for arbitration storage. The shelf life was 3 years. For the entire period of storage of sample 3, sedimentation, delamination, discoloration and gas formation were not observed.

[0107] • The second part of the obtained sample was sent for biological activity studies and laboratory tests.

[0108] Testing of biological efficiency was carried out in the poultry farm of the Leningrad region, on chickens allocated for slaughter and with the absence or significant decrease in egg production. A 5% aqueous solution was prepared from the sample, which was fed during drinking for 6 days.

[0109] The result of the tests was an increase or restoration of egg production.

[0110] Example 4 Preparation of sample 4 with a multicomponent composition based on Calcium lignosulfonate to assess the effect of transformed salts of lignosulfonic acids with biologically active microelements in chelated form on soil desalinization.

[0111] • The preparation of the multicomponent microelement composition was carried out in a laboratory equipped with a fume hood.

[0112] • A 2-liter glass reactor with a heated capacity and an adjustable magnetic stirrer was used.

[0113] • In a 15% aqueous solution of technical Calcium lignosulfonate with a volume of 900 ml, 35 ml of Nitric acid (concentration of 55.0%) was added.

[0114] • The duration of nitration was 35 minutes at a given temperature of +30.0°C.

[0115] • After the nitration is completed, the temperature in the reactor rises and is maintained in the range of +40.0+50.0°C

[0116] • With constant stirring, inorganic salts of biogenic metals "CP" are supplied in the following quantities: COSO4 7H2O - 5.0 g, CuSO4-5H2O - 15.0 g, MnSO4H2O - 25.0 g, ZnSO4H2O - 25.0 g, FeSO4-7H2O - 30.0 g, MgSO4-7H2O - 50.0 g, H3BO3 - 15.0 g, (NH4)6Mo7O24-4H2O - 2.0 g.

[0117] • Each subsequent ingredient is added to the reaction mixture after the previous one has been completely dissolved.

[0118] • After the complete dissolution of all components of the mixture, the heating of the reactor was turned off, in order to reduce foaming, the intensity of mixing decreased.

[0119] • Stabilization of chelation at the final stage was achieved by step-by-step addition of Ammonium hydroxide (concentration 25.0%) to the reaction mixture.

[0120] • The first stage of stabilization was carried out by adding 30 ml of Potassium hydroxide until the pH of the solution 3.0+3.5 was reached, the mixing time was about 40 minutes.

[0121] • The second stage of stabilization was carried out after the completion of the first, by adding the necessary amount of Ammonium hydroxide to achieve the pH of the solution 5.0+5.2, the mixing time was about 60 minutes • After stabilization is completed and the pH of the solution is 5.0+5.2 with constant stirring, 100 ml of 15% aqueous solution of fulvic-humic acid salts is added until the component is completely dissolved.

[0122] • The pH values of the aqueous solution were determined by laboratory pH- meter throughout the stabilization phase.

[0123] As a result of the reactions, multicomponent chelated complexes of transformed LST with the addition of a fulvi-humic composition with the following calculated values of components were obtained:

[0124] - Sulfur content - up to 2.2%

[0125] - Total Nitrogen content in solution - up to 0.8%

[0126] - Total dry matter content - 27,5%

[0127] - total content of biogenic microelements- 13.1% a.d.m.

[0128] - Boron content - 0.8% a.d.m.

[0129] - Molybdenum content - 0.3% a.d.m.

[0130] Of these, chelated:

[0131] - Manganese content - 2.5% a.d.m.

[0132] - Zinc content - 2.8% a.d.m.

[0133] - Iron content - 2.2% a.d.m.

[0134] - Magnesium content - 1.5% a.d.m.

[0135] - Calcium content - 1.5% a.d.m.

[0136] - Cobalt content - 0.3% a.d.m.

[0137] - Copper content - 1.2% a.d.m.

[0138] - content of fulvic-humic acid salts - 14.8% a.d.m

[0139] - total content of organic matter - 54.0% a.d.m

[0140] • The resulting sample 4 is divided into two parts.

[0141] • The first part was selected, placed in a plastic bottle and hermetically packed for arbitration storage. The shelf life was 3 years. For the entire period of storage of sample 4, sedimentation, delamination, discoloration and gas formation were not observed.

[0142] • The second part of the obtained sample was sent for biological activity studies and laboratory tests. The assessment of the impact of the sample on soil salinization was carried out in the Astrakhan Region Branch of the Russian Agricultural Center.

[0143] The experiments were carried out on soils with different levels of salinity: medium, weak and strongly saline, with a low humus content. The application rate and regulations for sample treatment are 4 treatments per growing season, with an equivalent application rate of 5 l / ha.

[0144] The results are shown in Table 1.

[0145] An increase in the level of soil provision with humus was noted at all three sites, the average increase was 63%.

[0146] The level of reaction of the soil environment decreased on average from 7.5 to

[0147] 6.2 (about 17%), which changed the level of soil acidity from neutral and slightly alkaline to slightly acidic.

[0148] A decrease in soil salinity was observed at all three sites. Example 5

[0149] Preparation of sample 5 with a multicomponent composition based on Sodium lignosulfonate to test biological efficacy in pre-sowing treatment of corn seeds Sample 5 was prepared according to the recipe of sample 1 with the addition of the melamine salt of bis(oxymethyl) phosphic acid to the finished liquid multicomponent microelement composition.

[0150] In the finished liquid microelement chelated composition at a temperature of +25.00 C with a volume of 980 ml, with constant stirring, 20 ml of an aqueous solution of melamine salt bis (oxymethyl) phosphic acid was added at a concentration of 10-4 %.

[0151] Complete and uniform mixing was provided after 30 minutes of operation of the magnetic stirrer, the content of the melamine salt of bis(oxymethyl) phosphic acid in the aqueous solution was 0.5-10-7%.

[0152] Comparative verification of biological efficacy according to the recipe of Example 5 was carried out on the basis of a comparative biotest on corn seeds at the Kuban State Agrarian University named after LT. Tribulin.

[0153] The biotest was carried out by germination of seeds in a 0.05% solution of samples 1 and 5. As a control the result of the test on distilled water and sample 1 without the addition of melamine salt bis(oxymethyl) phosphic acid was used. The increase in the biological activity of samples 1 and 5 was confirmed by an increase in the weight of corn sprouts; the results are shown in Table 2.

[0154] Table 2. Effect of samples based on a multicomponent microelement composition on the efficiency of corn seed processing

[0155] INDUSTRIAL APPLICABILITY

[0156] In the above examples, it is indicated that the process of step-by-step stabilization of the resulting solution leads to the fact that during storage for 3+4 years there is no precipitation, delamination, discoloration, gas formation was not observed.

[0157] The method reduces 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.

[0158] In the method according to Patent RU2660929, taken as a prototype, there are no stages of stabilization of the resulting nutrient mixture. The simultaneous addition of Ammonia water to pH 4+6 is not sufficient to obtain a fully homogeneous solution, which can lead to precipitation during storage, i.e. insufficient stability.

[0159] An important feature of the developed technology for the production of chelated complexes is the ability to create our own production of Complexones according to a single technological process, the ability to abandon expensive imported EDTA and Glycine complexons without loss of production capacity, since the concentration of chelated biogenic metals reaches 16% in terms of a.d.m.

[0160] References

[0161] 1) F.E. Browns and DABrown, "Lignin Chemistry", "Forest Industry", Moscow, 1964. UDC 668.474:54

[0162] 2) K.V.Sarkanen and K.H. Ludwig, "Lignins", "Forest Industry", Moscow, 1975. UDC 634.0.813.11

[0163] 3) N.LAfanasyef, S.E.Tel'tevskaya, N. A. Makarevich, L.N. Parfenova, "Structure and Physicochemical Properties of Lignosulfonates" Ural Branch of the Russian Academy of Sciences, Yekaterinburg, 2005. UDC 541.183:634.0.864

[0164] 4) M. I. Chudakov, "Industrial Use of Lignin", "Forest Industry", Moscow, 1972. UDC 634.0.864

[0165] 5) Dospekhov B.A. Field Experiment Methodology I B.A. Dospekhov. - M.: Kolos, 1985.

[0166] 6) Barchukova A.Ya. Efficiency of Growth Regulators in Winter Wheat Cultivation Technology / A.Ya. Barchukova, Ya.K. Tosunov, N.V. Chernysheva, S.G. Fat. Proceedings of the Kuban Agrarian University, 2009

[0167] 7) Kodanev I.V. Improving Grain Quality / I.V. Kodanev. - M.: Kolos, 1976.

Claims

1. Method for obtaining chelate complexes, including the transformation of technical lignosulfonates by nitration using 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% to a 15+20% aqueous solution of lignosulfonates with constant stirring and while maintaining the temperature in the range from +25.0 to +35.0°C, and the salts of inorganic biogenic metals are added with constant stirring and while maintaining the temperature in the range from +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 the pH reaches 3.0+3.5 within 30 minutes, after dissolving all components, the solution is finally stabilized by adding Potassium hydroxide or Ammonium hydroxide until the pH reaches 4.5+5.5 for 60 minutes.

2. Method of claim 1 wherein the inorganic salts of the biogenic metals Copper, Zinc, Manganese, Iron, Calcium, Magnesium, Cobalt are added to their individual or total content up to 16% in terms of a.d.m.

3. Method of claim 1 , wherein in order to increase the biological activity when the pH reaches 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 a.d.m.

4. Method of claim 1 , wherein in order to increase the biological activity when the pH is reached 5.0+5.5, the melamine salt of bis(oxymethyl) phosphic acid is added to the solution with constant stirring - until its content in the solution is from 10-6% to 10-7%.

Images