Method of producing organic complexes of biogenic microelements based on humic acid salts

Abstract

A method for producing organic microelement complexes based on humic acid salts is characterized in that an aqueous solution of lignosulfonate is mixed with dry or aqueous solutions of copper, zinc, manganese, iron, cobalt, ammonium molybdate sulfates, boric acid or potassium metaborate to achieve a total mass concentration of microelement ions in the range of 0.5-4.0% of the absolutely dry matter. An alkaline agent is added. The resulting working solution undergoes intensive mixing with cavitation treatment. The solution is loaded into a reactor, sealed, pressurized to 22 bar, and heated to 150°C. The synthesis of microelement complexes based on humic acid salts occurs for 120-150 minutes at a pressure of 22-23 bar, temperature of +170-180°C with an air flow rate of 60-80 1 / h passing through the reactor. The synthesis process is stopped when the pH drops below 8.5 by turning off the heating and air supply. The finished product is unloaded after natural cooling below 70°C. The invention enhances the stability of organic complexes based on humic acids with high concentrations of retained biogenic microelements.

Description

[0001] METHOD OF PRODUCING ORGANIC COMPLEXES OF BIOGENIC MICROELEMENTS BASED ON HUMIC ACID SALTS TECHNICAL FIELD

[0002] The method relates to producing organic complexes of biogenic microelements (m / e) based on humic acid salts (HA) and lignosulfonic acids (LST). The usage of organically bound biogenic m / e with humic complexes increases their efficiency for use in agriculture, as an independent microfertilizer, as a component of organomineral fertilizers, in animal husbandry, as an activator of microbiological processes in cattle and poultry, as a feed additive, and in industry for creating environmentally friendly drilling fluids.

[0003] Mixing humic preparations with m / e is a common method of increasing the efficiency of both preparations. It is known that most humic preparations, especially those based on Leonardite, are capable of retaining biogenic metal cations, although in relatively small quantities - less than 0.5% of the dry matter (DM) mass. Significantly higher m / e concentrations can be obtained by using a mixture of HA and chelate complexes based on modified LST or ethylenediaminetetraacetic acid (EDTA) salts. However, the possibilities of obtaining industrial products on this basis have a number of limitations, namely, most chelate complexes are stable only in an acidic environment and are unstable even in a slightly alkaline environment, typical for HA. Therefore, such compositions are limited for practical usage.

[0004] BACKGROUND OF THE INVENTION

[0005] The Patent RU 2237643 published 10.10.2004 “METHOD OF PRODUCING COMPLEX HUMIC FERTILIZERS” is known from the field of technology. The method consists in producing chelate complexes of m / e with HA for obtaining complex humic fertilizers.

[0006] The method includes mixing alkali metal humates with sulfates of iron, copper, manganese, zinc and cobalt, as well as boric acid and molybdic acid salts. Mixing of m / e salts with alkali metal humates is carried out in the form of their aqueous solutions at a pH value in the range of 7.0 / 7.8. The total amount of milligram equivalents of metals added in the form of sulfates should not exceed 30% of the exchange capacity of the alkali metal humate solution. The condition for achieving the technical result is maintaining the pH of the medium during the chelation process in the range 7.0 / 7.8. This is due to the fact that sulfates of polyvalent metals, when dissolved in water, give an acidic reaction, while the original solution of sodium humate has an alkaline reaction (pH 8.0 / 9.0). When the solution is acidified to a pH below 4.0, humic acids precipitate, and this process is irreversible. At the same time, ions of polyvalent metals at a pH above 8.0 also precipitate in the form of hydroxides. Since the acidity of the solution of sulfates of polyvalent metals (pH 2.0 / 3.0) is significantly higher than the alkalinity of the sodium humate solution (pH 8.0 / 9.0), when mixing these solutions, the pH of the medium will quickly shift towards an acidic medium. Therefore, it is necessary to introduce constantly an alkaline agent into the mixture so that the pH value does not go beyond the boundaries of the above range (7.0 / 7.8).

[0007] In this case, solutions of sulfates m / e, as well as, if necessary, boric acid is gradually introduced into the sodium humate solution with constant stirring and pH control, to maintain which potassium carbonate is added to the mixture in an amount that allows maintaining the pH value in the specified range at the moment the pH approaches the lower of the specified limits. The invention makes it possible to obtain water-soluble chelate complexes of humic acids with multivalent metals, which can be effectively used as fertilizers.

[0008] The closest in technical essence and taken as a prototype is the Patent for invention of the Russian Federation 2205166 dated 19.12.2001 "METHOD OF PRODUCING SALTS OF HUMIC ACIDS". The method includes high- temperature treatment of an aqueous suspension of plant materials in a continuous mode in two stages in the presence of an oxidizing agent of air with a specific flow rate of 20 / 65 nm3 / m3h. At the first stage, pre-oxidation is carried out in a circulation circuit at 50 / 1900 C and pressure of 0.5 / 3.0 MPa until the pH value is reached 10.5 / 12.0. At the second stage, the main oxidation takes place with stirring with simultaneous activation of the mixture of raw materials and an alkaline agent, at 170 / 2100C and pressure of 0.5 / 3.0 MPa until a pH of 8.5 / 10.0 is achieved. Then the mixture is mixed with an alkaline agent - sodium hydroxide, oxidized and cooled. At the second stage of heat treatment or after cooling the finished product to 70-^1000C, dry salts containing m / e in the composition are additionally introduced: MnSO4 • 5H2O, CuSO4 • 5H2O, ZnSO4 • 7H2O, Co(NO3)3 • 6H2O, (NH4)6Mo7O24 and boric acid. By-products of cellulose production by the sulfite method - LST and lignin - a by-product of hydrolysis production are used as plant raw materials.

[0009] The disadvantage of the prototype is that due to the relatively small Due to the complexing capacity of the synthesized HA, as well as the high pH values of these compounds, the creation of stable organic complexes based on HA with a high concentration of biogenic m / e with the introduction of acidic mineral salts is virtually impossible. The studies and experience in the industrial release of HA using this technology have shown that the declared total content of m / e associated with HA in the finished product does not exceed 0.3 / 0.5% of the absolutely dry matter (a.d.m.). A further increase in the introduction of acidic mineral compounds into the finished humic product no longer provides an organic bond with HA, and accordingly does not significantly increase the biological efficiency of the product. It is noted that an increase in the content of mineral components in such a mixture by more than 0.5% of the a.d.m. increases the precipitation of insoluble sediments, which leads to a decrease in the stability of the final product.

[0010] SUMMARY OF THE INVENTION

[0011] The technological problem is to develop a method for obtaining stable organic complexes with a high concentration of biogenic m / e based on HA.

[0012] The technical result is to increase the stability of organic complexes based on HA with a high concentration of retained biogenic m / e.

[0013] The technical result is achieved by using a known method of two-stage synthesis of humic compounds during oxidative-hydrolytic destruction of LST lignosulfonates and introducing m / e mineral compounds into the reaction mixture. In this case, m / e in the presence of an oxidizer and at high temperature are ionized and incorporated into the humic compounds formed during polymerization. In the resulting compounds, m / e ions are in an organic complex and are stable in an alkaline medium, characteristic of most humic compounds. The essence of the invention is that acidic inorganic salts of copper, zinc, manganese, iron, cobalt, ammonium molybdate, as well as boric acid or potassium metaborate with a total concentration of ion(s) m / e in the range of 0.5+4.0% on an a.d.m.basis are introduced into an aqueous solution of LST (pH 4.3+4.6) before mixing with an alkaline agent (potassium or sodium hydroxide). After mixing with an alkaline agent, the resulting working solution (WS) is subjected to intensive mixing by cavitation treatment at the rate of at least 3 times passing the entire volume of WS processed through the structural elements of the cavitator.

[0014] The first stage of high-temperature WS treatment with pre-oxidation is carried out at a temperature of 160+2100C and pressure of 2.0+2.7 MPa until a pH value of 10.0+11.0 is achieved. The second stage of post-oxidation is carried out at a temperature of 165+2100C and a pressure of 2.0+2.7 MPa until a pH value of 8.5+9.0 is reached. In this case, the storage time of PP from the moment of adding the alkaline agent to the aqueous solution of LST with dissolved inorganic m / e should not exceed 48 hours. Thus, WS should be fed to the reactor within 2 days after preparation.

[0015] If the pH of WS with added m / e decreases by a pH value of more than 0.5 from the pH values of WS without added m / e, the pH is corrected by adding a potassium hydroxide solution, with an acceptable pH deviation of no more than 0.2 from the pH values of PP without m / e, with further additional circulation.

[0016] After the second stage of oxidation and unloading of the finished product from the reactor, it is cooled to 700C and then aqueous solutions of mixed or individual organically bound or chelated microelements of copper, zinc, manganese, iron, cobalt based on chelate complexes of modified lignosulfonic acids or EDTA, DTPA, EDDHA are introduced, as well as inorganic compounds: ammonium molybdate, boric acid or potassium metaborate with a total or individual mass concentration m / e - up to 9.0% on a.d.m. The second stage of high-temperature treatment and additional oxidation are carried out until pH 7.5+8.5 is achieved, by increasing the concentration of the oxidizing agent in the liquid phase or increasing the oxidation time, due to a decrease in the rate of unloading of the finished product from the reactor after the second stage of high-temperature treatment.

[0017] To increase the biological activity of the finished product, an aqueous solution of melamine salt of bis(oxymethyl)phosphinic acid with a mass concentration of 10-5 % / 10-6 % in the finished product is added to it stepwise with constant stirring.

[0018] The main features of the method are: primary dissolution of inorganic compounds of biogenic m / e in an aqueous solution of LST, the balance of ingredients, the concentration and sequence of dissolution of the components, the time and speed of mixing of the WS. The temperature and pressure of the reaction mixture are within the limits specified in the prototype.

[0019] During the research it was determined:

[0020] - the storage time of the WS from the moment of adding the alkaline agent to the aqueous solution of LST with dissolved inorganic m / e should not exceed 48 hours. Thus, the WS should be fed to the reactor within 2 days after preparation.

[0021] - the creation of stable m / e complexes based on HA by this method with a total concentration of individual or the sum of m / e in the finished product is possible in an amount not exceeding 4.0% in terms of dry matter (DM).

[0022] - to further increase the total amount of m / e in the product over 4.0% on an absolutely dry matter basis, it is necessary to add chelate complexes of copper, zinc, manganese, iron, and cobalt based on EDTA to their individual or total content in the chelate-humic complex up to 9.0% on an absolutely dry matter basis.

[0023] - with an increase in the mineral part of m / e in the finished product, the humic part proportionally decreases, which leads to a decrease in biostimulating properties. To compensate the biological efficiency of the organic part, an aqueous solution of melamine salt of bis(oxymethyl)phosphinic acid is added stepwise with constant stirring - up to a mass content of 10-5 % -5- 10-6 % in the finished product.

[0024] In accordance with the developed method, we present two stages of the method implementation with a description of the following actions and examples. Stage No. 1. Obtaining of Working Solutions for Subsequent Synthesis of Microelement Complexes Based on Humic Acid Salts

[0025] For a comparative assessment of the results of obtaining WS for obtaining Examples No. 1-6, six samples of WS with a set of different mineral m / e were prepared using the method described below. In this case, WS for example No.1 does not contain added m / e compounds and is a reference for comparing the physicochemical indicators of different WS.

[0026] The procedure for preparing WS samples with m / e for obtaining examples No. 1-6:

[0027] The recipes for preparing WS (base) are given in Table 1

[0028] • Inorganic m / e are consistently added to a 20.75% aqueous solution of technical LST with constant and intensive stirring. The stirring duration was 30 minutes at a given temperature of +30.00C. The weight of each m / e component given in Table 1 is determined by calculation with a given concentration of the biogenic ion in the finished WS.

[0029] • A 28% solution of potassium hydroxide was added with constant stirring to the resulting aqueous solution of LST with m / e. The stirring duration was 30 minutes at a temperature of +35.00C.

[0030] • Intensive stirring of the finished WS was carried out using a laboratory cavitator based on at least 3-time passage of the entire volume of the processed RR through the structural elements of the cavitator.

[0031]

[0032]

[0033] • After mixing is complete, the pH of the WS is recorded and if it decreases (Sample No.3 and No.6) by a pH value of more than 0.5 relative to Sample No.1 , the pH of the WS is corrected by adding a potassium hydroxide solution to the pH values of Sample No. 1 , with an acceptable pH deviation of no more than 0.2 with further intensive circulation.

[0034] • From each formulation of the obtained WS, 100 ml of an average sample are taken into glass bottles, hermetically packed for arbitration storage and control in a dark room at a temperature of +200C.

[0035] • After 72 hours, insignificant precipitation was observed in Samples 2 and 6, from 0.2-^-0.3% of the total mass of the sample, which is acceptable for feeding to the reactor for synthesis.

[0036] • Based on visual inspection of the samples, a conclusion was made about the advisability of limiting the storage time of WS with m / e before feeding into the reactor to no more than 48 hours.

[0037] • For a longer storage period of WS with m / e, WS must be subjected to intensive mixing before loading them into the reactor.

[0038] Stage No. 2. Synthesis of microelement complexes based on humic acid salts in a pilot reactor

[0039] Samples of Examples No. 1- / -6 were obtained in a 1.5 liter laboratory reactor made of stainless steel. The reactor is equipped with a system for heating reaction products, a stirrer, and an air bubbler.

[0040] The two-stage synthesis process in a pilot reactor is achieved by simulating the key process parameters of industrial reactors, namely, achieving the pH value at specified average temperatures at the final stage and changing the synthesis time and the consumption of the oxidizing agent. The order of loading, heating, and starting the synthesis processes in the reactor, as well as completing the synthesis and unloading the finished product in the pilot reactor, are carried out identically to the regulations for industrial equipment of a two-stage cycle. Procedure for obtaining samples of Examples No. 1+6

[0041] • The tested WS with a volume of 1000 ml was loaded into the reactor and sealed, the pressure in the reactor was increased to 22 bar, the contents in the reactor were heated to 1500C, after which air was supplied.

[0042] • The synthesis of GC proceeded for 120+150 min, at a pressure of 22+23 bar, temperature of +170+1800C with an air flow rate passing through the reactor of 60+80 l / h, constant stirring and with periodic pH monitoring.

[0043] • The synthesis process was stopped when the pH dropped below 8.5, by turning off the heating and air supply. The unloading of the finished product of each sample was carried out after natural cooling of the product in the reactor below 700C.

[0044] • As a result of the sequentially carried out synthesis on samples No.1+6, examples of finished products of m / e complexes based on HA were obtained, the composition parameters of which are given in Table 2

[0045]

[0046] As can be seen from Table 2, the confirmed result of the conducted synthesis of working solutions was obtaining samples of examples No. 1-45 with target concentration values (Ctotal) of biogenic m / e (for examples No.2-45) in the range of 0.5-5-4.0% on an a.d.m. in the finished product and with a content of HA salts in the range of 45-5-62% in organic matter. The obtained samples are stable during the observed period of time and contain the amount of insoluble suspended particles acceptable for the target product.

[0047] Procedure for obtaining sample example No. 7

[0048] Sample example No.7 was prepared to increase the proportion of chelate complexes in the composition of the obtained HA complexes to a total m / e content of 9.0% on a.d.m.

[0049] • Solutions of m / e chelate complexes based on EDTA were consistently added to sample No.5 with a volume of 400 ml, with constant stirring and a set temperature of +30.00C in the following quantities:

[0050] -Cu EDTA - 26.46 g, anhydrous salt based on the mass of WS

[0051] -Mn EDTA - 40.18 g, anhydrous salt based on the mass of WS -Zn EDTA - 50.96 g, anhydrous salt based on the mass of WS

[0052] • Each subsequent ingredient is added to the reaction mixture in 30 minutes after the previous one.

[0053] • The calculated content of organically bound and chelated m / e obtained in the example was 9.0% on an a.d.m., the content of HA salts in organic matter was 28.2%, dry matter - 38.5%, suspended particles content was 0.9%, pH 7.9.

[0054] Procedure for obtaining sample example No.8

[0055] Sample example No.8 was made to increase the biostimulating properties of sample No.7, where the reduction in the humic part reached 50% of the initial mass of HA.

[0056] • An aqueous solution of melamine salt of bis (oxymethyl) phosphinic acid with a calculated concentration in the finished product of 10-5 % -5- 10-6 % was added to sample No.7 with a volume of 200 ml. • Low concentration of melamine salt of bis (oxymethyl) phosphinic acid in the finished product slightly changes the concentrations of m / e, HA salts and dry matter content in general, but increases biostimulating properties and activity of the product in general by up to 10%.

[0057] • From each obtained sample of Examples No. 1 / 8, average samples of 100 ml were selected and divided into two equal parts.

[0058] The first part of 50 ml from all obtained samples each was placed in glass bottles and hermetically sealed for observation and arbitration storage in a dark room at a temperature of +200C, for 12 months.

[0059] For 12 months of storage of arbitration samples of examples No.1 / 8, precipitation, stratification, color change and gas formation was not observed, which characterizes the high stability of the final product.

[0060] The second part of the obtained examples was sent for studies of biological activity and laboratory tests.

[0061] Procedure for obtaining sample of example No. 9

[0062] The following were used as components for obtaining sample of example No.9:

[0063] - 500 ml of the initial sample prepared as a 22.5% aqueous solution according to the recipe of Example No.2, the content of chelated iron in sample No.2 in solution is 1.01% or 4.0% in terms of a.d.m.;

[0064] - 300 ml of added 32.5% aqueous solution of chelated iron based on modified lignosulfonic acids, the iron content in the solution is 3.43% or 10.55% on a.d.m.

[0065] • 300 ml of chelated iron solution based on modified lignosulfonic acids were added to the initial sample of Example No. 2 with a volume of 500 ml with constant stirring and a set temperature of +27.00C.

[0066] • Mixing was carried out for 50 minutes after the end of the second component feed.

[0067] • After the end of the mixing of the solutions the precipitation, stratification, colour change and gas formation were not observed. The total calculated content of chelated iron in the solution based on both components in the product was 1.9% or 7.9% on a.d.m.

[0068] The content of HA salts in organic matter was 39.0%, DM - 24.07%, suspended solids content was 0.2%, pH 7.3.

[0069] The resulting solution sample was stable during the observed period of time and contained the amount of insoluble suspended solids acceptable for the target product.

[0070] Procedure for obtaining sample No. 10

[0071] The following were used as components for obtaining sample No.10:

[0072] - 500 ml of the initial sample prepared as 22.5% aqueous solution according to the recipe of Example No.2, the content of chelated iron in sample No. 2 in solution is 1.01 % or 4.0% in terms of a.d.m.

[0073] - 300 ml of the added sample, in the form of a 32.5% aqueous solution of chelated iron based on the chelated complex Fe DTPA, the content of iron based on DTPA in the solution is 3.3% or 10.9% in terms of a.d.m.

[0074] • 300 ml of the solution of the chelated complex Fe DTPA were added to the initial sample of Example No.2 with a volume of 500 ml, with constant stirring and set temperature of +30.00C. • Stirring was carried out for 30 minutes after the end of the second component feed.

[0075] The total calculated content of chelated iron in the solution based on both components was 1.99% or 7.74% on an a.d.m. in the product.

[0076] The content of HA salts in organic matter was 32.1%, DM - 25.74, suspended solids content was 0.78%, pH 7.5. The resulting solution sample was stable during the observed period of time and contained the amount of insoluble suspended solids acceptable for the target product.

[0077] Procedure for obtaining sample of example No.11

[0078] The following components were used to obtain the sample:

[0079] - 500 ml of the initial sample prepared as a 22.5% aqueous solution according to the recipe of Example No.2, the content of chelated iron in sample No.2 in solution is 1.01% or 4.0% in terms of a.d.m.;

[0080] - 300 ml of the added sample in the form of a 32.5% aqueous solution of chelated iron based on the chelate complex Fe EDDHA, the iron content in the solution is 1.87% or 6.19% on a.d.m.

[0081] • 300 ml of an aqueous solution based on the chelate complex Fe DTPA were added to the initial sample of Example No. 2 with a volume of 500 ml, with constant stirring and set temperature of +30.00C.

[0082] • Stirring was carried out for 30 minutes after the end of the second component feed.

[0083] The total calculated content of chelate m / e contained in the sample of Example 2 and added from the solution of Fe EDDHA salts in the product was 1.99% or 7.74% on a.d.m.

[0084] The content of HA salts in organic matter is 32.1%, DM - 25.74%, the content of suspended particles is 0.78%, pH 7.5.

[0085] The resulting sample is stable during the observed period of time and contains the amount of insoluble suspended particles acceptable for the target product.

[0086] Procedure for obtaining sample No. 12

[0087] The following were used as components for obtaining sample No.12: - 500 ml of the original sample, prepared as a 21.4% aqueous solution according to the recipe of Example No.5, which has the following content of organically bound and chelated m / e:

[0088] - Co - 0.057% in solution or 0.256% on a.d.m.,

[0089] -Mo - 0.02% in solution or 0.089% on a.d.m.,

[0090] -Cu - 0.052% in solution or 0.231% on a.d.m.,

[0091] -B - 0.023% in solution or 0.105% on a.d.m.,

[0092] -Zn - 0.053% in solution or 0.235% on a.d.m.,

[0093] -Mn - 0.075% in solution or 0.337% on a.d.m.,

[0094] The total content of organically bound and chelated m / e in the solution of Example 5 is 0.28% in solution or 0.99% on a.d.m.

[0095] - 300 ml of the added sample in the form of a 29.5% aqueous solution of a mixture of chelate complexes of Co, Zn, Mn, Cu based on modified lignosulfonic acids. The content of chelate m / e in the added sample:

[0096] - Co in solution - 0.1% or 0.33% on a.d.m.,

[0097] - Zn in solution - 1.34% or 4.53% on a.d.m.,

[0098] - Mn in solution - 1.2% or 4.04% on a.d.m.,

[0099] - Cu in solution - 0.58% or 1.97% on a.d.m.,

[0100] The total m / e content in the added solution is 3.21% in solution or 10.87% on a.d.m.

[0101] • 500 ml of a mixture of chelate complexes of Co, Zn, Mn, Cu based on modified lignosulfonic acids were added to the initial sample of Example No.5 with a volume of 500 ml, with constant stirring and set temperature of +25.00C.

[0102] • Stirring was carried out for 30 minutes after the end of the supply of the second component.

[0103] • After the completion of mixing of the solutions the precipitation, stratification, colour change and gas formation were not observed. The final calculated individual and total content of microelements in Example 12, obtained on the basis of the sample of Example 5 and modified lignosulfonic acids in the resulting solution of the sample of Example 12 was:

[0104] Co - 0.079% in solution or 0.308% on a.d.m., Mo - 0.01% in solution or 0.039% on a.d.m., Cu - 0.327% in solution or 1.276% on an a.d.m., Boron - 0.011% in solution or 0.043% on a.d.m., Zn - 0.723% in solution or 2.82% on a.d.m., Mn - 0.662% in solution or 1.315% on a.d.m., Total m / e content 1.809% in solution or 7.06% on a.d.m.

[0105] The total dry matter content of the obtained sample is 27.9%

[0106] Content of HA salts in organic matter is 30.1%, dry matter content is 25.62%, suspended particles content is 0.7%, pH is 6.3.

[0107] The obtained sample is stable during the observed period of time and contains the amount of insoluble suspended particles acceptable for the target product.

[0108] Procedure for obtaining sample No.13

[0109] The following were used as components for obtaining sample No.13:

[0110] - 500 ml of the original sample, prepared as a 25.2% aqueous solution, made according to the recipe of sample Example No.3, containing organically bound Boron in an amount of 0.92% in solution or 3.5% in terms of a.d.m., the content of HA salts in organic matter is 48.2%;

[0111] - Dry reagents were used as additional components:

[0112] 26.0 g. of dry potassium metaborate, containing 10.4% Boron in the reagent;

[0113] - 3 g. of dry ammonium molybdate, containing 54.4% Molybdenum in the reagent.

[0114] • 26.0 g of potassium metaborate and 3 g of ammonium molybdate were added to a 500 ml sample of Example No.3 with constant stirring and set temperature of +35.00C.

[0115] • Stirring was carried out for 40 minutes after adding the third component.

[0116] • After the dry ingredients were completely dissolved and the solution was stirred, no precipitation, color change, or gas formation were observed. As a result, a sample of Example No.13 was obtained, which is characterized by the following composition:

[0117] - total dry matter content of the obtained sample - 27.9%

[0118] - calculated mass content of Boron - 1.23% in solution or 4.4% in terms of a.d.m.;

[0119] - calculated mass content of Molybdenum - 0.253% or 0.9% in terms of a.d.m.;

[0120] - total m / e content - 1.48% in solution or 5.3% in terms of a.d.m.;

[0121] Content of HA salts in organic matter - 41.1%, content of suspended particles - 0.5%, pH 8.0.

[0122] The obtained sample is stable during the observed period of time and contains the amount of insoluble suspended particles acceptable for the target product.

[0123] INDUSTRIAL APPLICABILITY

[0124] An important feature of the method is the ability for the manufacturer of m / e complexes to refuse or reduce the use of expensive chelate complexes based on EDTA and Glycine and implement the production of chelate m / e complexes and humic acid salts in one technological chain. At the same time, the initial raw material technical LST and salt inorganic m / e are more economically advantageous and affordable raw materials for the production of organomineral fertilizers, growth stimulants, feed and food additives and even pharmaceuticals.

Claims

CLAIMS1. Method for producing organic microelement complexes based on humic acid salts, characterized by mixing an aqueous solution of lignosulfonate with an alkaline agent - potassium or sodium hydroxide, wherein dry or aqueous solutions of copper, zinc, manganese, iron, cobalt, ammonium molybdate sulfates, as well as boric acid or potassium metaborate are introduced into the aqueous solution of lignosulfonate before mixing with the alkaline agent to a total mass concentration of microelement ions in the range of 0.5-4.0% on a.d.m, after mixing with the alkaline agent, the resulting working solution is subjected to intensive mixing with cavitation treatment at the rate of at least 3 times passing the entire volume of the processed working solution through the structural elements of the cavitator, and the storage time of the working solution from the moment of adding the alkaline agent to the aqueous solution of lignosulfonate with dissolved inorganic microelements is no more than 48 hours before feeding into the reactor, then the tested working solution with a volume of 1000 ml. is loaded into the reactor, which is sealed, the pressure in the reactor is increased to 22 bar, the contents in the reactor are heated to 1500C, after which air is supplied, the synthesis of microelement complexes based on humic acid salts occurs within 120-150 minutes, at a pressure of 22-23 bar, temperature of +170 - 1800C, with an air flow rate passing through the reactor of 60-80 l / h, constant stirring and with periodic pH monitoring, the synthesis process is stopped when the pH drops below 8.5, by turning off the heating and air supply, the unloading of the finished product is carried out after natural cooling of the product in the reactor below 700C, carrying out the synthesis in the presence of an oxidizing agent of air.

2. Method of claim 1 wherein after natural cooling of the product in the reactor below 700C and unloading of the finished product, solutions of mixed or individual organically bound chelate microelements of copper, zinc, manganese, iron, cobalt or solutions of chelate complexes of modified lignosulfonic acids or EDTA, DTPA, EDDHA, as well as inorganic compounds are added: ammonium molybdate, boric acid or potassium metaborate with a total or individual mass concentration of microelements of up to 9.0% on an a.d.m.

3. Method of claim 1 wherein in order to increase the biological activity of the finished product, an aqueous solution of melamine salt of bis(oxymethyl)phosphinic acid is added to it in stages with constant stirring until the mass concentration of melamine salt of bis(oxymethyl)phosphinic acid in the finished product is 10-5% - 10-6%.

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