RU2479559C2 - Method of producing granular organomineral nano-fertilisers - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to agriculture. The method of producing granular oranomineral nano-fertilisers, which involves mixing dry starting mineral components selected from: carbamide, ammophos, diammonium phosphate, ammonium nitrate, superphosphate, double superphosphate, ammonium sulphate, potassium chloride, potassium sulphate, potash, ground phosphorite; mineral components containing trace elements: Mg, B, Mn, Zn, Cu, Ni, Co, Cr, Mo; and an organic component selected from humic substances, wherein dynamic conditions in the moulding zone - thermobaric conditions in a rotary pelleting press: pressure of 20-35 MPa and temperature of 100-125°C, lead to mechanical and chemical processes to form nano-sized complexes of humic substances with mineral components of the mixture, having growth stimulant properties, prolonged action and high biological activity.

EFFECT: invention enables to obtain granular organomineral nano-fertilisers using an energy-saving, single-step wasteless technique, wherein the granules have excellent mechanical properties, do not clump, are nonhygroscopic; the activated humic complexes encapsulated into the granules do not aggregate and do not lose biological efficiency during storage.

5 cl, 7 dwg, 7 tbl

Description

 The invention relates to a method for producing granular organic-mineral nanofertilizers.

Most modern developments in the field of technologies for producing granular fertilizers are aimed at increasing the efficiency of fertilizers by balancing their composition, as well as by modifying the structure, which leads to a prolonged action and growth-stimulating effect [O.S. Bezuglova. Fertilizers and growth stimulants. Rostov-on-Don. 2002].

Of particular interest in this regard are organic-mineral fertilizers (OMU) using as an organic component humic substances (HV) of various origins: water-soluble salts of humic acids (humates), peat, sapropels, brown coal, animal waste [patent application of the Russian Federation No. 2000131688, IPC 7688, IPC ⁷ C05G 5/00, C05C 9/00, C05B 19/00; RF patent No. 2184102, IPC ⁷ C05 F3 / 00, C05G 3/04; RF patent application No. 2001118759, IPC ⁷ C05 F 11/02, RF patent application No. 2002106256, IPC ⁷ C05 F 11/02, RF patent application No. 2002118471, IPC ⁷ C05F 11/02, US patent No. US-2009 / 0126432 IPC ⁷ C05G 1/00, FBR patent No. 2307678, IPC ⁷ C05F 11/02]. It was established that such WMDs containing nanostructures in their composition have increased efficiency [RF patent No. 2104988, IPC ⁶ IPC ⁷ C05F 11/02, application for patent of the Russian Federation No. 971000360, Egorov NP et al. Development and conduct of an experimental evaluation of the effectiveness of the application of new types of fertilizers in crop production using nanotechnology, suev @ nnov.ru. 20.09.08].

The patent literature describes methods for producing WMD, which are nanomaterials.

For example, a polyvinyl acetate or polyacrylamide polymer film is obtained with HS encapsulated in it [N. Egorov. et al. Development and conduct of an experimental assessment of the effectiveness of the application of new types of fertilizers in crop production using nanotechnology, suev@nnov.ru.20.09.08].

The disadvantages of this method is the high cost of the product, the imbalance of the composition: this fertilizer does not contain the basic elements of the mineral nutrition of plants: nitrogen, phosphorus, and potassium, therefore, when applying it, additional fertilizers must be added, and low-tech application in agriculture.

There is a simple method for producing organic-mineral nanofertilizers with increased efficiency, which consists in highly efficient grinding of dry urea and brown coal [RF patent No. 2104988, IPC ⁶ C05F 11/02]. The microstructure of the grinding product is a nanotube.

The disadvantages of the method are the imbalance of the composition (the product does not contain phosphorus and potassium), low-tech application and the difficulty of storing highly dispersed powder.

There is a method for producing highly effective granular nanofertilizers of balanced composition from nanoscale emulsion of HS in a solution of sodium hydroxide, urea, potassium and ammonium salts (phosphates, chlorides, sulfates), followed by neutralization and evaporation of the emulsion, granulation in a roll granulator [patent No. CN 10122510, C05 00, European application no. (ECLA) CN 20071000899 20070117].

The disadvantages of the method include multi-stage, high energy consumption, the use of aggressive substances: sodium hydroxide, acids, and the main disadvantage: when the emulsion is evaporated, nanoscale complexes are aggregated into larger ones, which reduces the biological activity of the product.

Known non-energy-intensive non-waste method for producing granular WMD of a given composition, which consists in pressing fertilizer mixtures with a moisture content of 1-3% by weight, consisting of a typical mineral nitrogen, phosphorus and potassium-containing raw materials and HS selected from the series: water-soluble humates of potassium and sodium, peat, biohum in a typical rotary molding granulator (GFR), the closest in technical essence to the claimed [RF patent No. 2225382 IPC ⁷ С05С 9/00, C05G 1/00].

To obtain granules with improved mechanical characteristics: the static strength of granules 3.1-3.9 MPa, non-caking, it is necessary to additionally introduce reinforcing additives - talc, perlite, carbon black in an amount of 0.1-0.3% and a water-repellent additive - polymethylhydrosiloxane liquid GKZH - 94 in an amount of 0.04-0.4%.

The method has the following disadvantages:

- the thermobaric regime due to the shape of the pressing channel of the GFR matrix (cylinder of constant radius at the inlet and outlet) is not hard enough: the dynamic pressure in the pressing zone does not exceed 12 MPa and the temperature is 50-100 ° C depending on the composition and humidity of the mixture, therefore, nanoscale no structures are formed. WMD data do not show increased efficiency: growth-stimulating effect has not been established, utilization rates 64-75%;

- the strength increase of the granules at the outlet of the pressing channels of the GFR matrix is not fast enough, therefore, to improve the mechanical characteristics, reinforcing and hydrophobizing additives are introduced, which complicates the technology and makes the product more expensive;

- the method will not allow the use of coals as HS, which are the most affordable, cheap, concentrated in terms of the content of humic acids natural raw materials, since without transferring them to a highly dispersed (<100 nm) state they cannot enter the root system of plants [A.A. Klimova et al. Effect of humic preparations on plant growth processes. In: Scientific works of the Tyumen Agricultural Institute. "Humic preparations" vol. XIV, pp. 188, 189, 1971].

The essence of the invention is a one-stage low-energy non-waste method for producing granular organic-mineral nanofertilizers, including mixing dry initial mineral components selected from the series: carbamide, ammophos, diammonium phosphate, phosphoric flour, ammonium nitrate, superphosphate, double ammonium sulfate, double superphosphate, potassium, potash; mineral components containing trace elements: Mg, B, Mn, Zn, Cu, Ni, Co, Cr, Mo and HS; granulation and sieving of granules, characterized in that the granulation is carried out in a rotary press granulator (RPG) in thermobaric mode: the pressure in the pressing zone is 20-35 MPa, the temperature is 100-125 ° C, which leads to mechanical-chemical processes with the formation of nanoscale HS complexes with mineral components (from 100 to 10 nm), possessing the properties of growth stimulants, prolonged action and increased bioactivity, which lasts for a long time, since bioactive nanocomplexes encapsulated in a rigid matrix - g ranul WMD are not aggregated; allows the use of HS of any origin, in particular coal; the introduction of reinforcing and water-repellent additives is not required. The method is illustrated by drawings and photographs (Fig.1-7). Figure 1 shows the design of a rotary press granulator, which creates a thermobaric pressing mode, ensuring the achievement of the goal. The development of the desired pressure and temperature is determined by the shape of the pressing dies of the RPG matrix, having a conical part - the pre-compression zone. In total, the matrix contains 5200 pressing dies.

RPG design elements indicated in FIG. 1:

1 - initial mixture;

2 - annular rotating matrix;

3 - the first pressing roller;

4 - second pressing roller;

5 - wedge clearance;

6 - conical part of the die (pre-compression zone);

7 - pressing channel of the die;

8 - expansion well dies;

9 - a granule;

10 - fixed knife for cutting granules.

The initial mixture enters the inner surface of the annular matrix. When the matrix rotates, the mixture is carried away into the wedge gap between the inner surface of the matrix and the pressing rollers. As the product moves in the wedge gap of the first roller, the pressure increases, which leads to the filling of the conical part of the die (pre-compression zone) and the formation of a uniformly distributed product layer on the inner surface of the matrix. The minimum clearance between the second roller and the matrix ensures maximum compression of the product in the conical part of the die and the movement of the product in the press channel of the die. Channel resistance and an adjustable matrix rotation speed provide compression of the product to a pressure of 20 to 35 MPa. In this case, the mixture is heated from 100 to 125 ° C, the components of the mixture (urea, ammophos, ammonium sulfate, ammonium nitrate) melt with the formation of a visco-plastic state of the mixture. The movement of the mixture from the press channel into the expansion well of the die is accompanied by an instantaneous change in pressure and cooling of the compressed mass to 50-70 ° C. Formed cylindrical granules at the exit of the die are cut off with a fixed knife. The length of the granules is governed by the location of the knife with respect to the matrix. Cleaning of the fine fraction and cooling of the granules is carried out by the method of pneumatic sorting.

The conditions arising in the press channel of the spinnerets (thermobaric effect) and the concentration of humic substances (HW) in the initial mixture are the determining factors for complexation reactions involving HW and mineral components. The thermodynamic parameters of the granulation process (pressure and temperature) are set by the shape of the pressing channel and are controlled by the rotation speed of the matrix. The technological parameter for this regulation is the current load on the granulator motor equipped with a frequency converter. The degree of nanosized complexation, which determines the target properties of the product, is controlled by the weight dosing of the HS at the stage of preparation of the mixture (other components of complexation are always present in excess).

Both synthetic and natural mineral raw materials were used as initial raw materials for the preparation of mixtures:

1. Phosphate rock, natural mineral raw materials, as an individual fertilizer, can be absorbed by plants only on acidic soils - podzolic and peat soils, in which Ca ₃ (PO ₄ ) ₂ gradually passes into Ca (H ₂ PO ₄ ) ₂ · H ₂ hydrophosphate available to plants O. The assimilation of phosphate rock is favored by the fineness of grinding, as well as its introduction into the soil together with acidic fertilizers, for example, with (NH ₄ ) ₂ SO ₄ , contains a wide range of microelements;

2. Ammophos. Mainly composed of monoammonium phosphate, NH ₄ H ₂ PO ₄ and partially diammonium phosphate, (NH ₄ ) ₂ HPO ₄ , synthetic raw materials;

3. Diammonium phosphate. Mainly composed of (NH ₄ ) ₂ PO ₄ , synthetic raw materials;

4. Potassium chloride, KCl, a natural mineral raw material, contains a wide range of trace elements;

5. Urea, NH ₂ CONH ₂ , the source of nitrogen most available to plants, synthetic raw materials;

6. Ammonium sulfate, (NH ₄ ) ₂ SO ₄ , used for alkaline soils, synthetic raw materials;

7. Potassium sulfate, K ₂ SO ₄ , synthetic raw materials;

8. Potassium carbonate (potash), K ₂ CO ₃ , synthetic raw materials;

9. Superphosphate (2CaSO ₄ · Ca (H ₂ PO ₄ )), double superphosphate (Ca (H ₂ PO ₄ )), synthetic raw materials;

10. Water-soluble humates of potassium and sodium, a synthetic raw material obtained by the extraction of humic acids from coal with solutions of caustic alkalis;

11. Peat, natural raw materials;

12. Biohum, synthetic raw materials, a product of microbiological processing of bird droppings;

13. Brown coal with a high content of fulvic acids (not less than 60%) or naturally oxidized coal of the Gramoteinsky deposit with a humic acid content of not less than 67%.

For an example, Table 1 shows the elemental composition of naturally oxidized coal from the Gramoteinsky deposit.

When working out the thermobaric regime, temperature and pressure were controlled by changing the humidity of the initial mixture in the range from 1 to 4% and the RPG rotor speed. These factors have a very significant effect on the processes of mechanical friction of the mixture substance in the channels of the RPG matrix and the distribution of local stresses in the mixture crystals. The energy released is sufficient to melt the urea. Due to the achievement of elevated temperatures and pressures in the reaction zone, as well as the presence in the mixture of fusible urea and salts, a plastic state was achieved.

The trace element composition was regulated by introducing certain amounts of salts of the corresponding trace elements and humic substances (GW) into the initial mixture.

When developing a method for producing WMD, we studied the chemistry of the process that occurs during granulation: the role of hydrolysis, thermolysis, and complexation processes is clarified.

At an elevated temperature of 100-125 ° C, to which the mixture is heated in a granulator, various chemical reactions can occur:

- thermal decomposition of urea with the formation of ammonium cyanate, NH ₃ , biuret and cyanuric acid

- hydrolytic cleavage of urea

CO (NH ₂ ) ₂ + H ₂ O → NH ₂ CONH ₄ → (NH ₄ ) ₂ CO ₃ + NH ₃ ↑ + H ₂ O → NH ₃ + CO ₂ + H ₂ O;

- hydrolysis of salts of Ca, Mg, Sr, which are part of the phosphate rock,

Me (H ₂ PO ₄ ) ₂ + yH ₂ O↔MeHPO ₄ + H ₃ PO ₄ + (y-1) H ₂ O

10MeHPO ₄ + zH ₂ O↔Me ₁₀ (PO ₄ ) ₆ (OH) ₂ + (z-2) H ₂ O + 4H ₃ PO ₄ ;

- complexation

CO (NH ₂ ) ₂ · NH ₃ ; CO (NH ₂ ) ₂ · KCl; CO (NH ₂ ) ₂ · H ₃ PO ₄ ; CO (NH ₂ ) ₂ · MeH ₂ PO ₄ , CO (NH ₂ ) ₂ · HS; [Me ²⁺ · HB] · HPO ₄ .

To establish the nature of chemical processes during granulation, the following experiments were carried out:

- 100 kg of fertilizer mixtures were prepared in a vibration mill with an NPK content of 16-16-16 and 12-12 11, GV - 3%, humidity ~ 1.5%. A mixture of water-soluble humates of potassium and sodium (initial fertilizer mixtures) was used as HS;

- the initial mixture was heated for 4 hours in a thermostat at 110 ° C with the introduction of 1 time in 20 minutes of water to 1.5% (heated mixture);

- spent the granulation of the initial mixtures in the RPG (granular WMD);

- analyzed all mixtures for the content of total nitrogen (N); water soluble phosphorus (P ₂ O ₅ ) and calcium (Ca); assimilable phosphorus (P ₂ O ₅ ); biuret; water insoluble residue; pH of the aqueous extract. The analyzes were carried out using the tested methods [GOST 30181.1-4, GOST 2081-92, GOST 20851.2-75, GOST 20851.4-75, GOST 24596.5-81]. The results are shown in table 2.

table 2 The composition of the organic-mineral mixtures: urea-phosph. flour-KCl-humate " The name of the mixture M / d total nitrogen (N) in dry matter,% M / d H ₂ O,% M / d biuret,% pH of an aqueous extract, units pH M / d P ₂ O ₅ ,% M / d water soluble Ca,% M / d residue, insoluble in water,% water soluble digestible one 2 3 four 5 6 7 8 9 1. Original 16-16-16 16.1 ± 0.1 1,6 0.15 ± 0.05 8.65 ± 0.05 0.006 0.37 0.20 47.9 ± 0.2 2. Original 12-12-11 11.9 ± 0.1 1.8 0.12 ± 0.05 8.72 ± 0.05 0.003 0.29 0.17 31.4 ± 0.2 3. Warmed up 16-16-16 16.0 ± 0.1 1,5 0.17 ± 0.05 8.60 ± 0.05 0.007 0.39 0.32 47.5 ± 0.2 4. Warmed up 12-12-11 11.9 ± 0.1 1,6 0.11 ± 0.05 8.73 ± 0.05 0.003 0.30 0.24 31.0 ± 0.2 5. OMU 16-16-16 16.1 ± 0.1 0.5 0.14 ± 0.05 8.70 ± 0.05 4,54 12.3 ± 0.1 4.2 ± 0.1 6.1 ± 0.2 6. OMU 12-12-11 11.9 ± 0.1 0.4 0.15 ± 0.05 8.68 ± 0.05 4.09 9.2 ± 0.1 3.3 ± 0.1 4.7 ± 0.2

From the data of table 2 it can be seen that the role of hydrolytic and thermal decomposition can be neglected, these reactions proceed in trace amounts. Judging by the increase in water solubility of granular WMDs as compared to the initial mixtures and those heated at atmospheric pressure, it can be concluded that the thermobaric effect carried out in an RPG granulator leads to reactions involving humates with the formation of new structures.

Such a sharp increase in solubility in water as a result of granulation in RPG mineral mixtures was not observed. It can be assumed that at high pressure under conditions of dynamic pressing in RPG, complexation occurs with the participation of HS and mineral components. Because water-soluble humates are nanomaterials, then, obviously, this interaction proceeds at the nanoscale.

When studying the solubility in water of granular WMDs, it was found that even when the content of phosphorite flour insoluble in water in the mixture is up to 50%, the mass fraction (m / d) of the water-insoluble residue does not exceed 7.1% (see examples 5.11 of table 4).

The UV spectra of humates, initial mixtures, heated mixtures and granular WMD were recorded on an SF-4 spectrophotometer, the concentration of humates in all solutions was 0.01 mg / ml, the solvent and the comparison solution were water, and the thickness of the light-absorbing layer was 10 mm.

The spectra are shown in figure 2:

1 - UV spectrum of humates;

2 - UV spectrum of the initial mixture 12-12-11;

3 - UV spectrum of the initial mixture 16-16-16:

4 - UV spectrum of the heated mixture 12-12-11;

5 - UV spectrum of the heated mixture 16-16-16;

6 - UV spectrum of granular WMD 16-16-16;

7 - UV spectrum of granular WMD 12-12-11;

A is the optical density, units optical density;

λ is the wavelength, nm.

The UV spectra of the ungranulated starting and heated mixtures almost coincided with the spectrum of humate. The spectra of the OMU granular in RPG in shape are the same as the humate spectrum (curves 6, 7), but a shift in the absorption intensity to the short-wavelength region (hypsochrome) is observed (see FIG. 2).

There is data in the scientific literature regarding the study of the UV spectra of complexes of humates with metal chelates, donor-acceptor complexes formed in solutions [D.S. Orlov. Soil chemistry. M. 1972]. In all the cases described, a bathochromic shift is noted. Obviously, when granulating, other structural transformations occur. Similar effects: an increase in solubility in water, and a shift in the absorption intensity to the short-wavelength region of the spectrum was noted during the mechanochemical treatment of peat with carbamide, which was carried out by heating at high pressure and efficiently dispersing mixtures in order to obtain nanostructured compositions for building materials, with oxidative degradation of peat hydrogen peroxide [Yu.S. Sarkisov et al. Physico-chemical features of the processes of activation and modification of peat in the technology of building materials. In: Bulletin of TSPU, issue No. 4, pp. 26-30, 2008].

Studies of the microstructure of samples of mineral fertilizers and WMD were conducted at the Institute of Catalysis named after G.K. Boreskov by scanning electron microscopy using a JEOL, JSM-64660 instrument (the lower limit of instrumental resolution for the studied samples is 10 nm).

Electron microscopic examination of the samples of WMD with a GW content of 4.8 to 10.5% showed the presence of dendritic structures with sizes less than 100 nm.

For example, Fig. 3 shows an electron microscope image of WMD with a humate content of 4.8%, taken at a maximum magnification of (50,000), which allows one to detect nanosized particles (from 100 to 40 nm) without signs of crystallinity (type 1), grouped in agglomerates on the surface of larger particles and having a developed surface area. Similar nanosized particles were found in all the studied WMDs, while for all the studied mineral fertilizers obtained in the RPG, only large particles with sizes larger than 100 nm of the crystalline structure with faces and chips characteristic of crystals were detected (type 2).

Thus, the treatment of humate-containing WMDs at a temperature of 100-125 ° C and a pressure of 20-35 MPa leads to the formation of highly dispersed HS particles on the surface of the mineral substrate.

A fundamentally important experimental fact is the presence of such structures only in WMDs containing HV and processed in RPG at a pressure in the range from 20 to 35 MPa and a temperature from 100 to 125 ° C. In all other samples, such finely dispersed structures were not observed (absent).

It is also important to note that the formation of particles with sizes less than 1 μm due to only mechanochemical disintegration is impossible, therefore, is the result of dynamic thermobaric treatment.

The particle size distribution obtained for samples of humate-containing WMD is shown in Fig. 4 (the ordinate axis is “N” is the number of particles,%; the abscissa axis is the particle size, nm), it shows that particles with sizes less than 100 are present in them nm, providing a high surface area of hot water.

Comparison of particle sizes of a single molecule of humates, previously determined in independent studies [N.N.Danchenko. The functional composition of humic acids: Determination and relationship with reactivity. Diss. Cand. Chem. Sciences, M. 1997], and obtained in WMD by the proposed method, shows that the observed type 1 formations can consist of a small number of molecules or even single HS molecules. Such a state of HS, apparently, provides an increased specific concentration of active centers of HS responsible for the exchange of macro- and microelements in the filtration zone of the plant root system and thereby the ability of humate-containing WMDs to stimulate their growth.

When the synthesis conditions in the technological process changed — at pressures below 20 MPa and temperatures below 100 ° C — humate-containing WMDs were obtained, in which only type 2 particles were observed, and type 1 particles were absent. The presence of growth stimulant properties for these samples was not confirmed.

The surface study of fertilizer samples containing no HS (NP and NPK), in order to detect the presence of fine particles, was carried out by atomic force microscopy (AFM) on an SMM2000T instrument in air in contact mode using a scanner with a scanning field (X × Y × Z : 6 μm × 6 μm × 1 μm). For this, the sample — a granule ~ 7 mm long — was fixed on the microscope stage. No additional preliminary surface preparation procedures were carried out.

5, for example, presents a three-dimensional image of the surface obtained for the sample NPK-16-16-16 (columns), the scanning field (5.8 μm × 3.4 μm × 914 nm). On the surface images of samples of mineral fertilizers like NPK and NP that do not contain HS, no particles with sizes less than 500 nm were observed.

In other samples of mineral fertilizers of various compositions that do not contain HS, such structures were also not observed.

We studied the solubility of granular WMD 16-16-16 and non-granulated fertilizer mixture of the same composition in dynamic mode by stoichiographic differentiating dissolution at the Institute of Catalysis named after G.K.Boreskova. The solubility curves of the components of the non-granulated fertilizer mixture are shown in FIG. 6, the solubility curves of the components of the WMD are shown in FIG. 7 (the ordinate axis is “a” is the mass fraction of the component in the solution,%; the abscissa axis is “t” is the dissolution time, min). The image size of the surface is made in the scale corresponding to the following segment of 500 nm. A sample of the sample was placed in a flow reactor of a stoichiograph and the solvent was supplied at a rate of 3.6 ml / min, gradually changing the composition of the solvent and raising the temperature from 20 to 85 ° C.

In step I, H ₂ O was passed through the reactor for 7 minutes.

In stage II, they passed from H ₂ O to a 1.2 M HCl solution.

At stage III, HF with a continuously increasing concentration from 0.01 M to 1.0 M was used as a solvent. After the reactor, the flow was directed to a detector-analyzer of elemental composition - an atomic emission spectrometer with inductively coupled plasma (AIS-ICP) from BAIR. The concentration of elements in the solution was determined with a frequency of 5 seconds and a relative error of 5%. In the case of a sample of non-granulated fertilizer mixture, the solubility at each stage was significantly less than the sample of WMD.

As can be seen from Fig.6, in water there is a dissolution of the readily soluble part of the sample of non-granulated fertilizer mixture, which amounts to about 25% of the initial mass. The composition of this part includes the elements P, K, Na, S.

In stage II, immediately after exposure to the sample with a HCl solution, dissolution of Ca, Fe, Mg, P, Al, and S is observed. This part of the sample is about 30%.

At stage III, with a gradual transition to HF, the dissolution of Si, Fe, Mg, and Al occurs. This part of the sample is about 45%.

The solubility of the WMD sample after treatment in RPG at a temperature of 120 ° C and a pressure of 30 MPa changed significantly (Fig. 7).

The solubility of WMD in water increased to 87%. Such a significant difference in solubility indicates the occurrence of chemical reactions at the granulation stage of WMD.

From the obtained data it can be concluded that under technological conditions in the melt of urea and other low-melting mineral components without thermal decomposition of the latter and the formation of gaseous ammonia, reactions of the formation of new compounds with greater solubility in water occur.

For WMD obtained on the prototype by granulation in geophosphate, a similar increase in solubility was not found.

The proposed method is illustrated by the examples shown in tables 3 and 4.

Table 3 Norms of a technological mode Component Name Example number, feed loading, kg / t product one 2 3 four 5 6 7 8 9 10 eleven 12* 13* fourteen* fifteen* 1 Urea GOST 2081 918.0 918.0 250.6 329.3 175.7 122.8 - 348.0 395.0 - 98.8 918.0 175.7 329.3 122.8 2 Ammophos GOST 18918 - - - 421.2 - - 31.8 - - 126.2 - - - 421.2 - 3 Diammonium phosphate GOST 8515 - - 212.8 - - 242.4 371.4 200,0 - - - - - - 242.4 4 Ammonium nitrate GOST 2 - - - - - 60.0 355.0 - - 311.9 - - - - 60.0 5 Ammonium sulfate GOST 9097 - - - - 96.2 - - - - - 216.4 - 96.2 - - 6 Potassium chloride GOST 4568 - - - - 160.3 - 160.3 - 594.0 - 144.3 - 160.3 - - 7 Potassium sulfate TU 48-0114-66-91 - - - 201.0 - 466.2 - - - 209.6 - - - 201.0 466.2 8 Potash GOST 10690 - - 235.3 - - - - - - - - - - - - 9 Phosphate flour GOST 5716 - - 271.5 - 505.0 - - - - - 500,5 - 505.0 - - 10 Superphosphate GOST 5956 - - - - - - - - - 318.9 - - - - - 11 Superphosphate double GOST 16306 - - - - - - - 437.0 - - - - - - - 12 Σ Microelements (Mg, Mn, Zn, Cu, B, Ni, Co, Cr, Mo) according to ND 50,0 50,0 - - - - 21.5 - - - - 50,0 - - - 13 Biohum GOST R 50335 - - - - - - - - - 20,0 - - - - - 14 Gumat TU 2189-004-41764643-98 - 41.0 - - - - - - - - - - - - - 15 Nutritious peat ground (peat) TU 2387-016-02952213-97 - - 16 Brown coal GOST R 51972 41.0 - - 57.6 - 30,0 - - 21.0 - - 41.0 - 57.6 30,0 17 Naturally oxidized coal of the Gramoteinsky deposit - - 39.8 - 72.8 40,0 70.0 25.0 - 23,4 - - 72.8 - 40,0 Thermobaric mode Dynamic pressure in the pressing zone, MPa 22 21 thirty thirty 35 31 32 27 25 22 31 10 12 10 eleven Temperature in the pressing zone, ° C 115 105 120 120 125 120 123 116 110 109 125 83 96 87 88 The moisture content of the mixture,% of the mass. 1,2 1,5 1,1 1,0 1,2 1.3 1,2 1.3 1,2 1.3 1.4 1,5 1,2 1,0 1.3 * Note: the results shown in examples 12-15, obtained by granulation in the granulator of the FIU according to the prototype method.

Table 4 Physico-chemical properties of fertilizers Table example number The ratio of N: P ₂ O ₅ : K ₂ O,% wt. The static strength of the granules, MPa Friability,% The output of granules with a size of (1-4) mm,% M / d residue, insoluble in water,% M / d nanosized particles based on the initial HS,% wt. * one 45-0-0 3.6 one hundred 97 0.2 3.9 2 45-0-0 3,7 one hundred 98 0.15 4.0 3 16-16-16 3.9 one hundred 96 2,8 3.9 four 20-20-10 3.8 one hundred 96 0.8 5.5 5 10-20-10 3,7 one hundred 95 6.4 7.2 6 12-12-24 3.8 one hundred 94.7 0.7 7.0 7 20-10-20 3.8 one hundred 95 0.52 6.9 8 20-19-0 3.9 one hundred 94 0.91 2,3 9 18-0-38 3.8 one hundred 98 0.37 2.1 10 12-12-11 3.9 one hundred 95 6.0 4.9 eleven 20-9-9 3.9 one hundred 97 7.1 7.2 12* 45-0-0 2,4 one hundred 51,4 51,4 Ots. 13* 10-20-10 2.6 one hundred 23.7 Ots. fourteen* 20-20-10 2,5 one hundred 27.4 Ots. fifteen* 12-12-24 2.6 one hundred 28.0 Ots. * Note: the mass fraction of nanosized particles was calculated according to the results of electron microscopic studies.

The effectiveness of the fertilizers received was monitored at the farms of a number of independent organizations involved. Evaluation of agrochemical effectiveness consisted in comparing the increase in yield (for cereals and potatoes) in the control plot of sowing / planting (without the use of fertilizers) and the test (using the studied fertilizer).

Agrochemical studies conducted by independent scientific and accredited centers in different areas of the Kemerovo, Irkutsk and Tomsk regions revealed the following:

- WMDs have increased efficiency, the utilization rates of WMDs are set at 90-95%, in contrast to traditional 25-65% (34-65% according to the prototype method);

- WMD exhibit the effect of stimulating growth;

- WMD in all phases of growth create the necessary concentration of trace elements in plants (Mn, B, Zn, Co, Ni, Cr, Cu, Mo);

- a positive effect on the soil is noted when WMD is introduced in the rotation link: the content of humus, exchange phosphorus and potassium increases, the exchange capacity increases, and the acidity decreases;

- noted the excellent quality of the crop.

So, in the report of the Kemerovsky agrochemical center, the results of a study of the influence of the WMD “urea humated” and OMU 18-6-26 with the content of humates 1.1% and 2.5%, respectively, on the fields of the Beregovoi state farm in the 2000- crop rotation link are presented 2003 years under the wheat variety "Iren".

The tests were carried out in accordance with OST 10 / 106-87 “Field experiments with fertilizers. Order of conduct". The soil of the experimental field is medium humus, heavy loamy medium-thickness chernozem.

In the experiments, the effect of WMD on the yield and quality of wheat grain was studied; on soil properties (agrochemical, accumulation of heavy metals, radioactivity). The experiments were carried out in four replicates according to the 10-variant scheme. As a control, a non-granulated mixture of urea and humates with a content of the last 1.1% and a non-granulated mixture of 18-6-26 and humates with a content of the last 2.5% were used. Control mixtures were added at a dose of 200 kg / ha. The results are shown in table 5.

Table 5 The impact of WMD on the crop of wheat "Iren" Experience number Fertilizer applied, kg / ha Average crop, kg / ha Increase in control Payment of 1 kg a.v. increase and yield, kg / kg, a.v. Utilization rate% in physical mass in active substance (AI) c / ha % one 2 3 four 5 6 7 8 one* 200 N ₉₂ G _2.2 32,4 - - - - 2 200 N ₉₉ g _2.2 37.3 +4.9 15.1 5.2 95 3 300 N ₁₃₈ G _3.3 39.5 +7.2 22.2 5.18 94.8 four 400 N ₁₈₄ g _4.4 42.1 + 9.7 29.9 5.16 94.3 5 450 N ₂₀₆ g _4.95 43,2 +10.8 33.3 5.14 94 6 500 N ₂₂₇ g _5.5 43.8 +11.4 35,2 4.92 90 7 600 N _{273g 6.6} 46.0 +13.6 42 4.87 89 8 700 N _{318g 7.7} 46.66 +14.26 44 4.38 80 9 800 N _{364g 8.8} 48.73 +16.33 54,4 4.38 80 10 900 N ₄₀₉ g _9.9 49.75 +17.05 52.6 4.16 76 one* 200 N ₃₆ P ₁₂ K ₅₂ G ₅ 33.1 - - - - 2 200 N ₃₆ P ₁₂ K ₅₂ G ₅ 39,4 + 6.3 19 5.8 96 3 300 N ₃₆ P ₁₈ K ₇₈ G _7.5 42,2 +9.1 27.5 5.8 96 four 400 N ₃₆ P ₂₄ K ₁₀₄ G _1.0 45,2 +12.1 36.6 5.74 95 5 450 N ₃₆ P ₂₇ K ₁₁₇ G _11.5 46,4 +13.3 40,2 5.62 93 6 500 N ₃₆ P ₃₀ K ₁₃₀ G _12.5 47.4 +14.3 43,2 5.44 90 7 600 N ₃₆ P ₃₆ K ₁₅₆ D ₁₅ 49.8 +16.7 50,4 5.3 88 8 700 N ₃₆ P ₄₂ K ₁₆₂ G _17.5 50.1 +17 51,4 4.9 81 9 800 N ₃₆ P ₄₈ K ₁₈₂ G ₂₀ 52.1 +19 57.4 4.8 80 10 900 N ₃₆ P ₅₄ K ₂₃₄ G _23.5 53 +29.9 60.1 4.22 70 * Note: Experience N1 - control (non-granulated mixture of the same composition as WMD at a dose of 200 kg / ha), G-humate.

From the data of table 5 it can be seen that the effectiveness of WMD in the same dose is significantly higher than in the control. The optimal doses for WMD are 200-300 kg / ha, while the utilization rates are 94.8-96%, for gumatized urea and WMD 18-6-26, respectively.

In the crop rotation link from 2003 to 2004, when using WMD in doses up to 900 kg / ha, there was no increase in the content of heavy metals in soils, an increase in the content of exchange potassium, phosphorus and humus by 0.14-0.6% was noted.

When studying the influence of WMD on the yield and quality of potatoes at the Department of Chemistry and Agrochemistry of the Kemerovo State Agricultural Institute, two grades of OMU were tested: OMU 12-12-24 with a content of HW (brown coal) of 2.4% and OMU 15-15-18 with a content of humates 5.0% in the early cultivar Lyubava and mid-early cultivar Nevsky on podzolized chernozem with a humus content of 7.8% on the farm of Beregovoi LLC in the Kemerovo region in 2004-2005. The experiments were carried out in accordance with OST 10 / 106-8.

The aim of the research was:

- study of the influence of WMD on growth processes;

- determination of the yield and marketability of potatoes;

- determination of the accumulation of starch and nitrate nitrogen in marketable potatoes;

- determination of the content of heavy metals in tubers;

- study of the effect of WMD on soil quality;

- study of the aftereffect of WMD (prolongation effect);

- study of the effectiveness of WMD.

As a control in studying the effect of WMD, we used: a plot without fertilizing (control No. 1) and a plot where a granular mixture of composition 15-15-18 and 12-12-24 with the content of HW was added, as in WMD (control 2 and 3, respectively). The experiments were performed in triplicate. The results are shown in table 6.

Table 6 The impact of WMD on the yield and quality of potatoes Option Fertilizer applied, kg / ha Productivity, t / ha Increase Product
nost Efficiency ratio% in physical mass in kg a.v. (NPKG) t / ha % % one 2 3 four 5 6 7 8 Early grade "Lyubava" control 1 - - 15,5 - - 92 - control 2 300 45-45-54-15 18.8 3.3 21,2 93 35.9 control 3 300 36-36-72-7.2 19.1 3.6 23,2 94 39.1 OMU 15-15-18 300 45-45-34-15 20.6 5.1 32.9 97 91.4 OMU 15-15-18 500 75-75-90-25 26.0 10.0 68.0 98 94.7 OMU 12-12-24 300 36-36-72-7.2 21.0 5.5 35.5 98 98.5 OMU 12-12-24 500 60-60-120-12 25.8 10.3 67.0 98 94.9 Middle early grade "Nevsky" control 1 - - 18.3 - - 92 - control 2 300 45-45-54-15 20.9 2.6 14.2 93 34.0 control 3 300 36-36-72-7.2 21.1 2,8 15.3 93 34.8 OMU 15-15-18 300 45-45-34-15 22.6 4.3 23.5 98 89 OMU 15-15-18 500 75-75-90-25 26.9 8.6 47.0 98 90 OMU 12-12-24 300 36-36-72-7.2 23.8 5.5 30,0 99 91.2 OMU 12-12-24 fifty 60-60-120-12 28.0 9.7 53.0 99 93,4 Note: yield increase,%, was calculated in relation to control 1.

From the data of table 6 it is seen that WMD is more effective than non-granulated mixtures. Using WMD, products with higher marketability were obtained (97-99% versus 92-94% in the control), i.e. tuber damage when using WMD is reduced. During the growing season, we observed the timing of the phases of potato development according to the Gossortset method.

The results are shown in table 7.

Table 7 The effect of WMD on phenophases of potato development No. p / p Option Phenophase date of % of the total number of seeds one 2 3 four 5 one control 1 Shoots (formation of stolons) 05/29 3 2 control 2 05/27 8 3 control 3 May 26 9 four OMU 15-15-18 05/24 21 5 OMU 15-15-18 23.05 twenty 6 OMU 12-12-24 05.22 22 7 OMU 12-12-24 05.22 23 one control 1 Budding 6.06 5 2 control 2 6.06 7 3 control 3 5.06 10 four OMU 15-15-18 4.06 34 5 OMU 15-15-18 4.06 39 6 OMU 12-12-24 3.06 39 7 OMU 12-12-24 2.06 45 one control 1 Bloom 12.06 fifteen 2 control 2 11.06 twenty 3 control 3 11.06 21 four OMU 15-15-18 9.06 48 5 OMU 15-15-18 9.06 52 6 OMU 12-12-24 8.06 54 7 OMU 12-12-24 8.06 56 one control 1 Primary digging * b / w 45 days 13 2 control 2 17 3 control 3 16 four OMU 15-15-18 thirty 5 OMU 15-15-18 31 6 OMU 12-12-24 33 7 OMU 12-12-24 34 Note: the primary digging determines the number of marketable tubers in a sample of 100 bushes,% of the total number of tubers.

Similar results were obtained for Nevsky potatoes: the number of marketable tubers at primary digging was 27-32%, all growth phases also accelerated significantly.

Thus, the increased effectiveness of WMD has been established, and the growth stimulation effect has been identified - all phases of potato development are accelerated, the potato marketability at primary digging increased by 5-7%, and productivity - by 64-115%. A positive effect of WMD on soil quality was also noted: the content of metabolic potassium and phosphorus in it increased.

When studying the prolonged action of WMD in 2005, the same potato varieties were planted on the same plots without fertilizing. In the plots, where non-granulated fertilizer mixtures were used in 2004, the yield increase was 5-6% in relation to control 1, whereas in the plots where WMD was used, the increase was from 13 to 32%, depending on the variety and dose 2004 year

The presence of the effect of stimulating plant growth was reliably established only for humate-containing WMD obtained under the process conditions in RPGs at a pressure of 20-35 MPa and a temperature of 100-125 ° C with a concentration of HB from 1 to 7.8%. The effect of stimulating plant growth is attributed to the properties of finely dispersed HS particles formed in WMD in the indicated thermobaric mode. The regulation of the process of formation of finely dispersed HS particles in WMD is achieved by changing the relative content of the HS and the thermobaric regime implemented in the technological process.

It is very important that the formation of finely dispersed structures with sizes up to 100 nm on the surface was observed only for humate-containing samples of WMD obtained in RPGs at a temperature of 100-125 ° C and a pressure of 20 to 35 MPa. Highly dispersed structures in this case are formed by humic substances (HS).

The implemented method for producing grounded organo-mineral nanofertilizers using energy-saving one-stage non-waste technology has no analogues in the world in terms of obtaining nanofertilizers of a given composition corresponding to the agrochemical needs of specific agricultural crops and soil types. The product is high-tech when used in agriculture: granules have excellent mechanical characteristics, do not cake, are non-hygroscopic, activated humic complexes encapsulated in a granule do not aggregate and do not lose biological efficiency during storage.

The increased biological activity of WMD is confirmed by the results of agrochemical studies: the effect of growth stimulation, the protective effect against pathogenic microflora, the increased agrochemical efficiency, the environmental friendliness in the crop rotation link is revealed. The proposed method is a new method of chemical activation of HS by thermobaric treatment of dry organo-mineral fertilizer mixtures under dynamic pressing conditions in RPGs.

Information sources

1. RF patent No. 2104988, IPC ⁷ C05F 11/02.

2. CN Patent No.CN 10122510, IPC ⁷ C05G 5/00. Publ. 07/23/2008

3. RF patent No. 2223582 IPC ⁷ C05C 9/00, C05G 1/00. Publ. BIPM 03/10/04 (prototype).

Claims (5)

1. A method of producing granular organic-mineral nanofertilizers, comprising mixing dry initial mineral components selected from the series: urea, ammophos, diammonium phosphate, ammonium nitrate, superphosphate, double superphosphate, ammonium sulfate, potassium chloride, potassium sulfate, potash, phosphoric flour; mineral components containing trace elements: Mg, B, Mn, Zn, Cu, Ni, Co, Cr, Mo, and an organic component from a number of humic substances (HV), characterized in that the dynamic conditions in the pressing zone are the thermobaric regime in a rotary press RPG granulator: pressure of 20-35 MPa and temperature of 100-125 ° C lead to the occurrence of mechanochemical processes with the formation of nanoscale complexes of HS with mineral components of the mixture, which have the properties of growth stimulants, prolonged action and increased biological activity. 2. The method according to claim 1, characterized in that the concentration of HS in the granular organic-mineral fertilizer (WMD) is 1.0-7.8 wt.%. 3. The method according to claim 1, characterized in that the nanocomplexes encapsulated in a mineral matrix — an organomineral fertilizer (OMU) granule — are not aggregated and the effectiveness of the OMU during storage does not decrease. 4. The method according to claim 1, characterized in that it allows to obtain granular nanofertilizers of a given composition. 5. The method according to claim 1, characterized in that any humate-containing raw material is used as a GW.

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