RU2336257C1 - Method of obtaining complex prolonged fertiliser - Google Patents

Abstract

FIELD: chemistry, agriculture.

SUBSTANCE: method of obtaining complex fertiliser of prolonged action on the basis of adsorption additive - tripoli, includes 5 stages. On the first stage tripoli is mixed with solution K₃[Al(OH)₆], obtained suspension is exposed in autoclave during 4 hours at pressure 5 atm and temperature 150°C, obtaining complex adsorbent. Mixture is washed with water in ratio mixture: water equal 1:3 and aboiled, obtained suspension is neutralised with hot phosphoric acid with concentration 30.7 wt % continuously mixing until solution with pH = 7.0 is obtained, suspension is dried to 1% humidity. On the second stage peat is processed with 30% solution of KOH while boiling during 0.5 hour with output of biologically active humic fraction. On the third stage nitrating mixture, consisting of P₂O₅ and HNO₃ in ratio 1:2 is obtained, it is combined with peat in ratio 1:1 mixing thoroughly and subjected to cooling during 0.5 hour in crystalliser with ice obtaining organic nitrogen-containing fraction of fertiliser. On the fourth stage biologically active humic and organic nitrogen-containing fraction of fertilizer are mixed, mixture is neutralised with 25% solution of ammonium, until solution with pH=7.0 is obtained, and dried. On the fifth stage complex adsorbent and mixture of organic and humic fractions are combined in ratio 1:2.7, crushed, and fertilizer, which contains in its composition the following elements: wt %: nitrogen N-21.96; phosphoric anhydride P₂O₅ 15.73; potassium oxide K₂O 11.20; silicon oxide SiO₂ 12.54; aluminium oxide Al₂O₃ 1.65; calcium oxide CaO 1.92; magnesium oxide MgO 0.30; iron oxide Fe₂O₃ 0.96; manganese oxide MnO₂ 0.14; peat and organic substances 33.6, is obtained.

EFFECT: reduction of obtained complex fertiliser cost and enhancing efficiency of prolonged impact of complex fertiliser on soil fertility.

1 cl, 2 tbl, 1 ex

Description

The invention relates to the field of agriculture, and in particular to a technology for producing complex fertilizers that regulate the dosed introduction of trace elements and the absorption of toxic components, including radioactive elements, from the soil, and can be widely used to improve soil fertility and improve their environmental safety.

Various types of fertilizers are known for improving soil fertility and increasing crop yields.

For example, “A method for producing an encapsulated slowly acting mineral fertilizer”, including impregnating a solution of mineral fertilizers with natural porous granular products, using sapropel as natural products and impregnating with a 3-4-fold cycle for 5-10 minutes. Each 80-90% aqueous solution of mineral fertilizers, followed by drying of the product.

RF patent No. 2038347, MKI 6 C05G 3/04, publ. 06/27/95

The well-known "Method of producing complex long-acting fertilizer", including the interaction of potassium - and phosphorus-containing compounds with zeolite-containing raw materials, and a mixture of monocalcium phosphate monohydrate, potassium nitrate and zeolite-containing raw materials is subjected to mechanical activation in high-energy and grinding devices with the following ratios of components, wt.%:

monocalcium phosphate monohydrate 15-65 potassium nitrate 10-25.

RF patent №2137739, MKI 6 C05G 3/04, publ. September 20, 1999

The well-known "Method for the production of biologically active phosphorus-zeolite fertilizers of prolonged action", comprising mixing phosphorite with natural zeolite, while phosphorite with a size of fractions up to 0.5 mm is mixed with mordenite-containing tuff with a size of fractions up to 2 mm saturated with phosphate mobilizing microorganisms.

RF patent №2255922, MKI 6 С05В 17/00, C05G 3/04, publ. September 20, 1999

The closest analogue to the present invention is the “Method of soil fertilizer”, including the introduction of mineral fertilizers into the soil together with an adsorption additive, and tripoli in the amount of not less than 60% of the weight of mineral fertilizers is used as an adsorption additive.

RF patent No. 2088557, MKI 6 C05G 3/04, publ. August 27, 1997

The disadvantages of the above methods are the lack of effectiveness in increasing soil fertility and low adsorption capacity and absorption capacity.

The technical result includes reducing the cost of complex fertilizers obtained by using cheap natural raw materials in the form of tripoli and simple technological processing, as well as increasing the effectiveness of the prolonged action of complex fertilizers on soil fertility by using a complex adsorbent that regulates the dosed introduction of trace elements with simultaneous absorption with high selectivity from the soil toxic components, including radioactive elements.

The technical result is achieved due to the fact that the method of obtaining a complex fertilizer of prolonged action on the basis of an adsorption additive consists in using tripoli as an adsorption additive, moreover, they produce complex fertilizer of a prolonged action in five stages, while

at the first stage, a complex adsorbent is obtained from tripoli, for this purpose tripoli is mixed with a solution of an aluminum hydroxocomplex with potassium K ₃ [Al (OH) ₆ ], the resulting suspension is placed in an autoclave and incubated for four hours at a pressure of 5 atm and a temperature of 150 ° C. Then the mixture is removed from the autoclave by washing with water in a mixture: water ratio of 1: 3, and brought to a boil. The resulting alkaline suspension is subjected to neutralization with hot phosphoric acid with a concentration of 30.7 wt.% With continuous stirring to obtain a solution whose pH is 7.0, followed by drying of the suspension to a moisture content of 1%.

At the second stage, a biologically active humic fraction of fertilizer is obtained by treating peat with a 30% KOH potassium hydroxide solution while boiling for 0.5 hours.

At the third stage, an organic nitrogen-containing fertilizer fraction is obtained by obtaining a nitrating mixture consisting of phosphoric anhydride P ₂ O ₅ and nitric acid HNO ₃ in a ratio of 1: 2. Then peat and nitrating mixture are combined in a ratio of 1: 1 with thorough stirring in the reaction vessel and subjected to cooling for 0.5 hours by placing the reaction vessel in a crystallizer with ice.

At the fourth stage, biologically active humic and organic nitrogen-containing fertilizer fractions are mixed. The mixture is neutralized with 25% ammonia solution to obtain a solution whose pH is 7.0, followed by drying.

In the fifth stage, the complex adsorbent obtained in the first stage and the mixture of organic and humic fractions obtained in the fourth stage are combined in a ratio of 1: 2.7, crushed and a fertilizer is obtained, which contains the following elements, wt.%:

Nitrogen N 21.96 Phosphoric Anhydride P ₂ O ₅ 15.73 Potassium oxide K ₂ O 11.20 Silicon Oxide SiO ₂ 12.54 Alumina Al ₂ O ₃ 1.65 Calcium oxide CaO 1.92 Magnesium Oxide MgO 0.30 Iron Oxide Fe ₂ About ₃ 0.96 Manganese Oxide MnO ₂ 0.14 Peat and organic matter 33.6

The molar ratio of SiO ₂ : Al ₂ O ₃ is 12.90.

An example of a specific implementation of the method of obtaining complex fertilizers of prolonged action.

To obtain a prolonged-action complex fertilizer, the following operations are performed (per 1 kg of the initial mineral raw material - tripoli):

Stage 1. Preparation of a complex adsorbent:

1. Preparation of 1 dm ³ solution with potassium aluminum hydroxo - K ₃ [Al (OH) _6]:

1) 0.450 kg of potassium hydroxide - (KOH) is dissolved in 0.1 dm ³ H ₂ O upon boiling.

2) 0.100 kg of aluminum hydroxide - Al (OH) ₃ is added to the hot solution and the resulting suspension is maintained at the boiling point until the aluminum hydroxide is completely dissolved and the solution clears.

3) The solution of the hydroxocomplex of aluminum with potassium is brought to a volume of 1 dm ³ , when boiled, in small portions of hot H ₂ O (avoiding intense spraying and cloudiness of the solution).

2. The resulting solution of K ₃ [Al (OH) ₆ ] is introduced into Tripoli grade M80 (grinding fineness <80 μm) and thoroughly mixed, the resulting suspension is placed in a sealed autoclave and heated to a temperature of 150 ° C, the pressure in the autoclave is maintained in the range of 5 -5.2 atm. The autoclaving time after reaching the temperature is 4 hours.

3. The material extracted from the autoclave is placed in a metal (stainless steel) or glass container with a volume of more than 10 dm ³ . The walls of the autoclave are washed with water from the remnants of the mixture and the washings are combined with the bulk of the mixture. Ultimately, the mixture extracted from the autoclave should be diluted with water at least 3 times. Next, this mass is brought to a boil.

4. The resulting alkaline suspension is neutralized with hot phosphoric acid diluted with water to a concentration of 30.7 wt.% Or 3.71 mol / dm ³ until the solution is neutral (pH 7.0), with thorough stirring. The neutralization consumes 0.575 dm ³ N ₃ PO ₄

5. The resulting suspension after neutralization is placed in an evaporation bath and dried.

Thus, to obtain 1,777 kg of a complex adsorbent, dried to an air-dry state (humidity 1%), 0.100 kg of Al (OH) _{3 is} expended. 0.450 kg KOH, 1 kg tripoli, grade M80, and 2.13 mol (0.209 kg) H ₃ PO ₄ .

Stage 2. Preparation of biologically active humic fraction.

1. 0.5 kg of peat (it is possible to use crop residues, hydrolysis lignin, etc.) is placed in a glass or metal container, filled with 1.5 dm ^{3 of a} 30% solution (m: v) of potassium hydroxide (0.300 kg KOH per 1 dm ³ solution) and boils on an electric stove for 0.5 hours.

Stage 3. Obtaining an organic nitrogen-containing component.

A nitrating mixture is prepared consisting of phosphoric anhydride (P ₂ O ₅ ) and nitric acid (HNO ₃ ) in a ratio of 1: 2 by weight of pure substances (meaning the mass of anhydrous P ₂ O ₅ and the calculated mass of 100% HNO ₃ ), in a heat-resistant container when cooled.

2.2 kg of peat are placed in porcelain, teflon or glass dishes and 2 liters of nitrating mixture are poured (in small portions with thorough mixing). To prepare the required amount of nitrating mixture takes 2 DM ³ HNO ₃ (ρ = 1.39), having a concentration of 65 wt.%, And 0.910 kg of P ₂ O ₅ . The mixture was incubated for 0.5 hours. In this case, the reaction vessel must be cooled, for example, placed in a mold with ice.

Stage 4. The obtained biologically active humic fraction and the organic nitrogen-containing component are combined and neutralized with a 25% aqueous ammonia solution until neutral (pH about 7.0), accompanied by the appearance of a faint smell of ammonia. 5.8 dm ³ solution of NH ₄ OH is consumed for neutralization.

The resulting mixture is placed in an evaporation bath and dried. The total mass of the organic component in the resulting product per 1.777 kg of the mineral component (complex adsorbent) is 4.969 kg, therefore the ratio between the complex adsorbent and the mixture of organic and humic fractions is 1: 2.7.

Step 5. Obtaining a complex fertilizer of prolonged action.

The complex adsorbent (stage 1) and the organic component (stage 4) are combined and ground (together) in a mill (ball). Thus, the total mass of the obtained product is 6.746 kg.

To assess the effectiveness of complex fertilizers (Suprodita) in 2005-2006. Vegetation experiments were carried out on technologically contaminated sod-podzolic medium loamy soil under barley of the Hyp variety. The applied dose of fertilizer is from 0.2 to 0.5 g / kg of soil (as applied to field conditions, approximately 600-1500 kg / ha).

As observations have shown, the introduction of Cd in a soddy-podzolic light loamy soil at a dose of 6 mg / kg of soil reduces grain yield by 1.3 times compared to the background. When Zn was added at a dose of 600 mg / kg of soil and Cu at a dose of 390 mg / kg of soil, the decrease in grain yield compared to the control was 1.6 and 1.1 times (Table 3).

The use of complex fertilizer (suprodite), which has a high absorption capacity, increases the yield on soddy-podzolic medium loamy soil contaminated with Cu to the level of 116% of the control, and eliminates the negative effect of Zn ₆₀₀ and Cd ₆ on the grain yield, bringing the level of the latter to 81 -82% of the control.

The addition of complex fertilizer to the contaminated soil reduces the content of ¹³⁷ Cs in barley grain by 35% compared to the version without ameliorant. The introduction of suprodite into the contaminated soil (Cd ₆ and Zn ₆₀₀ ) soil reduces the content of Cd and Zn in barley grain by 17-27% compared with the options without applying ameliorant (fertilizer)

Table 1.
The effect of long-acting complex fertilizer (suprodite) on the productivity of barley and the accumulation of HM in the crop on technologically contaminated sod-podzolic medium loamy soil No. p / p Option Grain harvest, g / vessel Grain Content ¹³⁷ Cs, Bq / kg Grain Content, mg / kg Cd Zn Cu one Von NPK 20.1 ± 0.7 - 0.8 46.6 9,4 2 Background + ¹³⁷ Cs 22.0 ± 0.8 4388 ± 94 - - - 3 Background + ¹³⁷ Cs + fertilizer (suprodit) 22.1 ± 0.5 3246 ± 75 - - - four Background + Cd ₆ 15.0 ± 1.1 - 1.4 - - 5 Background + Cd ₆ + fertilizer (Suprodit) 17.0 ± 0.8 - 1,1 - - 6 Background + Zn ₆₀₀ 12.9 ± 0.9 - - 224.4 7 Background + Zn ₆₀₀ + fertilizer (Suprodit) 16.2 ± 0.8 - - 192.0 - 8 Background + Cu ₃₉₀ 18.2 ± 0.3 - - - 13.9 9 Background + Cu ₃₉₀ + fertilizer (suprodit) 23.3 ± 0.8 - - - 14.1 Hcp ₀₅ - - 0.1 19.5 2.1

2 more variants of a prolonged-release complex fertilizer were tested - with a low and high potassium content. It turned out that the introduction of fertilizers with a low potassium content into the same soil contaminated with Cd ₆ and Zn _{600 has} almost no effect on the barley grain yield, and in the soil contaminated with Cu ₃₉₀ , the barley grain yield barely reaches the control level (Table 4). The content of Cd and Zn in barley grain during the application of this fertilizer did not significantly change compared to the options where the ameliorant was not applied.

Table 2.
The effect of long-acting complex fertilizers with reduced (1) and increased (2) potassium content on barley productivity and TM accumulation in the crop on technologically contaminated sod-podzolic medium loamy soil No. p / p Option Grain harvest, g / vessel TM content in grain, mg / kg Cd Zn Cu one Von NPK 20.1 ± 0.7 0.8 46.6 9,4 2 Background + Cd ₆ 15.0 ± 1.1 1.4 - - 3 Background + Cd ₆ + fertilizer (1) 15.9 ± 0.8 1.3 - four Background + Cd ₆ + fertilizer (2) 17.3 ± 0.9 1,1 - - 5 Background + Zn ₆₀₀ 12.9 ± 0.9 - 224.4 - 6 Background + Zn ₆₀₀ + fertilizer (1) 14.0 ± 0.8 - 210.0 - 7 Background + Zn ₆₀₀ + fertilizer (2) 16.6 ± 0.5 - 186.3 - 8 Background + Cu ₃₉₀ 18.2 ± 0.3 - - 13.9 9 Background + Cu ₃₉₀ + fertilizer (1) 19.0 ± 0.7 - - 14.1 10 Background + Cu ₃₉₀ + fertilizer (2) 24.0 ± 0.8 - - 13.5 NDS ₀₅ - 0.1 18.8 2.0

The effect of fertilizers with a high potassium content on the barley crop and the accumulation of HM in grain is practically no different from the effect of a classical fertilizer with a potassium content of 25.2%, but due to the increased doses required to obtain KOH fertilizer it is slightly higher, so it content of K ₂ O = 11.2% is optimal in cost and effect on the grain yield and the accumulation of HM in the grain, at least under the conditions of growing experiments under barley on sod-podzolic soils.

Therefore, the proposed method for producing complex fertilizers of prolonged action makes it possible to obtain complex fertilizer from cheap natural raw materials in the form of tripoli by means of simple technological processing, which effectively affects soil fertility by using a complex adsorbent that regulates the dosed introduction of trace elements with the absorption of toxic components with high selectivity from the soil , including radioactive elements.

Claims (1)

A method of producing a prolonged-action complex fertilizer based on an adsorption additive, which uses tripoli as an adsorption additive, characterized in that they produce a prolonged-action complex fertilizer in five stages, and at the first stage, a complex adsorbent is obtained from tripoli, for this, tripoli is mixed with a solution of a hydroxocomplex of aluminum with potassium K ₃ [Al (OH) ₆ ], place the resulting suspension in an autoclave and incubated for four hours at a pressure of 5 bar and t temperature of 150 ° C, then the mixture is removed from the autoclave by washing with water in a ratio of mixture: water equal to 1: 3, and brought to a boil with further neutralization of the resulting alkaline suspension with hot phosphoric acid with a concentration of 30.7 wt.%, with continuous stirring to obtain a solution whose pH is 7.0, followed by drying the solution to a moisture content of 1%, in the second stage, the biologically active humic fraction of the fertilizer is obtained by treating peat with a 30% potassium hydroxide solution KOH when boiling for 0.5 h, in the third stage the floor ayut organic nitrogen-containing fraction fertilizer by obtaining nitrating mixture consisting of phosphoric anhydride P ₂ O ₅ and HNO ₃ nitric acid in the ratio 1: 2, then peat and nitrating mixture was combined in 1: 1 ratio with vigorous stirring in a reaction vessel and subjected to cooling in for 0.5 h, placing the reaction vessel in a crystallizer with ice, at the fourth stage, biologically active humic and organic nitrogen-containing fertilizer fractions are mixed, the mixture is neutralized with 25% ammonia solution to obtain a solution, the pH of the cat equal to 7.0, followed by drying, at the fifth stage, the complex adsorbent obtained at the first stage and the mixture of organic and humic fractions obtained at the fourth stage are combined in a ratio of 1: 2.7 with further grinding and obtaining fertilizer, containing in its composition the following elements, wt.%: nitrogen N 21.96 phosphoric anhydride P ₂ O ₃ 15.73 potassium oxide K ₂ O 11.20 silicon oxide SiO ₂ 12.54 Alumina Al ₂ About ₃ 1.65 calcium oxide CaO 1.92 magnesium oxide MgO 0.30 iron oxide Fe ₂ About ₃ 0.96 manganese oxide MnO ₂ 0.14 peat and organic matter 33.6