SU1270149A1 - Method of producing zinc-containing long-acting fertilizer - Google Patents

Abstract

This invention relates to a technology of mineral fertilizers and can be used to obtain fertilizers containing trace elements. The aim of the invention is to increase the zinc content of the fertilizer with a simultaneous decrease in the duration of the process and an increase in the effectiveness of the fertilizers in the year they are applied to the soil. The goal is achieved by a method of obtaining a zinc-containing long-acting fertilizer, according to which a solid carrier, a synthetic cation exchanger, is treated with a spent emulsion etching solution of zinc cliches with a pH of 9.3-9.6 in a gram-equivalent ratio of zinc and ammonium cations in solution 1:

Description

The invention relates to the field of fertilizers for agriculture and can be used for the production of long-acting fertilizers, which together with the microelement contains nitrogen in the form of ammonia, which is easily assimilated by plants. The chain of the invention is an increase in the zinc content in the fertilizer with a simultaneous decrease in the duration of the process and an increase in the effectiveness of the fertilizers per year applied to the soil. The technology of the method is as follows. The spent solution of the emulsion etching of zinc plates is first purified from organic substances by ultrafiltration through Vladopor fluoroplastic membranes (pore diameter 20-30 nm). An aqueous solution of zinc nitrate and nitric acid (filtrate) passes through the membranes and virtually no organic matter passes (filtration rate 400 l / hrm. To the filtrate thus obtained, a solution of ammonium hydroxide is added with constant stirring ammonia complex (Zn (NHj) (NOj)). Then the solution containing the zinc-ammonia complex is passed through ion exchange columns with a solid cationite carrier, which absorbs the complex cation (Zn (NH) 2) with it. quality solid carrier, a cation exchanger synthesized from lignin containing cellulose-paper wastes — sulphite liquors — is used to control the zinc content of the solution leaving the column and finish at a concentration of zinc in it not more than 0.3-0.6 g / l (0.03- 0.06 wt.%). The solution purified from zinc contains, g / l: nitric acid 80-120 (812 wt.%); Zinc nitrate 0.5-1 (0.05-0.1 wt.%); ammonium nitrate. 0.5-1 (0.05-0.1 wt.%); Pb surfactants about 0.3 (0.03 wt.%); diatilbenzene, not more than 0.0025 (0.00025 wt.%), it is returned during the etching process (to prepare a working etching solution). 9 Example 1. 120 l of the spent solution containing, g / l: zinc nitrate 95.0 (9.5 wt.%); nitric acid 94.0 (9.4 wt.%); Organic substances 20 (2.0 wt.%) in the amount (a mixture of surface-active substances and diethylbenzene) are pumped onto ultrafiltering elements with Vladopor fluoroplastic membranes (average pore diameter of 2030 nm) and filtered for 20 minutes. 116 l of filtrate contain, g / l: zinc nitrate 95 (9.5 wt.%); nitric acid 94 (9.4 wt.%); surface active substances (not more than 0.6 (0.06 wt.%), diethylbenzene not more than 0.005 (0.0005 wt.%). Then 177 liters of ammonium hydroxide solution containing 90 g are added to the filtrate with constant stirring. l (9.0 wt.%) W.-, OH. The resulting solution of the zinc-ammonia complex (content of | Zn (NHj) - (NOj) 55 g / l (5.5 wt.%), pH 9.3- 9.6) is passed through an ion exchange column with 110 kg of solid carrier (cationite). Then the finished product is dried at 70 ° C for 2 hours until the water content is 17% by weight. The solution passed through the column contains, g / l: zinc nitrate 1 (0.1 wt.%); Nitr ammonium t 0.5 (0.05 wt.%); surfactants 0.3; diethylbenzene 0.0025, nitric acid 76 (7.6 wt.%). The solution is returned to the etching process to prepare working etching solutions. The degree of utilization of zinc is 98%. The yield of the finished product is 146.7 kg. The finished fertilizer is granules of 1-4 mm in size and contains, in wt.%: Ammonium zinc cation 4; W; 4; water 17; polymer base 75. Example 2. 120 l. Of the treated solution containing, g / l: zinc nitrate 140 (14.0 wt.%); nitric acid 120 (12.0 wt.%); a mixture of surfactants and diethylbeneol 30 (3 wt.%), is pumped onto Vladipor ultrafiltration membranes (average pore diameter 30 nm) and filtered for 25 minutes. The filtrate in the amount of 114 l contains, g / l: zinc nitrate 140 (14.0 wt.%); nitric acid 120 (12 wt.%); surfactants not more than 0.6 (0.06 wt.%); diethylbenzene is about 0.005 g / l (0.0005 may L). To the filtrate, 243 liters of ammonium hydroxide solution containing 90 g / l (9.0 wt.%) Are added gradually with constant stirring. The resulting solution, containing a zinc-ammonia complex (content of Zn (NH3) 4 (NO, j). 78 g / l (7.8 wt.% PH 9.3-9.6), is passed through an ion exchange column with 140 kg of solid carrier ( cation exchanger.) The finished product is then dried for 2 hours until its water content is 15% by weight. The solution passed through the column, which contains, g / l: zinc nitrate 1 (0.1% by weight); ammonium nitrate 1 (0.1 wt.%); Surfactants 0.2 (0.02 wt.%); Diethylbenzene 0.0025 (0.00025 wt.%) Nitric acid 82 (8.2 wt.%), Air rotates into the etching process (to prepare working etching solutions). The zinc utilization rate is 98%. The yield of the finished product is 184 kg. The finished fertilizer is granules of 1-4 mm in size and contains, in wt.%: ammonium zinc cation 4.8; NH 4.3; water 15; polymer base 75, 9. Example 3. A spent solid solution containing, g / l: zinc nitrate 95.0 (9.5 wt.%); Nitric acid 94.0 g / l, 4 wt.% Organic matter in the amount of 20 (2, 0 wt.%) (A mixture of surfactants and diethylbenzene), in the amount of 480 l, is pumped to ultrafiltrating elements with Vladipor fluoro-plastic membranes (average pore diameter of 20-30 them), and filtered 20 minutes. The filtrate in the amount of 464 l contains, g / l: zinc nitrate 95.0 (9.5 wt.%); nitric acid 94.0 (9.4 wt.%); surface active substances of not more than 0.6 (0.06 wt.%); diethylbenzene is not more than 0.005 (0.0005 wt.%). Then to filter

At this time, with constant stirring, 708 l of a solution of 50 cation (hp (Shz) 2 solution) is added, which allows ammonium hydroxide containing higher zinc extraction

90.0 g / l (9.0 wt.%) NH40H. Received from spent pickling solution

a solution of zinc-ammonium salt of 98%, and also to increase the effective complex (content (NHj) (NOj) of the effect of the received fertilizer

55 g / l. (5.5 wt.%), PH 9.3-9.6) pro-55a crops

allowed through an ion exchange column (due to the presence of nitrogen bound to 110 kg of solid support (cation exchanger). Then the finished product is dried

zinc polymer base in

with trace element - zinc). At the same time, the optimal conditions for conducting 9 are at 70. ° C for 2 hours until the content of water in it is 17 wt.%. The solution passed through the column contains, g / l; zinc nitrate 1.0 (0.1 wt.%); ammonium nitrate 170.5 (17% by weight); surfactants 0.3 (0.03 wt.%); diethylbenzene 0.0025 (0.00025 wt.%); . nitric acid 20 (2 wt.%). It is passed once more through an ion exchange column with a solid carrier to obtain a long acting fertilizer containing an ammonium cation. The solution after extraction of ammonium cations from it contains, g / l: zinc nitrate 110; ammonium nitrate 1.0 (0.1 wt.%); surfactants 0.3 (0.03 wt.%); diethylbenzene 0.0025 (0.00025 wt.%); nitric acid 76 (7.6 wt.%). This solution is returned to the etching process to prepare working etching solutions. A yield of finished product 162 kg. The finished fertilizer is granules with a size of 1-4 mm and contains, wt%: zinc-ammonia cation 15.0; W (1.0; water 17; polymer base 67.0. Ultrafiltration makes it possible to separate up to 90% of the protective preparation from the pickling solution and thus avoid contamination of the microelemental fertilizer with it. Filtration is enough for 20-25 minutes to separate the mixture superficially - active substances and diethylbenzene from the spent solution of the emulsion etching of zinc plates. waste solution. When ammonium hydroxide is added to a solution purified from surfactants and diethylbenzene, the zinc-ammonia complex (gp (Shz), (NO03) g) is formed. Chemical bonding process of introducing the complex into the carrier are: concentration ratio, cations zinc and ammonium in solution 1: (2.5-3.5), g-eq, pH of solution 9.3-9.6. When treating solid carrier with a ratio of cations of zinc and ammonium 1: 1 g-eq and pH 5 , 7 (sour medium) it does not contain a zinc-ammonia cation. When the ratio of zinc and ammonium cations in the solution is greater than 1: 3.5 g-eq and the pH is greater than 9.6, the content of the zinc-ammonia complex in the fertilizer sharply decreases.

In tab. Figure 1 shows the dependence of the content of zinc, zinc-ammonia cation and ammonium cation in fertilizer on the ratio of cations of zinc and ammonium in solution and on the pH of the solution at a ratio of copolymer: solution of 10: 10 (according to the prototype method).

In the case of the proposed method, the content of zinc and ammonium cations in the initial solutions for preparing a solution of the zinc-complex complex is meant.

In the proposed method, cation exchanger synthesized from pulp and paper waste (sulphite liquor) is used as a solid carrier, which makes it possible to ensure the production of fertilizers from cheap raw materials, reduce the fertilizer cost, and also dispose of waste products of pulp and paper industry to ensure environmental protection This cation exites sulfoxy, carboxyl and hydroxyl groups; it is possible. enter up to 21.5 wt.% zinc-ammonia cation. According to its properties, cation exchanger is quite suitable as a solid carrier of micronutrients (it is ecologically safe, over time it decomposes in the soil before the formation of humus, does not contain substances that are biologically harmful to humans and plants).

Using an aqueous solution of a mixture of salts of microelements as an aqueous solution of an emulsion etching solution makes it possible, in addition to accomplishing the main purpose of the invention, to obtain long-acting zinc-containing fertilizers, to reduce the fertilizer cost, to protect the environment from these wastes, to return to the pickling process the nitric acid solution obtained after chemical bonding of zinc in the form of a zinc-ammonia complex of a carrier-synthetic cation exchanger with a polymer base.

Drying zinc-ammonium fertilizers on a polymer base at temperatures above 90 ° C leads to the decomposition of the complex and a decrease in the nitrogen content in the fertilizer. Suisha at a temperature below 70C is impractical, because its time increases. In view of this, drying should be carried out at 70-90 ° C.

The fertilizer must be dried to a water content of 15t5% by weight. It gives its trace elements to the soil by exchanging them for cations of the soil, so for the ion exchange process to take place, it is necessary that the fertilizer contain as much water as possible. However, too much water content in the fertilizer is undesirable, since, on the one hand, water is evaporated from the fertilizers from them, which changes the relative content of the zinc-ammonium complex, on the other hand, a large amount of water contributes to the clumping of fertilizers, leads to the destruction of granules of micronutrients during their transportation and storage in unheated rooms (at a temperature of 0 ° C or lower).

It has been experimentally shown that when the water content is more than 20 wt.% When mixing micronutrients with other hygroscopic fertilizers, water is redistributed and the mixture is tracked, which, according to agrochemical tests, does not allow it to be applied to the soil by existing agricultural machines. Thus, a mixture of micronutrient fertilizer with hygroscopic microfertilizers (urea, ammonium nitrate) in a ratio of 1: 3 does not cake when the water content of the microfertilizer is 10-20% by weight and is cake at a water content of 30-60 May

When the water content in the fertilizer is 1545 wt.%, It is evaporated in small quantities, and the fertilizer granules do not stick. Such a water content in the fertilizers ensures fast swelling in the soil.

It was established experimentally that when the water content in the fertilizer is more than 20 wt.% At a temperature of 0 ° C or below, the excess water above

7

the value crystallizes, and the ice crystals formed in the fertilizer lead to the destruction of the polymer base. Thus, even the inclusion of fertilizers in the production process (when stored in unheated rooms and transported in unheated cars), their granules can be destroyed and agrochemical characteristics deteriorate. To prevent the destruction of fertilizer granules due to the crystallization of water in them at 0 ° C, it is necessary to produce fertilizers with an amount of water not exceeding 20% by weight.

In tab. 2 shows: the dependence of the particle size distribution of micronutrients on its water content after the granulation of 1-4 mm for 5 hours at a temperature from 0 to -50 ° C.

; The ratio of solid carrier and solution passed through ion-exchange columns can be varied within (1: 1) - (1:15) dp of obtaining microfertilizer with the required content of nutrients.

In tab. Figure 3 shows the dependence of the nutrient content of the fertilizer on the mass ratio of the solid carrier (cationite) and solution (other conditions, as in Example 1).

The optimum mass ratio of the solid support and the solution passed through the ion exchange column is (1: 3) (1: 4). With a further increase in the mass ratio of the solid support and solution, the content of the zinc-ammonia complex in the fertilizer remains constant, but the concentration of zinc nitrate and ammonium nitrate in the solution leaving the column increases; a decrease in the mass ratio of the carrier and the solution (less than 1: 3) sharply reduces the content of zinc-ammonia complex in the fertilizer, although the degree of utilization of zinc and ammonium cations from the spent solution increases (examples 1, 2).

The preparation of zinc-containing fertilizers, including the ultrafiltration of the spent solution, the preparation of the zinc-ammonia complex, the treatment of the solid carrier and the drying, under the proposed technological conditions, will reduce the time

701498

it is 60 times and to increase the zinc content in the fertilizer by 2.5 times compared with the prototype.

In tab. 4 shows a comparative analysis of the duration of the process of obtaining micronutrients by the known and proposed methods.

According to the method prototype for 15.5 h receive 1.25 kg of fertilizer, 10 the proposed method for 29.33 h 147 kg (example 1). The time spent on obtaining 1 kg of fertilizer composition t prototype 12 hours, the proposed method is 0.2 hours

15 In table. 5 shows the comparative characteristics of fertilizers obtained by the known and proposed methods on both types of solid carrier.

On 1 hectare of crops need 50-100 kg of the proposed fertilizer. It is applied to the soil together with macrofertilizers or seeds. Agrochemical

25 field and production tests of polymer-based micronutrients (annually 3-5 tons), made into different soil-climatic zones of the country and on various agricultural plants, showed that the proposed fertilizer increases the yield by 10-30% and improves product quality.

Claims (4)

1. A method for producing a long-acting zinc-containing fertilizer by treating a solid carrier of synthetic cation exchanger with an aqueous solution of inorganic salts and drying, which, in order to increase the zinc content of the fertilizer while reducing the duration of the process and increasing the effectiveness of fertilizers in the year they are applied to the soil, As an aqueous solution of inorganic salts, a used solution of emulsion etching of zinc cliches with a pH of 9.3-9.6 is used, in a gram-equivalent ratio to thiones zinc and ammonium in solution 1: (2.5-3.5) and the mass ratio of the solid support and a solution (1: 3) (1: 4) and drying the final product is carried out until a water content of wt.%. 2 .. Method 1, characterized in that the spent the pickling solution is an aqueous solution of a mixture containing, g / l: zinc-ammonia complex 50-80; ammonium nitrate 120-160 ;; ammonium hydroxide 10-20; surface active substances not more than 0.3 and diethylbenzene 0.0025. 3. The method according to claim 1, characterized in that cation exchanger synthesized from waste of pulp and paper industry by means of polycondensation of lignosulfonates 5 sulfite liquors is used as a solid carrier. 4. The method according to claim 1, characterized in that the drying is carried out at 70-900 ° C. Table 1 Table 2 13 U 1270149. Table Tltr a $ Sh1btrats., Solution Preparation of the solution Solid media processing Fertilizer washing Drying Total Solid support copolymer of methacrylic acid with triethylene glycol dimethacrylate Disturbances 5.8 Suggested 10.7 Solid cation carrier synthesized from pulp and paper waste 0.33 0,50,5 10,026,5 0.5x, 0 3.0 2.0 15.5 29.33 Table 5 2-5 5.7 18-20 50