RO116081B1 - Fertilizer composition and process for preparing the same - Google Patents

Abstract

The invention relates to a fertilizer composition for crops and to a process for preparing the same. According to the invention, the composition comprises 12% total nitrogen, 5.33% nitrogen from amino-acids and peptides, 2.3% ammonia nitrogen, 4.5% nitrogen from nitrates, 6.4% ionic potassium, the percentage being expressed by weight, as well as metal microelements in soluble metal-proteic complexes 80...3,000 ppm Fe, 160...1,000 ppm Mn, 40...900 ppm Zn and 30...220 ppm Cu. According to the invention, the process for preparing the fertilizer composition consists in using the sludge from the non-ferrous metal extraction industry, from which the waste metal microelements are extracted and further combined with amino-acids and peptides from animal proteic sources and vegetable gluco-proteic sources.

Description

The invention relates to a fertilizing composition, based on residual nutrients from mining sludge and to a process for obtaining it, used for curative and additional fertilization, to stimulate agricultural crops.

It is known that a variety of simple and complex fertilizers with macro- and microelements, applicable in soil and on the foliage of plants, produced from pure salts (for example, copper salts, zinc, etc.) are used for fertilizing crops. , microelements deficient for the agricultural fertilizer industry. These fertilizing compositions have the following disadvantages: they require, for obtaining, pure raw materials and elaborated technologies, the cost of such fertilizers is high, and the sludge that results after the extraction of minerals and the concentration of salts-sources of nutrients it accumulates under the open sky, in ponds and dumps, constituting sources of chemical pollution of the environment and, in addition, the current processes of obtaining and using simple and complex fertilizers, based on pure salts of nutrients, are not integrated in a system. unitary to allow the full utilization of both the nutrient of fertilizers, as well as of the residual sources of the raw materials that were used to produce these fertilizers.

The technical problem, which the invention solves, is to obtain a foliar, complex, fertilizing composition with a curative and stimulating role of agricultural crops through a process using sludge extracts from the non-ferrous metal extraction industry, which are pure sources of microelements.

The composition according to the invention removes the mentioned disadvantages, in that it consists of: 12% total nitrogen, 5.33% nitrogen from amino acids and peptides, 2.3% ammoniacal nitrogen, 4.5% nitrate nitrogen, 6.4% ionic potassium , as well as metallic microelements in soluble metal-protein complexes, containing 80 ... 3000 ppm Fe, 160 ... 1OOO ppm Mn, 40 ... 900 ppm Zn and 30 ... 220 ppm Cu.

The process according to the invention removes the mentioned disadvantages, in that sludges from the recovery of ores with nonferrous metals, free of sulphides and of compounds of the polluting metallic elements: Cd, Pb, Ni and Cr - containing maximum (ppm) 5.0 Cd, 50 , 0 Pb, 25.0 Ni and 50.0 Cr and less than 1.5% Mg in their dry matter, are extracted cold, for 80 minutes, with 5,5N nitric acid in relation to 1 part gravimetric slurry with 2 volumetric acid parts, the extracts thus obtained are hydrolyzed at 100 ° C residual protein sources, of vegetable origin, whose hydrolysis products, alone or together with synthetic complexes, bind the metal microelements extracted from sludge into metal-organic complexes. of chelated type, soluble in water and stable in neutral-weak alkaline environment, after which acid extracts from sludge, containing metal-organic complexes of chelated type are partially neutralized with ammonium and potassium hydroxides, thus However, after diluting the concentrate 100 ... 200 times with irrigation water the pH of the diluted solutions should be 6.0 ... 7.0, and the acid sludge from which the residual useful elements have been extracted will be neutralized with powder of lime or dolomite and applied to the soil as a source of nitrogen.

By applying the invention, the following advantages are obtained:

- pure sources of microelements are used by recovering from mining sludge, so that they are fully integrated in the fertilization circuit of agricultural crops;

- deficient nutrients are obtained for the production of special agricultural fertilizers;

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- the sludge storage sites from the mining operations are released, which are thus no longer subject to dissipation in the environment and pollution with their components in the environment, especially surface and groundwater;

- the minerals, as well as pure nutrients extracted from them, are fully recovered, in the form of fertilizers; 50

- the production cost of foliar fertilizers, produced by exploiting the residual sources of macro- and microelements from sludge, is substantially reduced;

- the consumption of chelating organic substances is reduced, by producing metal-protein complexes during the hydrolysis of the protein and glycoprotein residual sources. The following is an example of obtaining the fertilizer composition according to the invention.

In the first stage, the chemical composition of the sludge chosen for the recovery of nutrients of agrochemical interest is characterized. This consists in determining the nutrients to recover and the unwanted ones, which make extraction impossible. 60 materials containing sulphides and pollutants above the threshold values (ppm) Cd 5.0, Pb 50.0, Ni 25.0, Cr 50.0, U 50.0 are excluded. Because it requires high consumption of acids for nutrient extraction, sludges with more than 1.5% Mg are also excluded. Materials containing more than 2 ppm Hg and 15 ppm As are also considered to be excluded from use. 65

Following is the solution passage and the extraction of nutrients of agrochemical interest, which is made with cold 5,5N nitric acid (without heating), for 80 minutes, in relation to one part dry air sludge with 2 volumetric acid solution (having d 1.18 at 15 ° C, containing 346.5 g HNO ₃ or 380 cm ³ of concentrated acid with d 1.4 to 1 L, stirring from time to time. Nitrogen oxides, which may be released by treatment with nitric acid of sludge 70 with reducing substances (such as the residues of organic flotation agents) can be removed from the reaction vessel with a water tube. asbestos flakes.

The concentration of nutrients in the acid-nitric extract is determined by ICP or AA spectrophotometry (ppm of Mg, Fe, Mn, Co, Zn B and Mo). 75

The concentration of nutrients in extracts from pre-existing pure sources is supplemented, up to the level required for the type of composition different from those that would result only with the residual nutrients recovered by sludge extraction.

Next, the linking of metallic microelements in chelated metal-organic complexes follows the hydrolysis of residual protein and glycoprotein sources of origin 8 an animal (collagen, bone glue, technical casein) and vegetable (degreased soybeans, flower at 100 ° C, for 2 h, under stirring, in the ratio of 1 part gravimetric dry protein source to 3 volumetric parts of acidonitric sludge extract. If hydrolysis operation of residual protein or glycoprotein sources is not possible , the binding of the metallic microelements in soluble complexes of chelated type is made with EDTA 8 5 (ethylenediamine tetraacetic acid complexones I, II or III], EDDHA (ethylene diamino (ortho) diphenylhydroxyacetate) etc. in molar ratios Me: complexons of 1: 1. When determining the required complexon quantities, the sum of the molar concentrations of the metal micro-elements and molecular masses of the available complexes is considered.

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The partial neutralization with the ammonia and potassium hydroxide of the solution of bound nutrients in organic metal complexes follows, so that when the volume of the concentrated solution is filled with demineralized water (for example, at 1, 2 or 5 I) and after dilution of 1OO. ..200 times (1.0 ... 0.5%) with irrigation water, the pH of the diluted solution to be applied on plants should be between 6.0 and 7.0, after which the solution is packaged (suspension ) concentrated and partially neutralized until use in plastic bottles, elastic with screw cap, with a capacity of 1, 2 or 5 l, so that the re-homogenization of the content is possible by repeated overturning and plastic deformation of the bottles.

The content of nutrients and of organic and mineral substances in the fertilizer composition based on acidic extracts from the sludge is determined according to:

- the content of residual nutrients and their solubility in sludge,

- the complexogenic substances used to keep the micro-elements in solution,

- concentration of nutrients in the nitric acid solution,

- the nature of the residual sources of hydrolyzed protein and gluco-protein substances in acid-nitric extract from mining sludge,

- the nature of the bases used for the partial or total neutralization of the fertilizing compositions, based on acid-nitric extracts from sludge,

- the chemical nature and the concentration of the nutrient sources, added in the acid-nitric extract, in order to correct and possibly standardize them.

In the table below, data are presented regarding the concentrations of some of the metal nutrients in the acid-nitric extracts obtained by cold treatment of mining sludge in order to use the residual nutrients from them. Table 2 shows, together with the concentrations of (micro) metallic elements, linked (partially) in metalprotein complexes and the contents of organic and mineral nitrogen made in the fertilizing composition based on acid-nitric extracts from mining sludge by hydrolyzing in them some residual protein sources.

The application on plants is done by repeatedly sprinkling 2 ... 3 times of their foliage in the first part of the vegetation period with solutions (suspensions) of the fertilizers, diluted 100 ... 300 times (1,0 .., 0, 33%) with channel water. In order to be applied to plants, diluted solutions can be mixed with diluted solutions of phyto-pharmaceutical substances, proving their chemical compatibility beforehand.

Table 7

Concentrations of metal-nutrients for plants in acid-nitric extracts from mining sludge ¹¹

Origin of sludge Metals solubilized in HNO ₃ 5.5N, ppm element in nitric acid extracts mg Fe Mn Zn With Baita, Maramures 14100 4500 2400 80 160 Colbu 1, Maramureș 1950 41500 300 750 420

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Colbu 2, Maramureș 1600 5400 250 1350 535 Cavnic, Maramures 1100 9100 735 700 120 Straja, Maramureș 1850 25000 335 120 two hundred Bobânta, Maramureș 3300 12900 2300 300 350 Brass Bath, Gorj 10400 11200 355 50 160

135 ¹¹ obtained by cold treatment, for 80 min, in relation to 1 part gravimetric dry sludge with 2 parts volumetric nitric acid 5.5N; relative to the amount of sludge, the concentrations of the elements in the nitric acid extract are 2 times higher

Table 2

Content of nutrients and organic substances In the fertilizer composition based on acid-nitric extracts from mine sludge

140

145

Origin of sludge Nutrients (Macro) Metallic microelements, predominantly in soluble protein metal complexes N protein amino acids and peptides N-N0 ₃ n-nh ₄ Total N K Fe Mn Zn With g / l of concentrate ppm in concentrate * ¹ Colbu 1, Maramureș 53.3 45.0 23.0 121.3 64.0 80 two hundred 425 220 Colbu 2, Maramureș 53.3 45.0 23.0 121.3 64.0 110 160 880 120 Cavnic, Maramures 53.3 45.0 23.0 121.3 64.0 1500 400 705 30 watch, Maramures 53.3 45.0 23.0 121.3 64.0 2970 180 100 96 Bobânta, Maramureș 53.3 45.0 23.0 121.3 64.0 3000 1000 250 172 Brass Bath, Gorj 53.3 45.0 23.0 121.3 64.0 500 240 40 80

150

155

160 ^x) determined from SFM (spectro photometry with atomic adsorption of diluted solutions 0.25 ... 1% (from 1OO ... 4OO times) with channel water

Claims (2)

1. Composition of foliar fertilizer, complex, with curative and stimulating role of agricultural crops, based on residual nutrients from sludge, amino acids and peptides from protein sources of animal origin and protein glyc, of vegetable origin, characterized in that it is constituted of: 12% total nitrogen, 5.33% amino acid and peptide nitrogen, 2.3% ammoniacal nitrogen, 4.5% nitrate nitrogen, 6.4% ionic potassium, 170 175 180 185 RO 116081 Bl up to 0.03% Fe, respectively 0.001% Mn, 0.0009% Zn and 0.0002% With percentages by weight. 2. A process for obtaining the fertilizing composition, as defined in claim 1, characterized in that sludges from the recovery of non-ferrous metal ores, containing at least 0.15% Zn, 0.15% Mn, 0.2% Fe and 0, 05% Cu, as well as maximum 5 ppm Cd, 50 ppm Pb, 25 ppm Ni, 50 ppm U and 50 ppm Cr respectively 0.5% Mg, are extracted cold with 5.5N nitric acid for 80 min at 1 part gravimetric slurry with 2 volumetric parts of acid solution, the oxides of nitrogen being removed from the reaction vessel by water absorption, after which the liquid phase is separated by pressure filtration, and with the acid-nitric extract a residual protein source is hydrolyzed. animal origin in relation to 1 part gravimetric dry bone glue with 2 parts volumetric acid-nitric extract, after which nitric acid solutions containing soluble metal-protein complexes and other products of bone glue hydrolysis are partially neutralized with hydroxides of ammonium and potassium so that after dilution of 100 ... 300 times with channel water the pH of the diluted solutions should be 6.0 ... 7.0, and the acid-nitric solid residue in the sludge is completely neutralized with dolomite and dry.