CS200677B1 - Liquid fertilizer and process for preparing thereof - Google Patents

Description

The present invention relates to a liquid fertilizer suitable, in particular, for foliar fertilization of plants containing nitrogen, magnesium, sulfur and optionally also trace elements, vitamins, growth promoter and colorant and a process for its preparation.

One of the important epochs of increasing the yield of cultivated crops in the fields of agriculture, saddlery, horticulture, etc., is the utilization of plants' ability to receive nutrients by all above-ground organs, but notably by moldings.

Plants are able to absorb both basic and secondary nutrients as well as trace elements, and the rate of absorption of these nutrients and biologically active substances varies considerably. For example, Hudská G. (Agrochemistry 16, (5), 144, (1976)) gives the following values for the rate of sorption of some nutrients and trace elements:

Nutrient or trace element Time 50 & sorption amide nitrogen 0.5 - 2 hours phosphorus 5-10 days potassium 10 - 24 hours magnesium 2 - 5 hours calcium, manganese, zinc 1 - 2 days iron, molybdenum 10 20 days

I

200 877

Jurgens C. (Der Erwerbs-Gartner No. 17/26 / - April 1972) states that nitrogen is the most important nutrient for foliar fertilization. The author states in his work Sálej that besides nitrogen, magnesium and some trace elements are also very important for the extra-root nutrition of plants.

At present, a number of Special Liquid Fertilizers are produced abroad and in Czechoslovakia, which are recommended for foliar application.

For example, Folifertil (Murphy Chemical t / td., England), Wuxal (Aglukon and Philips-Duphar G. mb H. NSR), Kamasol blau (BASF, NSR), Plantan (without trace elements) , Chemie-Wien, Austria), Blattdunger 34 (BASF, Germany) and SalSie.

Among the commercially carved leaf fertilizers in the CSSR, for example, Vegaflor (n. Mr. Spolana Meratovice), Harmavit (n. Mr. CHZJD Bratislava), Floran (VD Chema Praha) and others.

In addition to the nitrogen fertilizer Blattdunger 34, the abovementioned types of liquid fertilizers have a versatile nature of leaf fertilizers and a relatively high level of basic nutrients (N, PgOij). In most cases they also contain trace elements (Fe, Cu, Mn, MG, Zn,

Co, B), growth stimulators, if any, are B-group vitamins, but the content of secondary nutrients (Ca, Mg, S), if present, is usually very low.

The varnish as well as the composition of these fertilizers contradicts the conclusions of the above-cited works, which clearly imply the inferiority of the high content, the strips of plants of good resorbable, amidic nitrogen and magnesium, even at the cost of lowering other nutrients.

Liquid nitrogen fertilizers based on urea and ammonium nitrate are suitable sources of nitrogen for foliar, out-root fertilization of some semi-farmers of important cultures.

Teren J., Courier R., Kotvas F. in their work (Agrochemistry 16/12 /, 344 (1976)) state that, based on this type of liquid nitrogen fertilizer and concentrated aqueous solution of magnesium nitrate, nitrogen-magnesium fertilizers can be prepared with arbitrarily adjustable nitrogen to magnesium ratio.

Although very good results were obtained with this type of liquid nitrogen-magnesium fertilizer, their disadvantage was that they did not contain nitrogen bound exclusively in the amidic form, which is the fastest resorbable form of nitrogen to the plant strips. A further disadvantage was that, besides nitrogen, magnesium and a small proportion of calcium, they did not contain any other biologically active substances at a higher concentration.

In view of the ever-increasing production and consumption of concentrated phosphoric fertilizers based on triple superphosphate, it has recently been an important requirement in practice to ensure sufficient assimilable sulfur content, which is particularly important in the cultivation of soybeans, legumes, etc.

Liquid foliar fertilizers produced at the present time, in most of the ingredients, also do not contain enough iron to prevent the occurrence of chlorosis in some plant species (fast vegetables, fruit trees, grape vines, tobacco, etc.) and thus are less suitable for removing its acute forms.

The deficiency of assimilable iron in podas is widespread and difficult to eliminate (Mortvedt JJ, Wallace Curley R. D. Fert. Solutions 21 (1), 26 (1977)).

200 077

It has now been golden that these deficiencies can be remedied by the use of liquid fertilizer suitable, in particular, for foliar fertilization of plants containing nitrogen, magnesium, sulfur and possibly also trace elements, vitamins, growth promoter and colorant which contain 25 to 100 parts by weight of the final product. 40 parts by weight of urea and 5 to 25 parts by weight of magnesium sulfate.

It has been found that on the basis of the ternary system MgSO 4 - CO (NH ₂ ) ₂ -? 3 ^mO ? ^N ? It prepared a liquid N-Mg-S fertilizer with high nutrient concentration, characterized by relatively high stability at low temperatures. At the same temperature, the dry matter content of the N-Mg-S solution is higher than the dry matter content of the saturated solutions of the basic components themselves. physico-chemical synergism.

I document this finding! for example, the following equilibrium data obtained at ° C.

The composition of the liquid phase of the MgSO 4 -CO (NHg) -HgO system at 0 ° C / wt. Folder, indication % by weight of the components C0 (NH _{2) 2} 40.3 - 39.13 37.91 31.48 MgS0 ₄ 21.31 14.57 21.06 21.75 h ₂ o 59.7 78.69 46.29 41.03 46.77 Dry matter 40.3 21.3 53.7 58.97 52.23 wt. MgSO ratio: CQ (NH _{2) 2} 1: 2.7 1: 1.8 1: 1.45

Especially preferred is the mass ratio between MgSO4 and SiO2, in the range of MgSO4; The urea may be added to the MgSO4 solution in solid form or in the form of a concentrated aqueous solution.

Addition of some chelates (EDTA, DTPA, EDDHA) and / or organic complexes (lignosulfonates, phenylpropane complexes, polyflavonoids) of iron, medium, manganese, zinc and cobalt to the prepared N, Mg, S containing solution allows the preparation of liquid leaf fertilizers with a significant high concentration of nutrients. The concentration of metal cations added in the above-mentioned forms is sufficiently high even for the curative elimination of plant diseases resulting from the deficiency of one of the trace elements (e.g. treatment of plants affected by chlorine with a liquid N-Mg-S fertilizer containing Fe in chelate or of any of the above organic k complexes).

Vitamin (mainly Group B, usually thiamine or aneurine), growth promoters (auxins, gibberellins, kinins) and some food colorings can be added to liquid Ν-Mg-S fertilizers prepared on the basis of urea and MgSO4.

It has also been found that liquid fertilizer according to the invention can be prepared by treating sulfuric acid at 50 to 110 ° C with an aqueous suspension of the magnesium-containing feedstock in the form of oxygen and / or carbonate and / or magnesium hydroxide. The magnesium sulfate is salified for each part by weight of magnesium sulfate

200 077 add 1 to 8 parts by weight of urea and optionally a complexing agent and iron (II) and / or copper (II) and / or zinc and / or manganese (II) and / or cobalt (II) and / or inorganic bromine and / or molybdenum compounds; a growth stimulator and a water-soluble dye. The solid, acid-insoluble fraction of the product is separated by sedimentation, filtration and / or centrifugation.

As the magnesium-containing raw material, it is preferred to use, for example, poppy-burned magnesite - sold under the designation of brick or steel flour, which generally contains more than 85.0% MgO and a CaO content not exceeding 3.5. disadvantage in that it contains a higher proportion of substances predominantly silicates - insoluble in HgSQ ^ and the like.

From a technological point of view, to ensure a smooth reaction of any of the above-mentioned magnesium feedstocks with sulfuric acid, it is preferable to first prepare an aqueous suspension from the summonary magnesium feedstock, which is then treated with H 2 SO 4. The amount of water for slurry preparation depends on the concentration of the basic raw materials as well as the desired concentration and composition of the product.

Sulfuric acid is added in an amount determined on the basis of the total alkalinity of the Mg feedstock so that the final pH of the product is close to 7.

The dčelom achieve the highest production capacity is maintained during the reaction the reaction temperature in the range of 50 ⁰ to 110C. It has been found that at a temperature below 50 ° C the reaction rate is relatively low and at temperatures above 100 ° C the decomposition is accompanied by intense foaming of the reaction mixture.

The overall thermal color of the decomposition is strong positively due to the exothermic nature of the reaction and the release of the solution heat of the sulfuric acid metered.

In order to prevent the crystallization of MgSO4 from the reaction mixture, urea must be added while warming to obtain a higher stability of the N-Mg-S solution. The highest possible stability of the N.Mg-6 solution at low temperatures is achieved at a ratio of 1 part by weight of MgSO4 to 1.7 part by weight of COCNHgJg.

If solid urea (crystalline or granulated) is added, its negative dissolution heat can be used to cool the reaction mixture.

After the reaction of the Mg-feedstock with H 2 SO 4, or after the urea feed, all of the preformed chelates and / or organic complexes of trace elements can be added to the reaction mixture. It is also possible and particularly advantageous to add chelating agents and / or organic complexing agents first to the reaction mixture, and then successively adding sulphates of the respective trace elements to ensure their chelates and / or organic complexes are formed directly in the reaction medium.

If necessary, inorganic boron compounds (boric acid, borax, etc.) can be dissolved in a similar manner gradually in the reaction medium or in the basic N-Mg-S solution,

Mo (e.g., ammonium molybdate), Salia is a suitable source of B-group vitamins, growth promoter and water-soluble, hygienically safe dyes.

If necessary, it can be added to the reaction mixture or to the basic N-MgS solution

200 077 surfactants favorably affecting the wettability of the leaf area of plants.

The most preferred method of separating the solids from the reaction mixture as compared to filtration and removal is a method based on sedimentation of the solids accelerated by the addition of a suitable flocculating agent.

The examples given below illustrate but do not limit the invention in any way.

Example 1

A stainless steel cauldron of about 130 liters, equipped with a reflux condenser, a stirrer and a thermometer, was charged with 71.4 kg (1) of process water and mixed with 17.4 kg of bricked soap with the following specification:

55.4 7b tot. Ca + Mg

54.46% tot. mg

3.77% tot. Fe 0.46% tot. Al

0.04% weight loss at 105 ° C (over 2 hours) total alkallta: 223.9 cm ³ 0.2 N 2 SO 4/1 g bricked, corresponding to 2.196 g MH-H ₂ SO ₄ .

A total of 37.2 kg of 93.15 contact H ₂ SO ₄ was gradually added to the prepared aqueous slurry of brickwash, which represented about 90.7 A for the required total alkalinity of brickwash (brickwash excess of about 10%). . The temperature of the reaction mixture was maintained by adding sulfuric acid in the range of 90-100 ° C. The entire amount of H ₂ SO ₄ (37.2 kg) was fed in 30 min. sulfuric acid was metered at a rate of 20.67 g. s ¹ . After the addition of the entire acid, the reaction mixture was stirred for an additional half hour. Thereafter, 73.8 kg of granulated (adhered) urea was added to the reaction mixture with stirring, resulting in a lower temperature of 86 ° C to 50 ° C. After the entire amount of urea was completely dissolved, 200 g of a 5% aqueous solution of flocculating agent Tiofloc B1 was added to the reaction mixture and, after thorough homogenization, it was allowed to stand still the next day. After sedimentation of the sludge, the clarified N-Mg-S solution was separated. 177.8 kg of clear N-Mg-S solution and 21 kg of sludge were obtained.

The N.Mg.S solution thus prepared had the following specification:

17.5% tot. amidického N

7,2% tot. MgO (4.34% Mg)

5,7% tot. The specific gravity d ₂₀ o _c = 1371.2 kg.m ^-1 pH ₂₀ o _c 8.0 crystallization temperature = -8 ° C.

The composition of the N-Mg-S solution indicated that it contained approximately 240 kg of N, 100 kg of MgO (59.5 kg of Mg) and 80 kg of S in 1 ar.

Example 2

The equipment and procedure were the same as those described in Example 1, the difference being

200877 in the type of magnesium material used. As Mg-aurovina was used magnesite drift, so-called. Romag on specification:

40.17% tot. Mg, ie. 66.6% MgO 1 25 total Ca 3.92% tot. 0.08% of total Fe AI

1.67% weight loss at 105 ° C in 2 hr.

. total alkalinity: 161.5 cm ⁵ 0.2 N H 2 SO 4/1 g Romag, corresponding to 1.584 g Mh-t 2 SO 4 per 1 g Romag.

The quantities of individual raw materials dosed were as follows:

72.6 kg technical water

24.46 kg of magnesia drift Romag 37.8 kg of 93.15% contact HgSO 4

75.1 kg of commercially granular urea.

As described above, 170 kg of clear liquid N-Mg-S fertilizer with similar properties to Example 1 were obtained.

Example 3

78.12 kg of technical water was charged to the apparatus as described in Example 1, and 13.0 kg of brick meal of the specification given in Example 1 was added with vigorous stirring.

Further, 26.54 kg of 93.15% contact SO 2 and 9.1 kg of ferrous sulphate (waste from the production of titanium dioxide by decomposition of ilmanite concentrate with sulfuric acid, consisting of:

18.05 * Fe (ie about 89.8% FeSO4.7 ^ 0)

5.10 ² - 1.10 ¹ 'h TiO ₂

1.0 - 1.5% MgO (0.6 - 0.9% Mg)

0.1 - 0.5% free

2.0 - 5.0% bound water.

After dissolution of ferrous sulphate, 12 kg of technical disodium ethylenediaminotetraacetic acid disodium salt was added gradually with stirring and after dissolution,

61.7 kg of granulated urea.

To the intensely brown-red, slightly turbid solution thus obtained, 200 g of a 100% aqueous solution of the flocculating agent Tiofloc < -1 was added and the sludge was allowed to settle after homogenization. After sedimentation of the sludge, the brown-red clear solution was separated from the sediment layer and 3.5 g of an aqueous solution of beta-indolylacetic acid potassium salt containing, in 1 g of L, 5 mg of said growth emulator was added with stirring.

Thus prepared liquid N-Mg-FeEDTA-5 fertilizer little this specification:

14.8% N

3.6 lb Mg (6% MgO)

0.82% of Fe bound in the form of a chelate

4.7% N

In 1000 kg of solution there is 5.25 g of heteroauxine.

Physico-chemical properties of this fertilizer:

v -3 specific weight ^ 0 ° C ⁼ ^^ 7 kg.m dynamic viscosity (20 ° C): 24,2 mPa.s (c) acidity phjQ 0q 6,0 crystallization point (determined by the method of disappearance of the last crystal) = - 15.9 ° C.

From this specification it follows that this type of liquid foliar fertilizer contains at ° G in 1 m and ³ approximately:

200 kg N, 80 kg MgO (48.24 kg Mg), 11 kg Fe (as FeEDTA), 63 kg S.

Example 4

To a 2.5 dm sulfonation flask equipped with a reflux condenser, a thermometer, a dropping funnel, and an effective stirrer, 510.7 g of water was added, and 17.0.0 g of calcined magnesite was added gradually with stirring. The soaked aqueous suspension of the magnesium raw material was fed in with a dropping funnel over a dropping funnel over a dropping funnel over 60 minutes with 331.7 g of contact sulfuric acid containing 93.15% w / w. h ₂ Sat ₄ .

In keeping with the medium dose rate of about 5.5 g with ^- ^ keeping the reaction temperature in the range 95-100 ° C. After the prescribed amount of sulfuric acid was added, the reaction mixture was stirred for about 30 minutes while the temperature dropped below 50 ° C.

Balej, the reaction was gradually added with stirring 610.0 g 30-ib solution water of the sodium salt of diethylenetriaminepentaacetic acid - ^C] _4 ^H iQ ^N ° 3 and 5 2.O ^At 113, 8 g of waste ferrous sulphate (copperas) of the same quality as in Example 3. After completely dissolving FeSO4 • H2O in the reaction mixture, 771.3 g of technical urea was dissolved under stirring.

To the syrup-like consistency reaction mixture was added 2.5 g of an aqueous flocculant solution (Tiofloc B-1) containing 0.25 g of active ingredient.

Within 2-4 hours the sludge solution completely sedimented the sludge fraction, allowing the clear dark red solution to be separated from the sedimented sludge.

In the above manner, 2,260 g of foliar liquid fertilizer were obtained, which was specified as follows:

I. Chemical composition: - amidic diatom content 14.80% N - magnesium content 5.24% MgO - iron content 0.75% Fe - sulfur content 4.55% S II. Physical-chemical features: - specific weight ^ qOq 1372.6 kg.m ³ P ^H 20 ° C 7.6

200 077

The liquid N-Mg-Fa-S fertilizer prepared by the described apoaob was used for foliar fertilization of fruit trees in arithmetic 1 t 400 with water.

Claims (2)

PEE DMETS OF THE INVENTION 1. Fertilizer suitable for foliar fertilization · rhetin, nitrogen, magnesium, sulfur and possibly also trace elements, vitamins, rash emulator and coloring agent, characterized in that it contains 100% by weight of the final product 25 to 40 parts by weight of urea; and 5 to 25 parts by weight of magnesium sulfate. * 2. A process for producing a liquid fertilizer according to claim 1, characterized in that the aqueous auepension of the magnesium-containing feedstock in the form of a calcium and / or carbonate and / or magnesium hydroxide is admixed with sulfuric acid at a temperature of 50 ° C to 110 ° C. of magnesium sulphate solution, 1 to 3 parts by weight of urea are added to each magnesium sulphate dial, and optionally the complexing agent and iron (II) and / or copper (II) and / or zinc and / or manganese and / or cobalt and / or inorganic boron compounds and / or or molybdenum, B-group vitamins, a raatimulator and a water-soluble dye, wherein the acid-insoluble solids were separated from the product by edimentation,