CS257125B1 - Suspension nitrogen-sulfur-magnesium and / or calcium fertilizer - Google Patents

Abstract

The solution relates to a suspension nitrogen-sulfur-magnesium and/or calcium fertilizer, in which the basis of the heterodisperse system is formed by a homogeneous phase of the binary system ammonium sulfate — water, or of the ternary system ammonium sulfate — urea — — water and a dispersed phase formed by particles of magnesium carbonate and/or calcium and/or magnesium oxide and/or calcium and/or magnesium hydroxide and/or calcium and/or calcium sulfate and optionally also by particles of ammonium sulfate. The homogeneous phase contains 28.0 to 43.6 wt. % ammonium sulfate, 31 to 72 wt. % water and optionally also contains urea. The heterodisperse system is stabilized and optionally also contains other basic, secondary and trace plant nutrients.

Description

(54) Suspension nitrogen-sulfur-magnesium and / or calcium fertilizer

2

The invention relates to a suspension of nitrogen-sulfur-magnesium-and / or calcium-based fertilizer in which the heterodisperse system is based on a homogeneous phase of the binary ammonium sulphate-water system or a ternary ammonium sulphate-urea-water system and a dispersed phase composed of magnesium carbonate particles and / or calcium and / or magnesium oxide and / or calcium and / or magnesium and / or calcium hydroxide and / or calcium sulfate, and optionally also ammonium sulfate particles. The homogeneous phase contains 28.0 to 43.6% by weight ammonium sulfate, 31 to 72% by weight water and optionally also contains urea. The heterodispersion system is stabilized and optionally also contains other basic, secondary and trace plant nutrients.

The invention also relates to the fertilization of low-magnesium sulfonic acid and calcium carbonate fertilizers.

Industrial fertilizers. predominantly, an important intensification factor; rastíáarBf. production and in relation to other factors. they affect> 30. <% plant production. High intensity and fertilization is also associated with the need for effective spending in this area. From domestic sources of nitrogen fertilizers we have enough ammonium sulphate, which is a byproduct mainly of caprolactam production. Its more efficient use often results in a society-wide desired increase in the production of the main reaction product (caprolactam, methacrylates, ferrous pigments and the like).

Despite the suitability of ammonium sulphate for some crops, and especially in pre-sowing and alkaline soils, it is less of an interest in agricultural - practice-less than supply. This is mainly due to the lower nutrient content (21% N), not the most suitable crystal for application! fíwmout and even above ·· high. physiological acidity. Its long-term use in insufficient liming increases acidity and thus deteriorates the physico-chemical properties of soils. In view of the above, it is necessary to look for forms and methods of use of ammonium sulfate that minimize its negative properties.

Plants contain, on average, okGi · 0 ^ 5 θ / ο. magnesium. It is bound in the form of spinach, phytin, inorganic compounds are practically insignificant, but its chelate bonds in physiologically important compounds are of primary importance. In the chlorophyll core, e.g. bound 15–20% of the total Mg content in plants, considerable content is also in mitochondria and cell walls. Magnesium also plays an important role in the activation of enzymatic processes and its presence also affects the metabolism of carbohydrates, lipids and nucleic acids. In the absence of Mg, the intensity of photosynthesis decreases as magnesium is required not only for the formation of chlorophyll, but also for the phosphorylation processes and also for the re-formation of ribulozodiphosphate.

Reduced carbohydrate production also results in reduced protein production and accumulation of nitrogen and free amino acids. The requirements of plants for magnesium depend mainly on the type of crops being grown. The cereals use 15–30 kg of hectare to harvest the crops, more demanding are clover, legumes, sugar beet and tobacco, which on average consume 30–60 kg Mg / ha.

As the concentration of nitrogen, phosphorus and potassium in industrial fertilizers is constantly lower in magnesium, it is necessary to count on magnesium as one of the important plant nutrients and eliminate its consumption by fertilization.

If we assess the magnesium content in the soil, we find that the mother rock contains less than 1% of the pDPfcu. The poorest on bitter & is] keeleddested soil.

The magnesium in the presence of calcium, favorably affects also. pH-soils as well as formation of huIM6H ...

The consumption of the plant as a secondary plant nutrient is much lower compared to its consumption for treating the acidic acid below and PFavdeppdobflua.-jQ; Sufficiently covered, it uses both natural and calcium-containing fertilizers (for example, single, enriched and triple superphosphate, precipitate, calcium salts, combined NPK fertilizers) ground and semi-decomposed phosphates and the like).

The need for limestone has an increasing trend due to a constant decrease in soil pH from pH 6.5-7 to 5-4. to some extent, the introduction of irrigation management, increasing the intensity of tillage, soil organic matter, and mainly the constant use of nitrogen in relatively high doses, the most important factor affecting the drop in pH myu dosíkaa

In the process of ammoniacal nitrogen conversion through nitrite nitrogen to nitrate nitrogen, the first stage of this nitrification process is a major cause of soil pH reduction, as shown in the following equations showing the nitrification of ammonia nitrogen:

HNH ₄ + + 3O ₂ - 2 NO ₂ - + H ₂ O + 4H ⁺ (first degree of nitrification is

NO ₂ - + O ₂ - 2 NO ₃ Harmful effect. acidity, "falls" ·· sa-. for example:.

—In ·, lower-exchange · ability? calcium horčík.ar5a_draslíkfl ₄ -vos higher výmeaafi) · skills. aluminum; result; it has a toxic effect, i.e., avo. The fixing-plus-ii .; phosphorus; as a result of which it decreases its resorbability —v? reduction of the activity of microorganisms,

- in imhifoici. mineralization of other organic substances, - in abnormal,. system; · rasfettnyí · which; due to the deterioration of resorbovatelnasti; nutrients ·, a.- similar-.

Micronised powdered limestone, dolomitic limestone, or trapped debris from shaft or rotary kilns, which mainly contain calcium and / or magnesium oxides, are most commonly used to adjust the pH of the soil. The application of these products in powder form is associated with a number of difficulties such as reduced work hygiene due to considerable dustiness, considerable drift even in moderate winds, not only during application but also from already treated areas, unevenness of application related to the heterodisperse nature of the substance used for liming and the like.

In an effort to overcome these deficiencies, the use of micronized limestone in liquid suspension form to adjust the pH of soils has been increasingly reported in recent years, especially in the US literature. Solns. 20 (3) 18 (1976), Ibid. 21 (4) 30-53 (1977), Ibid. 21 (6): 103 (1977)].

The importance of magnesium for proper plant nutrition was emphasized in our conditions by PRŮŠA, V. (Agrochemistry, 13, 1973, p. 285), NOVÁK, M. (Chemical industry, 23, 1973, p. 276), TEREN, J. et al. (Agrochemistry, 16, 1976, p. 344) and in particular FECENKO, J. (XXIX. Days of new technology in the chemistry of plant production, CHZJD n. P. Bratislava, 5 - 6 November 1985).

SSR has a rich base of raw materials containing magnesium, especially magnesium and dolomite. According to the results of a geological survey in the area of Lučenec - Košice in the length of 160 km, magnesite represents a reserve of about 100 mil. tons and dolomites are made up of whole mountains. Taking into account this fact and at the same time the lack of magnesium in the soils of some areas of Czechoslovakia, especially in eastern and southern areas of CSR, we have to say that the use of these domestic magnesium materials and the production of fertilizers containing magnesium are quite insufficient.

Magnesite is processed by decarbonisation to technical magnesium oxide, which is supplied as a so-called magnesium oxide. brick or steel fly. The entrapped escape from the decarbonisation magnesite furnaces, known under the commercial name ROMAG, also has a high magnesium content.

When processing sugar beet into sugar, the so-called. saturating sludges containing mainly fine-grained precipitated calcium carbonate and in addition also organic bound nitrogen, phosphorus and potassium, as well as a number of biologically active secondary plant nutrients and trace elements.

The average dry matter composition of sugar saturating sludge is approximately:

% CaO

3.8-4.0% MgO

0.4% of total N

0.8% P ₂ O ₅

0.4% K _2! ABOUT

15—31% organic matter.

Calcium is predominantly (about 2/3 of its content) in the form of finely flocculated aragenite and the rest (about 1/3) is bound to P ₃ O ₅ and organic substances. Nitrogen is usually in the form of proteins and their cleavage products (amides, peptones and the like), with a protein content of up to 90%.

In some manufacturing processes, such as citric acid, calcium sulfate-gypsum is produced as a by-product. Such gypsum contains 40-60 washes. water, forming sticky clumps and is therefore difficult to handle. Its chemical composition is very suitable for application to amelioration interventions in saline below. The undesirable physical properties of this gypsum make it difficult to handle that such use is costly.

The direct use of these saturating sludges for liming acidic substrates is greatly complicated by their unfavorable physical properties (high thixotropy, formation of hard agglomerates upon drying and the like), although they are particularly suitable for liming below their high biological value and neutralizing efficiency.

Because of these unfavorable physical properties from the direct application of fresh saturating sludge, sludge must be exported to the heaps during the sugar campaign, where they remain for several years. However, even after long-term storage, the saturation sludge does not lose its unfavorable physical properties, causing difficulties in handling, transport and application to such an extent that their use is sometimes impossible.

It has now been found that the disadvantages of using ammonium sulfate as a nitrogen fertilizer as well as the disadvantages associated with handling and / or lime matter in agricultural practice obviate the invention. SUMMARY OF THE INVENTION The present invention provides a suspension of nitrogen-sulfur-magnesium and / or calcium fertilizer, characterized in that the heterodisperse system is based on a homogeneous phase of the binary ammonium sulfate-water system or ternary ammonium sulfate-urea-water system and dispersed phase consisting of magnesium carbonate particles. and calcium and / or magnesium oxide and / or calcium and / or magnesium and / or calcium hydroxide and / or calcium sulfate, or else ammonium sulfate particles.

The homogeneous phase contains 28.0 to 43.6 weight percent ammonium sulfate, 31.0 to 72.0 weight percent water.

The heterodisperse system is stabilized and may contain other basic, secondary and trace nutrients.

An important advantage of the suspension fertilizers according to the invention is that their use partially or completely eliminates the physiological acidity of ammonium sulfate. Fertilizers are also suitable combinations of the physiologically acidic component - (NH / J2SO4 with physiologically basic components), which are also suitable sources of assimilable magnesium and / or calcium plants.

Pierre, WJ: "Determination of Equivalent Acidity and Basicity of Fertilizers", Industrial and Engineering Chemistry - Analytical Edition, Vol. 5, pp. 229-234; also Anonymous: FERTILIZER MANUAL, Development and Transfer of Technology Series No. 1 13, UNIDO - United Na7

257-1.25:

tions, New York 1980, p. 310.) is acidity (-), resp. (+) ammonium sulfate base Material

Ammonium sulphate (21.1% N)

Urea (46.6% N)

gypsum

limestone

Dolomitic limestone

The application of the suspension fertilizers according to the invention makes it possible to achieve a substantial reduction in transport costs, to negatively affect the passage of heavy mecthanisms on the agricultural field (so-called densification of the soil) and to efficiently utilize several valuable secondary raw materials containing calcium and calcium. magnesium also has a number of other important biologically active ingredients.

Suspension fertilizers within the meaning of the invention are also active in connection with desulphurisation of agricultural land (STROMBERG,

L.K. - TISDALE, S.L .: "Treating irrigated arid land soils with acid-forming sulphur compounds". Technical Bulletin Number 24, The Sulfur Institute, Washington, D. C., March 1979 j.

Another important advantage lies in a more suitable application form, which guarantees a reduction in labor intensity and a substantial increase in culture and work hygiene. Economically and technologically, the production of suspension fertilizers is less demanding than the production of solid fertilizers. Significant is the energy savings if the production is based on concentrated ammonium sulfate solutions from the production of caprolactam, methacrylates or from the production of iron pigments.

It has been found that finely ground dolomite [CaMg (CO ₃ ) ₂ ] or dolomitic-limestone can be used as a source of magnesium carbonate (MgCO ₃ ) and calcium (GaCO ₃ ) for the production of the suspension fertilizers according to the invention.

As a source of calcium carbonate, it is particularly preferred to use finely precipitated calcium carbonate for the preparation of the fertilizer according to the invention, in particular in the form of sugar confectionery sludge.

It has been experimentally confirmed that finely ground thermally refined - decarbonised magnesia can be used as a source of magnesium oxide (MgO) in connection with the production of grain-size supernatant fertilizers.

Particularly suitable for this purpose are captured dust collectors from magnesite furnaces:

As a very suitable source of calcium in its sulphate form, it has been shown to prepare a suspension! use some of the types of gypsum produced as secondary or waste material of several inorganic and organic technologies. Given the form and content of biologically active ingredients, it is particularly advantageous to use both, and some others, for this purpose. suspension fertilizer components within the meaning of the invention, as follows:

kg CaGO 3/100. kg of material —112 - 84 ´ +86 to- + 95 +9 (J to +106 precipitated calcium sulphate obtained in connection with citric acid isolation:

The foregoing examples illustrate but do not limit the scope of the invention in any way.

Example 1

540 parts by weight of an aqueous solution consisting of 311.5% by weight were introduced into a laboratory knife mixer. % ammonium sulphate, (NH 2 SO 4, 2T, 0 wt.% urea-GCPfNH (rt ₂ and 47; 5 wt.% f water, characterized by a phase stability of o ₎ and 15 wt. attapulgite (&quot; Mln-U-gel 200 &quot; from Floridin G5), 7 parts by weight of an aqueous solution of about 45% lignosulfonic acid (Adishol) and 438 parts by weight of technical magnesium oxide, so-called brick fly The fused brick meal was characterized by the following chemical composition:

55-4 ' ^: wt% Mg + -Ga 54.46 wt. % Mg

3-77 ¹ wt. % Fe 0.46 wt% Al - Loss on drying at 105 ° C / / 2 hrs: 4. 10 ^_2: wt% - total alkalinity: ZZ3; 9 cm® 0.2 N — H ₂ SO 3 / / 1 g brick meal, equivalent to 2.196 g · MH — H ₂ SO /, per 1 g brick meal.

The homogenization mixture · 1000 wt. parts of a sulfur-magnesium-magnesium-calcium suspension fertilizer of a weakly alkaline chemical reaction, comprising:

8:87 'wt. % tot. N (40.5% in the-form of _NH4 ⁺ and 59.5% in the amide form) ",

4.11 wt. ° / o sulfur,

39; 5 5 ~ wt. % MgO and 0.58 wt. % CaO.

Example 1 ^; 2 '

An average of 20'kg- 39'5% aqueous ammonium sulfate solution - (ΝΗ ₄ ) ₂ βΌ / "

8 7 1.2 5

3.7 kg of approximately 15% aqueous bentonite suspension from the locality Žiarska kottlina - Alder stream containing calcium lignosulfonate added in the form of thickened sulphite stillage and 9.3 kg of magnesite kiln drift supplied under the name Romag. The Romag used was specified as follows:

- magnesium content: 40.17 wt. % Mg (i.e.

66.6 wt. % MgO) - calcium content: 1.25% Ca - iron content: 3.92 wt. Fe - aluminum content: 0.08 wt. % Al - weight loss on drying at 105 ° C / 2 hr .: 1.67 wt. % - total alkalinity: 161,5 cm ³ 0,2 N. H ₂ SO ₄ / / g Romag, corresponding to 1,584 g MH - H ₂ SO ₄ per 1 g Romag.

By homogenization, an average of 33 kg of a weakly alkaline reaction suspension was prepared per minute, containing:

5.05 wt. % amniacal nitrogen,

5.79 wt. % sulfur,

18.77 wt. % MgO and 0.35 wt. % calcium.

Example 3

346.8 parts by weight of the sugar saturating sludge containing 62% by weight were introduced into an efficient homogenizer. % solids containing 50% CaO, 3.9% MgO, 0.4% N, 0.75% P ₂ O ₅ , 0.32% K ₂ O and 28% organic matter, and with stirring gradually it supplied 88.71 parts by weight of adhered urea, 100.0 parts by weight of crystalline ammonium sulfate - (NH ₄ ) ₂ SO _4, and 2.0 parts by weight of the Min-U-gel-200 attapulgite powder.

537.51% by weight of a stable nitrogen-sulfur-calcium-magnesium suspension were obtained, comprising:

11.8 wt. % of total nitrogen,

4.5 wt. % sulfur,

20.0 wt. ° / o CaO,

1.6 wt. % MgO,

0.3 wt. % P ₂ O ₅ and 0.1 wt. o / o K ₂ O.

Suspension fertilizer was suitable for ameliorative fertilizers on saline and acidic soil.

Example 4

500 g of a 41.5% aqueous solution (NH / J ₂ SO ₄₎ were gradually added to the laboratory mixer and 100 g of a 15% aqueous dispersion of natrified bentonite provenance was gradually added with efficient mixing. further added 600g of the filtered fresh calcium sulfate being obtained in the form of _CaSO4. 2 _H2O in the production of citric acid (the ex Slovlik - Leopold).

The wet filter cake used contained 48% dry matter, about 11% calcium and 8.6 wt. pen. sulfur.

By homogenization, 1,200 g of a suspension of nitrogen-calcium-sulfur fertilizer, which contained 3.6 wt. % _N-NH4,

5.5 wt. % Ca and 8.5 wt. % of total sulfur. The specific gravity of the suspension fertilizer was 1260 kg. m- ³ and its dynamic viscosity at room temperature was 370 cP.

Claims (5)

2 8 7 1.2 5 9 10 3.7 kg approx. 15 ° / o aqueous) suspension of fried bentonite from the Žiarska kotlina - Jelš stream containing calcium lignosulphonate added in the form of thickened sulphite stillage and 9, 3 kg of captured drift from the magnesite furnaces called Romag. The Romagbol used as follows: - magnesium content: 40.17 wt. % Mg (t.), 66.6 wt.% MgO) - calcium content: 1.25% Ca - iron content: 3.92 wt. % O / o Fe - aluminum content: 0.08 wt. % Al - drying loss at 105 ° C / 2h: 1.67 wt. % - total alkalinity: 161.5 cm3 0.2 N. H2SO4 // 1 g Romag, corresponding to 1.584 g MH-H2SO4 per gram of Romag. On average, an average of 33 kg of suspension or alkaline reaction was prepared per minute by homogenization, containing: 5.05 wt. % amniacal nitrogen, 5.79 wt. % sulfur, 18.77 wt. % MgO and 0.35 wt. % calcium. EXAMPLE 3 346.8 weight percent sugar saturation sludge containing 62 weight percent was introduced into an effective homogenization apparatus. % dry matter which contained 50% CaO, 3.9% MgO, 0.4% N, 0.75% P2O5, 0.32% K2O and 28% organic, and was gradually mixed with - dispensed 88.71 parts by weight of bound urea, 100.0 parts by weight of crystalline ammonium sulfate - (NH 4) 2 SO 4 and 2.0 parts by weight of attapulgite powder type "Min-U-gel-200". Thus 537.51 parts by weight of a stable nitrogen-sulfur-calcium-magnesium suspension was obtained containing: 11.8 wt. % total nitrogen, 4.5 wt. % sulfur, 20.0 wt. CaO, 1.6 wt. % MgO, 0.3 wt. % P2O5 and 0.1 wt. o / o K2O. The suspension fertilizer was suitable for melting fertilization on salted and acidic soil. EXAMPLE 4 500 g of a 41.5% aqueous solution (NH4SO4SO4) were gradually introduced into a laboratory rapid mixer and 100 g of a 15% aqueous dispersion of natrified bentonite nitrile monohydrate was added sequentially with effective agitation. 600 g of freshly filtered calcium sulphate disposed of in the form of CaSO 2, 2 H 2 O in the production of citric acid (from the plant SLOVLIK - Leopoldov) were added to the bentonite genesis with stirring, and the wet filter cake used contained 48% dry matter, about 11% calcium and 8, 1200 g of gaseous lime-calcium sulphate fertilizer was prepared by homogenization, containing 3.6% by weight of N-NH2, 5.5% by weight of Ca and 8.5% by weight of total sulfur. The specific gravity of the suspension fertilizer was 1,260 kg / m 3 and its dynamic viscosity at room temperature was equal to 370 cP. Suspension nitrogen-sulfur-magnesium and / or calcium fertilizer, characterized in that the heterodisperse base forms a homogeneous phase of the binary system of the ammonium sulfate-water or ternary ammonium-urea-water system and the dispersed phase it consists of particles of magnesium carbonate and calcium carbonate and / or magnesium and / or calcium oxide and / or magnesium hydroxide and / or calcium and / or calcium sulfate particles or ammonium sulfate particles, the homogeneous phase comprising 28 From 0 to 43.6% by weight of ammonium sulfate, 31 to 72% by weight of water, and the heterodisperse composition is stabilized. Suspension nitrogen-sulfur-magnesium and / or calcium fertilizer according to claim 1, characterized in that it contains fine-grained dolomite, CaMg (CO 3) 3 as the source of magnesium and calcium carbonate. 3. Suspension nitrogen-sulfur-magnesium and / or calcium fertilizer according to claim 1, characterized in that it contains, as the carbonate calcium carbonate, finely precipitated calcium carbonate, e.g. in the form of sugar saturation sludge. 4. Suspension nitrogen-sulfur-magnesium and / or calcium fertilizer according to claim 1, characterized in that it contains thermally calcined magnesium as the source of magnesium oxide, e.g. in the form of trapped dusts from magnesite furnaces. 5. Suspension nitrogen-sulfur-magnesium and / or calcium fertilizer according to claim 1, characterized in that it contains, as the source of calcium sulphate, precipitated sulphate calcium obtained in the production of citric acid.