CS260191B1 - Industrial nitrogen-magnesium-sulphur fertilizer or nitrogen-magnesium-calcium-surphur compacted fertilizer and method of its production - Google Patents

Description

The present invention relates to an industrial nitrogen-magnesium-sulfur-based or nitrogen-magnesium-calcium-sulfur compacted fertilizer on the ammonium side and to a process for its production.

Industrial fertilizers represent an important intensification factor of crop production and, in relation to other factors, affect 30% of crop production. The high intensity of fertilization is connected with the necessity of effective spending of resources - in this area, especially in economic terms, there will be no increase in the volume of supplies of industrial fertilizers in the future.

The necessary environmental protection is also a serious limiting factor. 7. In terms of energy and foreign exchange, nitrogen and phosphorus fertilizers are the biggest burden for our economy, because we import all the raw materials for their production (petroleum products, natural gas, phosphates, phosphoric acid, sulfur).

From domestic sources we have ammonium sulphate in nitrogen fertilizers, which is a by-product mainly from the production of caprolactam. Its more efficient use often depends on the society-wide required increase in the production of the main real product (caprolactam, methacrylates, ferrous pigments and the like).

Despite the suitability of ammonium sulphate for some crops, especially in pre-sowing and on basic grounds, it is less interested in agricultural practice than supply. This is mainly due to the lower nutrient content (21% N), in terms of application, the most unsuitable crystalline form and, above all, high physiological acidity. Its long-term use in insufficient liming increases acidity and thus deteriorates the physico-chemical properties of the pod. In view of the above, it is necessary to look for such forms and methods of utilizing ammonium sulfate that minimize its negative properties.

Plants contain about 0.5% magnesium on average. It is bound in the form of oxalates, phytin, inorganic compounds are practically insignificant, but its chelate bonds in physiologically important compounds are of primary importance. In the chlorophyll core, e.g. 15% to 20% of the total mg content in plants, a considerable content 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 since magnesium is required not only for the formation of chloro260191 yl but also for the phosphorylation processes and also for the re-formation of ribulozodiphosphate. The reduced production of glycides also results in reduced production of proteins and accumulation of nitrogen and free amino acids.

The requirements of plants for magnesium depend mainly on the type of crops being grown. The crops harvest 15-15 kg per hectare, more difficult are the woodpeckers, legumes, sugar beet and tobacco, which on average need 30 to 60 kg mg / ha. Due to the constant increase in the concentration of nitrogen, phosphorus and potassium fertilizers he has them constantly magnesium nlžšie representation is needed with magnesium count as one of the major vegetable live ^T 4N and is necessary to eliminate the consumption of fertilizer.

If we assess the magnesium content in the soil, it finds: not that the parent rock contains less than 1 ° / o of this element. The poorest on the miner are the acidic undersized stages.

Magnesium in the presence of calcium also positively affects the pH of the soil as well as the formation of humus.

The importance of fever for proper nutrition of growth in our conditions was emphasized by PROSA, V. (Agrochemistry, 13, 1973, p. 285), NOVAK, '1. (Chemical Industry, 23, 1973, p. 276), TEREN, J. et al. (Agrochemistry, 16, 1976, p. 344) and in particular FECENKO, J. ("Optimization of plant nutrition by magnesium in conditions of high fertilization intensity", VEDA - Bratislava 1986; XXIXth Days of New Technique in Plant Chemistry, CHZJD np Bratislava, 5 to November 6, 1985).

3SR 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 distance of 160 km, magnesite represents a reserve of about 100 mil. tons and dolomites are made up of whole mountains. Taking this into account and at the same time the lack of fever in the stages of some areas of the CSSR, especially in the eastern and southern areas of Czechoslovakia, it must be stated that the use of these domestic febrile raw materials and the production of fertilizers containing magnesium are quite inadequate.

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

It has now been found that the disadvantages of using ammonium sulfate as a nitrogen fertilizer and the problem of securing febrile agrochemically effective fertilizers. In a preferred manipulated-application form, the invention is solved.

The present invention is based on an industrial nitrogen-magnesium-sulfur-sulfur fertilizer or a nitrogen-magnesium-calcium-sulfur-compacted ammonium sulfate fertilizer.

The compacted fertilizer according to the invention contains 15 to 85 wt. % ammonium sulfate and 10 to 80 wt. % magnesium oxide (MgO), magnesium carbonate (MgCO3 and Mg / HCO3 / 2, respectively) or calcium-magnesium carbonate (MgCa / CO3 / 2).

It may further comprise other substances which improve the shelf life and increase the agrochemical efficiency of the final product.

As a source of ammonium sulphate in the context of the production of the compacted fertilizer according to the invention, a byproduct from the production of caprolactam and / or methacrylate or ammonium sulphate resulting from the production of special products based on iron compounds (ferrous pigments, and so on).

As a magnesium source, the compacted fertilizers according to the invention comprise magnesium oxide prepared by decarbonising magnesium carbonate (so-called steel or brick meal; trapped from decarbonising magnesite furnaces - "ROMAG" and the like), or containing magnesium carbonate in ground natural magnesite or dolomite.

As the shelf-life enhancers of the final fertilizer it is suitable to use one of the hydrocarbons or derivatives thereof and / or it is expedient to use natural zeolite and / or kaolin. Of the agrochemical and agronomic efficiency enhancers, it is advantageous if the fertilizer also contains secondary or possibly trace plant nutrients as well as thiourea or dicyandiamide, the presence of which significantly affects the use of mainly the pith component by plants. It has been proven that the plume or dicyandiamide content of the fertilizer cd corresponds to about 2 to 18% of the nitrogen supplied in the form of the subject additives of the total nitrogen content in the solid, under pressure compacted by the industrial fertilizer.

In the case of the application of carbon disulfide - carbon disulfide (CS2), it is expedient to incorporate 0.2 to 12 kg of carbon disulfide sorbically bound to a porous substance (eg natural zeolite, activated carbon, silica gel, etc.) ) per hectare of agricultural land.

The advantages of the proposed solution are as follows:

- Reduction, respectively. removing the effect of physiological acidity of ammonium sulphate. Fertilizer by its composition is a combination of physiologically acidic component - (NH4) 2SO4 and physiologically alkaline magnesium, resp. a magnesium-calcium component.

According to Pierre (PIERRE, W.H .: "Determination of Equivalent Acidity and Basicity of Fertilizers", Industrial and Engineering Chemistry - Analytical Edition, 1933, Vol. 5, p. 229-234), acidity (-), respectively. the basicity of (-I-) ammonium sulfate and calcium-carbonate, as follows:

and re-, -i η / ..τι ^k S CaCOs / 100 kg of ammonium sulphate (21.1 ° / o N) ------------- Yio ----- limestone + 80 to +95 dolomitic limestone +90 to +100 resp. on the already cited work PIERRa acidity, respectively. (FERTILIZER MANUAL. Development and Transfer of Technology Serlos No. 13, UNIDO-UNITED Nations, New York 1980, p. 309):

Corresponding acidity (-) or basicity (+) (kgCaCOs / kg element)

Kyslo póscbiace Fertilizer components: N - + 79 WITH 3.12 Alkaline multiplication of fertilizer component: ca +2.50 mg +4.12

- Achieving a higher effect and use of the magnesium component of the compacted fertilizer. Combination of ammonium sulphate with magnesium substrate:

(MgO, Mg / CO3) 2, MgCa (CO3) 2 is advantageous because ammonium sulphate, by its acidic physiological effect, contributes to the milling of otherwise hardly accessible forms of magnesium and magnesium, respectively. calcium.

· Reduction of transport costs and negative impact of the transition of heavy machinery on the agricultural land (compaction of soil).

The production of solid compacted industrial fertilizers according to the invention is less energy and technologically demanding compared to the production of conventional granular fertilizers, and the products prepared by compacting under the effect of pressure have better storage and handling properties.

In the application form, ratio and nutrient content, the fertilizers according to the invention are used in particular in the autumn and spring application for pre-stocking or amelioration fertilization with higher doses, while incorporating organic matter. The application to the stubble is advantageous. Fertilizer is suitable for fertilization mainly of grassland, woodpeckers, legumes, winter rape, hops, onions, beet, potatoes, caliber and oats, especially in the potato and wetter foothills. They are also suitable for stock fertilization before the establishment of fruit plantations and vineyards.

The solid pressure-compacted industrial fertilizers within the meaning of the invention can be produced by the fact that a mixture comprising ammonium sulfate and magnesium oxide or ground magnesia or dolomite is subjected without, or in the presence of a binder, to one or more stages of compression between rotating rollers. The prepared compressate is further partially disintegrated, the fraction of the desired size and shape of the compressor is separated from the disintegration product. The separated product fraction is optionally surface treated.

For compacting mixtures containing ammonium and magnesium sulphate, respectively. The magnesium-calcium substrate can be used by one of the commercially available continuously operating compacting equipment (manufactured by, for example, HUTT-BEPEX) or by using a suitable modified calendering machine, the use of which is common in plastics and rubber processing technologies.

Pressure granulation has found application particularly in fertilizer potassium salt granules. In this context, the technology of the following foreign companies is currently applied:

ALLIS-CHALMERS,

KOMAREK-Greaves

HUMBOLDT a

VULCAN-KOPPERS.

Out of a small number of specialist papers dealing with pressure granules, the following works can be mentioned:

KURTZ, Β. E. - BARDUHN, A. J .: "Compacting Granular Solids". Chemical Engineering Progress, 56 (1): 67-72, 1960;

Anonymous: FERTILIZER MANUAL, United Industrial Development Organization, Development and Transfer from Technology Series 13, p. 240-241, New York 1980;

KLASSEN, Ρ. V. et al., Chim. prom., 1973, no. 9, p. 669 to 672;

PE1CHL, R .: „Kompaktier - Granulatlon die zur Zeit Modernste Granulationstechnh +. Agrichem ‘84 - Chemistry in Agriculture, June 1984 - Bratislava;

PEICHL, R .: Kompaktier Granulation “. SC —— Zeitschrift 1983, Heft 4;

BARLOY, M .: Granulation d'engrais par

6 019.2} oompactage - Procede ABC '. Congress on the End-of-Life Development of Industrial Fertilizers - - Istambul (Turkey), 13-17 May 1985.

Production of compound fertilizers based on ammonium sulphate and magnesium oxide, or magnesium carbonate, respectively. The magnesium-calcium process according to the invention has a number of advantages over the conventional granulation process in a drum or tiler granulator, among which the following can be mentioned:

- reduced energy demand by 40 to 70. θ / ο, - lower investment in machinery, v. the product range produced, - the production method allows for rapid stabilization of the operating parameters, - the production has a significantly lower negative impact on occupational and environmental hygiene.

The following examples illustrate but do not limit the invention in any way. Example 1

50 kg of technical crystalline ammonium sulphate obtained after neutralization of acid sulphate liquors from the production of caprolactam and methacrylates in PCHZ n. p. Yeast with 48 kg of technical magnesium oxide. brick flour from SKZ n. p. Košice specified as follows:

Total chemical alkalinity:

223,9 cm ³ 0,2 N —- H2SO4 (1 g brick meal, ie 2,196 g MH — H2SO4)

With efficient homogenization, 4.8 kg of concentrated sulphate stillage containing about 48 wt. % dry matter.

The thickened sulphite stillage was heated to about 60 ^° C to reduce the viscosity. About 2.5 kg of water was introduced into the mixture as described above.

Further, 1.2 kg of technical thiourea (CS / NH2 / 2) was added to the mixture to reduce nitrogen losses by nitrification points.

The mixture thus prepared was processed by compacting between smooth, counter-rotating rollers. The prepared 4 mm depth compress was partially disintegrated to form a coarser pulp, from which a 2 to 4 mm fraction was separated using a separator. The fraction of the production fraction was approximately 40% relative to the weight of the mixture fed to the compacter.

The nitrogen-magnesium-sulfur fertilizer prepared as described above contained 10.5 wt. % total nitrogen and 43.3 wt. % MgO.

Example 2

In a conical homogenizer with a moving "Naltamix" helical stirrer, 70 kg of technical crystalline (NH 4) 2 SO 4 was mixed with 25 kg of captured magnesite drift from magnesite furnaces, so-called. Romagus specification:

40.17 wt. % tot. mg,

t. j. 66.6 wt. % MgO

1.25 wt. 0/0 tot. ca

3.92 wt. % tot. Fe 0.08 wt. ° / o tot. AI

1.67 wt. % weight loss by drying at 105 ° C in 2 hr.

total magnesium and calcium content total magnesium content iron content aluminum content weight loss by drying at 105 ° C (2 hours)

Total alkalinity, 'Romag':

55.4 Mg-i-Ca

161.5 cm ³ 0.2 N — H2SO4 / 1 g t. q,

t. j. 1.584 g ΜΉ — H2SO4 / 1 g Romagu t. q.

54.46 Mg

Next to the mixture of the already mentioned components

3.77 Fe added 5.0 kg of natural zeolite from the site

Nizhny Hrabovec, which follows its thermal

0.46 Al activation (350 hours in a stream of incandescent nitrogen) sorbed with carbon disulfide - carbon disulfide so that it contained

0.04 average 5.5 wt. % sorption-bound wt. % CS2.

% wt.

260

1.2 kg of molten paraffin was applied to a 100 kg homogenized mixture in a homogenizer using a nozzle atomizer. The mixture thus prepared was further processed in a manner analogous to Example 1.

In this way, a nitrogen-magnesium-sulfur-compacted fertilizer with a gradual - biologically, mechanically and physically controlled, nitrogen-containing component efficiency, with very good storage and handling properties of the final product was obtained.

Example 3

In accordance with Example 1, 60 kg of technical crystalline ammonium sulfate and 38 kg of dolomite (Solatin, Ruzomberok) were homogenized with the following composition:

Claims (6)

An industrial nitrogen-magnesium-sulfur-sulphate or nitrogen-magnesium-calcium-sulphurous compacted ammonium sulphate fertilizer, characterized in that it contains 15 to 85 wt. % ammonium sulfate and 10 to 80 wt. % of magnesium oxide, magnesium carbonate, or calcium-magnesium carbonate, and also contains substances which improve the shelf life and increase the agrochemical efficiency of the final product. 2. Fertilizer according to claim 1, characterized in that it contains ammonium sulphate formed as a by-product in the manufacture of caprolactam and / or methacrylate or in the manufacture of special products based on iron compounds. 3. Fertilizer according to claim 1, characterized in that it contains magnesium oxide prepared by decarbonising magnesium carbonate or contains magnesium carbonate in the form of ground natural magnesite or dolomite. 4. The industrial fertilizer referred to in point 1 above shall: CaO content 31.06 MgO content 21,00 CO2 content 47.42 FeO content 0.21 unspecified the rest the rest on the sieves 0.30 0.35 mm 0.30 0.25 mm 3.50 0.125 mm 18.40 0,04 mm 74.90 The H 2 O content of the mixture was adjusted to 5.4% by means of a spray nozzle. The raw material mixture thus treated was processed by pressure granulation - compression between the yard smooth rolls of 270 mm in diameter, 120 mm in length, at 8 rpm. and a force of 1000 N / cm. A compressed web of 3.8 millimeters was disintegrated in a hammer mill. A 2 to 4 mm particle fraction, which represented 49.3% of the weight charged to the compacter, was separated from the coarse pulp. The nitrogen-calcium-magnesium-sulfur fertilizer product contained 11.48% N, 7.60% MgO and 11.24% CaO. The invention is characterized in that it contains one of the hydrocarbons or derivatives thereof and / or ground natural zeolite and / or kaolin as substances which improve its shelf life. 5. An industrial fertilizer according to claim 1, characterized in that it contains dicyandiamide, thiourea or carbon disulphide sorbent on a porous support as substances improving its agrochemical efficiency. 6. The method of production of an industrial fertilizer according to claim 1, characterized in that the mixture containing ammonium sulfate and magnesium oxide, magnesium carbonate or calcium-magnesium carbonate is subjected in one or more stages to compression in rotating rollers in one or more stages. the prepared compressate is further partially disintegrated, the fraction of the desired size and shape of the compressor is separated from the disintegration product and this is optionally further surface-treated.