In many countries, the agricultural industry is experiencing a shortage of land resources due to the enormous growth rate of the agricultural industry and the depletion of agricultural land. It is not always possible to maintain soil fertility in a natural way - for accumulation nutrients the earth needs a long rest. The solution to the problem is to artificially fertilize the soil with chemical elements necessary for the full development of plants. In our country, this method is used with late XIX century, when production mineral fertilizers in Russia (phosphorus-based fertilizing) has acquired an industrial scale.
Before the development of the chemical industry, farmers used manure, ash, compost and other organic matter, on the basis of which modern ones are produced. The application of such fertilizers required significant labor costs, and plant nutrition began only after the decomposition of organic matter. The use of formulations with quickly digestible elements immediately gave a visible result - the yield of agricultural crops increased significantly. Positive effect from chemical fertilizing prompted scientists to conduct active research, which identified the main substances for the full development of plants - nitrogen, potassium and phosphorus. As a result, the production of mineral fertilizers in Russia (and in other countries of the world) was concentrated in these areas.
The mineral fertilizer segment accounts for a significant share of the domestic chemical complex. The gradation of production volumes of the main types of fertilizers has not changed for many years and is as follows: nitrogen fertilizers - 49%, potassium fertilizers - 33%, phosphate fertilizers - 18%. About a third of all fertilizers produced are exported, which is about 7% of the world market. Even in times of crisis, our country maintains a stable position, which is explained not only by large reserves of natural raw materials, but also by a modern production and technological base. Currently, Russia is one of the top three global exporters and satisfies the demand of many countries for nitrogen, potash and. Among the main consumers of domestic fertilizers, China and Latin American countries traditionally stand out.
Despite the overall stability, the production of mineral fertilizers in Russia did not escape the negative impact of the crisis, especially in the potash sector. The problems are associated with falling demand within the country - due to a decrease in the purchasing power of large agro-industrial complexes. The situation is saved by the export orientation of the potash sub-industry - up to 90% of the products are actively purchased by other countries. In addition, enterprises are supported by the state - the Russian government has an optimistic attitude, because the development of the global economy stimulates the growth of agriculture and maintains stable demand for mineral fertilizers. In such a situation, our country, with rich ore/gas deposits and well-established production, has every chance of becoming a world leader in the volume of production and sales of chemical fertilizers.
Modern agriculture cannot be imagined without the active use of mineral fertilizers. Thanks to them, agricultural enterprises today receive high yields, which are enough to feed an ever-urbanizing world. It is safe to say that without mineral fertilizers, food would be much more expensive, and their shortage would be a serious deterrent to the growth of the human population. That is why the production of mineral fertilizers is important industry domestic economy.
Mineral fertilizers are called inorganic substances, used to feed agricultural plants and accelerate their growth.
The nutrients contained in such fertilizers are in the form of mineral salts. Simple fertilizers contain only one element, for example, only phosphorus. Complex fertilizers contain at least two such elements.
All inorganic fertilizers are divided into phosphorus, nitrogen, potassium, complex and microfertilizers. They are obtained through complex chemical and physical reactions at chemical industry enterprises. These can be either large production complexes employing tens of thousands of workers, or relatively small workshops with several dozen or hundreds of specialists.
The soil initially contains a certain amount of all necessary for plants substances. However, their concentration is almost always extremely low and unbalanced. In other words, plants always lack one or more microelements, so development occurs more slowly.
By covering nutrient deficiencies in the soil, we are able to significantly accelerate plant growth, allowing them to reach their full potential, rather than just a fraction of it. In modern agriculture the use of fertilizers is a mandatory agrotechnical practice. Thanks to it, farmers can get higher yields from a smaller area of arable land. At the same time, progress does not stand still and the production of new mineral fertilizers, more and more advanced and effective, continues constantly.
The need to use fertilizers is explained by several key factors:
The use of fertilizers became a logical step in the development of intensive agriculture. Application practice organic fertilizers, primarily manure, dates back many thousands of years. With the development of chemistry, people began to think about the possibilities of using inorganic fertilizers, since they are more effective. The first enterprise for the production of mineral fertilizers opened in England in the first half of the 19th century. Soon the use of agrochemicals became widespread.
The main advantage of mineral fertilizers over organic ones is that they are more high efficiency. Since the minerals are in a form ready for plant nutrition and, after entering the soil, do not need to go through the decomposition stage, they begin to act much faster.
The production of fertilizers is one of the most important areas of the domestic chemical industry. Russian chemical plants not only fully satisfy the country's domestic needs for these products, but also actively export them abroad. According to statistics, more than 80% of mineral fertilizers produced in Russia are exported.
Today in our country there are more than three dozen large chemical plants and dozens of small workshops, collectively producing about 20 million tons of fertilizers per year, which is about 7% of world production. Such high figures on a global scale are explained mainly by the fact that Russia has large reserves of raw materials from which mineral fertilizers are produced - potash ores, natural gas, coke, etc.
The geography of the location of enterprises specializing in this type of production is based on the proximity of sources of raw materials. For example, the raw material for the production of nitrogen group mineral fertilizers is ammonia. It is obtained mainly from coke. For a long time, specialized divisions of metallurgical enterprises were engaged in the production of these fertilizers. The centers of such production are the cities of Chelyabinsk, Kemerovo, Lipetsk, Magnitogorsk, etc.
The development of technology has made it possible to develop another type of ammonia raw material - natural gas. Today, factories using this technology are no longer tied to production centers and can simply be located close to large gas pipelines.
There is a technology for the production of nitrogen group mineral fertilizers, which uses oil refining waste as raw materials. Such plants operate in Angarsk and Salavat.
When obtaining phosphorus compounds, enterprises are not so strongly tied to the raw material base. And taking into account the fact that phosphates in Russia are mined mainly in the Arctic, the location of enterprises far from mining sites is doubly justified: it is easier to transport raw materials to densely populated regions than to build a plant and housing for workers in the far north. The main production capacities of phosphate group fertilizers are concentrated much further south.
However, these fertilizers are also sold by metallurgical enterprises that use their own process gases as raw materials. One of the largest producers of this type is the city of Krasnouralsk.
For a long time, the production of mineral fertilizers in Russia was possible only at large giant enterprises. Constant improvement of technology in the chemical industry has changed the situation. Today, even private individuals can create a relatively small workshop for the production of inorganic fertilizers. However, there are a few key points to consider:
It should also be noted that a small fertilizer production enterprise can master only some of the most simple substances. The technology for the production of complex mineral fertilizers is still too tough for only large industrial complexes, the creation of which makes no sense to talk about here.
Today on the equipment market there are quite a lot of offers from both domestic and foreign manufacturers. It is noteworthy that domestic production lines for small enterprises producing fertilizers are practically in no way inferior to their Western counterparts. In this regard, there is no urgent need to buy more expensive imported equipment for the production of mineral fertilizers from the very beginning. On the contrary, domestic machines are even more adapted to Russian raw materials, with which they will ultimately have to work.
An important component of success when opening your own mineral fertilizer plant is the search for suppliers of raw materials. These are quite specific products that are not so easy to purchase. You should study this issue in advance and analyze everything possible options. It makes the most sense to open such a business near producers of raw materials.
Federal Agency for Education
Tver State Technical University
Department of Polymer Materials Technologies
Production of mineral fertilizers
Completed by: Tomilina O.S.
FAS, group BT-0709
Checked by: Komarov A.M.
Mineral fertilizers are salts containing elements necessary for plant nutrition and applied to the soil to obtain high and sustainable yields. Mineral fertilizers are one of the the most important species chemical industry products. Population growth poses the same problem for all countries of the world - skillful management of nature’s ability to reproduce life resources, and above all food. The problem of expanded reproduction of food products has long been solved by the use of mineral fertilizers in agriculture. Scientific forecasts and long-term plans provide for a further increase in the global production of mineral and organomineral fertilizers, fertilizers with a controlled duration.
The production of mineral fertilizers is one of the most important sub-sectors of the chemical industry, its volume worldwide is more than 100 million. t per year. The compounds produced and consumed in the greatest quantities are sodium, phosphorus, potassium, nitrogen, aluminum, iron, copper, sulfur, chlorine, fluorine, chromium, barium, etc.
Mineral fertilizers are classified according to three main characteristics: agrochemical purpose, composition and properties.
1. According to agrochemical purpose, fertilizers are divided into direct , being a source of nutrients for plants, and indirect, serving to mobilize soil nutrients by improving its physical, chemical and biological properties. Indirect fertilizers include, for example, lime fertilizers used to neutralize acidic soils.
Direct mineral fertilizers can contain one or more different nutrients.
2. Based on the amount of nutrients, fertilizers are divided into simple (single) and complex.
Simple fertilizers contain only one of the three main nutrients. Accordingly, simple fertilizers are divided into nitrogen, phosphorus and potassium.
Complex fertilizers contain two or three main nutrients. Based on the number of main nutrients, complex fertilizers are called double (for example, type NP or PK) or triple (NPK); the latter are also called complete. Fertilizers containing significant amounts of nutrients and few ballast substances are called concentrated.
Complex fertilizers are also divided into mixed and complex. Mixed are mechanical mixtures of fertilizers consisting of heterogeneous particles obtained by simple fertilizer mixing. If a fertilizer containing several nutrients results in chemical reaction in factory equipment. It's called complex.
Fertilizers intended to feed plants with elements that stimulate plant growth and are required in very small quantities are called microfertilizers, and the contents they contain nutritional elements– microelements. Such fertilizers are applied to the soil in very small quantities. These include salts containing boron, manganese, copper, zinc and other elements.
3. Based on their state of aggregation, fertilizers are divided into solid and liquid (ammonia, aqueous solutions and suspensions).
The physical properties of fertilizers are of great importance. Water-soluble fertilizer salts should be free-flowing, easy to disperse, not highly hygroscopic, and not cake during storage; must be such as to remain on the soil for some time, and not be washed away too quickly by rainwater or blown away by the wind. These requirements are best met by coarse-crystalline and granular fertilizers. Granular fertilizers can be applied to fields using mechanized methods using fertilizer machines and seeders in quantities that strictly comply with agrochemical requirements.
Phosphorus fertilizers, depending on their composition, are soluble to varying degrees in soil solutions and, therefore, are differently absorbed by plants. Based on the degree of solubility, phosphate fertilizers are divided into water-soluble, assimilated by plants, and insoluble phosphates. Water-soluble include simple and double superphosphates. To digestible ones, i.e. soluble in soil acids include precipitate, thermophosphate, fused phosphates and Thomas slag. Insoluble fertilizers contain difficult-to-digest phosphate salts that are soluble only in strong mineral acids. These include phosphate rock, apatite, and bone flour.
The raw materials for the production of elemental phosphate, phosphate fertilizers and other phosphorus compounds are natural phosphates: apatites and phosphorites. In these ores, phosphorus is in insoluble form, mainly in the form of fluorapatite Ca 5 F(PO 4) 3 or hydroxylapatite Ca 5 OH(PO 4) 3. To obtain easily digestible phosphorus fertilizers used in any soil, it is necessary to convert insoluble phosphorus salts of natural phosphates into water-soluble or easily digestible salts. This is the main task of phosphate fertilizer technology.
The solubility of phosphate salts increases as their acidity increases. The average salt Ca 3 (PO 4) 2 is soluble only in mineral acids, CaHO 4 is soluble in soil acids, and the most acidic salt CaH 2 PO 4) 2 is soluble in water. In the production of phosphate fertilizers, they strive to obtain as much of the phosphorus as possible in the form of monocalcium phosphate Ca(H 2 PO 4) 2. The conversion of insoluble natural salts into soluble ones is carried out by their decomposition with acids, alkalis, and heating (thermal sublimation of phosphorus). Simultaneously with the production of soluble salts, they strive to obtain phosphorus fertilizers with the highest possible concentration of phosphorus.
Chemical industry produces simple and double superphosphates. Simple superphosphate is the most common phosphate fertilizer. It is a gray powder (or granules) containing mainly calcium monophosphate Ca(H2PO4)2*H2O and calcium sulfate CaSO4*0.5H2O. Superphosphate contains impurities: iron and aluminum phosphates, silica, and phosphoric acid. The essence of superphosphate production is the decomposition of natural phosphates with sulfuric acid. The process of producing superphosphate by reacting sulfuric acid with calcium fluorapatite is a multiphase heterogeneous process, occurring mainly in the diffusion region. This process can be roughly divided into two stages. The first stage is the diffusion of sulfuric acid to the apatite particles, accompanied by a rapid chemical reaction on the surface of the particles, which continues until the acid is completely consumed, and the crystallization of calcium sulfate:
Ca 5 F(PO 4) 3 + 5H 2 SO 4 +2.5H 2 O=5(CaSO 4 *0.5H 2 O)+H 3 PO 4 +HF+Q (a)
The second stage is the diffusion of the formed phosphoric acid in the pores of undecomposed apatite particles, accompanied by a reaction
Ca 5 F(PO 4) 3 +7H 3 PO 4 +5H 2 O=5Ca(H 3 PO 4) 2 *H 2 O+HF+Q (b)
The resulting monocalcium phosphate is first in solution, and upon supersaturation it begins to crystallize. Reaction (a) begins immediately after displacement and ends in the superphosphate reaction chamber within 20-40 minutes during the period of setting and hardening of the superphosphate mass, which occurs due to the relatively rapid crystallization of slightly soluble calcium sulfate and recrystallization of the hemihydrate into anhydrite according to the reaction equation
2CaSO 4 *0.5H 2 O=2CaSO 4 +H 2 O
The next stage of the process is the maturation of superphosphate, i.e. the formation and crystallization of monocalcium phosphate occurs slowly and ends only in the warehouse (ripening) when the superphosphate is aged for 6-25 days. The low speed of this stage is explained by the slow diffusion of phosphoric acid through the formed monocalcium phosphate crust covering the apatite grains, and the extremely slow crystallization of the new solid phase Ca(H 2 PO 4) 2 *H 2 O.
The optimal mode in the reaction chamber is determined not only by the kinetics of reactions and diffusion of acids, but also by the structure of the formed calcium sulfate crystals, which affects the overall speed of the process and the quality of superphosphate. Diffusion processes and reactions (a) and (b) can be accelerated by increasing the initial concentration of sulfuric acid to the optimal temperature.
The slowest process is ripening. Ripening can be accelerated by cooling the superphosphate mass and evaporating water from it, which promotes crystallization of monocalcium phosphate and increases the rate of reaction (b) due to an increase in the concentration of H 3 PO 4 in the solution. To do this, superphosphate is mixed and sprayed in the warehouse. The content of P 2 O 5 in the finished superphosphate is approximately two times lower than in the initial raw material, and when processing apatites it is 19-20% P 2 O 5.
The finished superphosphate contains a certain amount of free phosphoric acid, which increases its hygroscopicity. To neutralize free acid, superphosphate is mixed with neutralizing solid additives or ammoniated, i.e. treated with ammonia gas. These measures improve the physical properties of superphosphate - they reduce humidity, hygroscopicity, caking, and during ammoniation, another nutrient element is introduced - nitrogen.
There are batch, semi-continuous and continuous methods for producing superphosphate. Currently, most operating factories implement a continuous production method. A diagram of a continuous method for producing superphosphate is shown in Fig. 1
The crushed apatite concentrate (or phosphate rock) is transferred from the warehouse to an automatic weighing dispenser by a system of conveyors and elevator screws, from which it is dosed into a continuous mixer.
Sulfuric acid (75% tower H 2 SO 4) is continuously diluted with water in a dosing mixer to a concentration of 68% H 2 SO 4, controlled by a concentrator, and fed into a mixer in which mechanical mixing of phosphate raw materials with sulfuric acid occurs. The resulting pulp from the mixer is transferred to a continuous superphosphate reaction chamber, where superphosphate is formed (setting and hardening of the pulp in initial period maturation of superphosphate mass). From the superphosphate chamber, crushed superphosphate is transferred by an under-chamber conveyor to the post-processing department - a superphosphate warehouse, over which it is evenly distributed by a spreader. To speed up the ripening of superphosphate, it is mixed in the warehouse with a grab crane. To improve the physical properties of superphosphate, it is granulated in rotating drum granulators. In granulators, powdered superphosphate is moistened with water supplied inside the drum by nozzles and “rolled” into granules various sizes, which are then dried, scattered into fractions and tared into paper bags.
The main apparatus for superphosphate production is the superphosphate chamber. It is fed with pulp from a mixer mounted directly above the chamber lid. For continuous feeding of superphosphate chambers, screw mixers and chamber mixers with mechanical mixing are used.
The disadvantage of simple superphosphate is the relatively low content of the nutrient element - no more than 20% P 2 O 5 from apatite concentrate and no more than 15% P 2 O 5 from phosphorites. More concentrated phosphorus fertilizers can be obtained by decomposing phosphate rock with phosphoric acid.
Most nitrogen fertilizers are obtained synthetically: by neutralizing acids with alkalis. The starting materials for producing nitrogen fertilizers are sulfuric and nitric acids, carbon dioxide, liquid or gaseous ammonia, calcium hydroxide, etc. Nitrogen is found in fertilizers or in the form of the NH 4 + cation, i.e. in ammonia form, in the form of NH 2 (amide), or the NO 3 - anion, i.e. in nitrate form; the fertilizer can simultaneously contain both ammonia and nitrate nitrogen. All nitrogen fertilizers are water-soluble and well absorbed by plants, but are easily carried deep into the soil during heavy rains or irrigation. A common nitrogen fertilizer is ammonium nitrate or ammonium nitrate.
Ammonium nitrate is a ballast-free fertilizer containing 35% nitrogen in ammonium and nitrate forms, so it can be used on any soil and for any crops. However, this fertilizer has physical properties unfavorable for its storage and use. Crystals and granules of ammonium nitrate spread in air or cake into large aggregates as a result of their hygroscopicity and good solubility in water. In addition, when temperature and air humidity change during storage of ammonium nitrate, polymorphic transformations can occur. To suppress polymorphic transformations and increase the strength of ammonium nitrate granules, additives introduced during its production are used - ammonium phosphates and sulfates, boric acid, magnesium nitrate, etc. The explosiveness of ammonium nitrate complicates its production, storage and transportation.
Ammonium nitrate is produced in factories that produce synthetic ammonia and nitric acid. The production process consists of the stages of neutralization of weak nitric acid with ammonia gas, evaporation of the resulting solution and granulation of ammonium nitrate. The neutralization step is based on the reaction
NH 3 +HNO 3 =NH 4 NO 3 +148.6 kJ
This chemisorption process, in which the absorption of a gas by a liquid is accompanied by a rapid chemical reaction, occurs in the diffusion region and is highly exothermic. The heat of neutralization is rationally used to evaporate water from ammonium nitrate solutions. By using high concentration nitric acid and heating the initial reagents, it is possible to directly obtain ammonium nitrate melt (concentration above 95-96% NH 4 NO 3) without the use of evaporation.
The most common schemes involve incomplete evaporation of ammonium nitrate solution due to the heat of neutralization (Fig. 2).
The bulk of the water is evaporated in a chemical reactor-neutralizer ITN (using the heat of neutralization). This reactor is a cylindrical vessel made of of stainless steel, inside which there is another cylinder into which ammonia and nitric acid are directly introduced. The inner cylinder serves as the neutralization part of the reactor (chemical reaction zone), and the annular space between the inner cylinder and the reactor body serves as the evaporation part. The resulting ammonium nitrate solution flows from the inner cylinder into the evaporation part of the reactor, where water evaporation occurs due to heat exchange between the neutralization and evaporation zones through the wall of the inner cylinder. The resulting juice steam is removed from the ITN neutralizer and is then used as a heating agent.
The sulfate-phosphate additive is dosed into nitric acid in the form of concentrated sulfuric and phosphoric acids, which are neutralized along with nitrogen ammonia in the ITN neutralizer. When neutralizing the initial nitric acid, a 58% solution of ammonium nitrate at the outlet from the ITN contains 92-93% NH 4 NO 3; this solution is sent to a pre-neutralizer, into which ammonia gas is supplied so that the solution contains an excess of ammonia (about 1 g/dm 3 free NH 3), which ensures the safety of further work with NH 4 NO 3 melt. The fully neutralized solution is concentrated in a combined plate tubular evaporator to obtain a melt containing 99.7-99.8% NH 4 NO 3 . To granulate highly concentrated ammonium nitrate, the melt is pumped by submersible pumps to the top of a granulation tower 50-55m high. Granulation is carried out by spraying the melt using cell-type acoustic vibrating granulators, which ensure a uniform granulometric composition of the product. The granules are cooled by air in a fluidized bed cooler, which consists of several successive cooling stages. Cooled granules are sprayed with surfactants in a drum with nozzles and transferred to packaging.
Due to the disadvantages of ammonium nitrate, it is advisable to manufacture complex and mixed fertilizers based on it. By mixing ammonium nitrate with limestone, ammonium sulfate, lime ammonium nitrate, ammonium sulfate nitrate, etc. are obtained. Nitrophoska can be obtained by fusing NH 4 NO 3 with phosphorus and potassium salts.
Urea (urea) ranks second among nitrogen fertilizers in terms of production volume after ammonium nitrate. The growth in urea production is due to its wide range of applications in agriculture. It has great resistance to leaching compared to other nitrogen fertilizers, i.e. less susceptible to leaching from the soil, less hygroscopic, can be used not only as fertilizer, but also as an additive to cattle feed. Urea is also widely used to produce complex fertilizers, time-controlled fertilizers, and for the production of plastics, adhesives, varnishes and coatings.
Urea CO(NH 2) 2 is a white crystalline substance containing 46.6% nitrogen. Its production is based on the reaction of ammonia with carbon dioxide
2NH 3 +CO 2 =CO(NH 2) 2 +H 2 O 
H=-110.1 kJ (1)
Thus, the raw material for the production of urea is ammonia and carbon dioxide, obtained as a by-product in the production of process gas for ammonia synthesis. Therefore, the production of urea in chemical plants is usually combined with the production of ammonia.
Reaction (1) – total; it occurs in two stages. At the first stage, carbamate synthesis occurs:
2NH 3 +CO 2 =NH 2 COONH 4 H=-125.6 kJ (2)
gas gas liquid
At the second stage, the endothermic process of water splitting off from carbamate molecules occurs, as a result of which the formation of urea occurs:
NH 2 COONH 4 = CO(NH 2) 2 + H 2 O H = 15.5 (3)
liquid liquid liquid
The reaction of ammonium carbamate formation is reversible, exothermic, and proceeds with a decrease in volume. To shift the equilibrium towards the product, it must be carried out at elevated pressure. In order for the process to proceed at a sufficiently high speed, elevated temperatures are also necessary. An increase in pressure compensates for the negative effect of high temperatures on shifting the reaction equilibrium in the opposite direction. In practice, urea synthesis is carried out at temperatures of 150-190 
C and pressure 15-20 MPa. Under these conditions, the reaction proceeds at high speed and to completion.
The decomposition of ammonium carbamate is a reversible endothermic reaction that occurs intensively in the liquid phase. To prevent crystallization of solid products in the reactor, the process must be carried out at a temperature below 98C (eutectic point for the CO(NH 2) 2 - NH 2 COONH 4 system).
More high temperatures shift the reaction equilibrium to the right and increase its rate. The maximum degree of conversion of carbamate into urea is achieved at 220C. To shift the equilibrium of this reaction, an excess of ammonia is also introduced, which binds the reaction water and removes it from the reaction sphere. However, it is still not possible to achieve complete conversion of carbamate into urea. The reaction mixture, in addition to the reaction products (urea and water), also contains ammonium carbamate and its decomposition products - ammonia and CO 2.
To fully utilize the feedstock, it is necessary to either provide for the return of unreacted ammonia and carbon dioxide, as well as ammonium carbon salts (intermediate reaction products) to the synthesis column, i.e. creating a recycle, or separating urea from the reaction mixture and sending the remaining reagents to other production facilities, for example, to the production of ammonium nitrate, i.e. carrying out the process according to an open scheme.
In a large-scale urea synthesis unit with liquid recycling and the use of a stripping process (Fig. 3), one can distinguish a high-pressure unit, a low pressure and granulation system. An aqueous solution of ammonium carbamate and ammonium carbon salts, as well as ammonia and carbon dioxide enter the lower part of the synthesis column 1 from the high-pressure carbamate condenser 4. In the synthesis column at a temperature of 170-190C and a pressure of 13-15 MPa, the formation of carbamate ends and the reaction of urea synthesis occurs . The consumption of reagents is selected so that the molar ratio of NH 3:CO 2 in the reactor is 2.8-2.9. The liquid reaction mixture (melt) from the urea synthesis column enters the stripping column 5, where it flows down through the pipes. Carbon dioxide, compressed in a compressor to a pressure of 13-15 MPa, is fed countercurrently to the melt, to which air is added to form a passivating film and reduce equipment corrosion in an amount ensuring an oxygen concentration of 0.5-0.8% in the mixture. The stripping column is heated with water steam. The vapor-gas mixture from column 5, containing fresh carbon dioxide, enters high-pressure condenser 4. Liquid ammonia is also introduced into it. It simultaneously serves as a working stream in injector 3, which supplies a solution of ammonium carbon salts from high-pressure scrubber 2 and, if necessary, part of the melt from the synthesis column to the condenser. Carbamate is formed in the condenser. The heat released during the reaction is used to produce water vapor.
Unreacted gases continuously come out of the upper part of the synthesis column and enter high-pressure scrubber 2, in which most of them condense due to water cooling, forming a solution of carbamate and ammonium-carbon salts.
The aqueous solution of urea leaving stripping column 5 contains 4-5% carbamate. For its final decomposition, the solution is throttled to a pressure of 0.3-0.6 MPa and then sent to top part distillation column 8.
The liquid phase flows in the column down the nozzle in a countercurrent to the vapor-gas mixture rising from bottom to top. NH 3 , CO 2 and water vapor come out from the top of the column. Water vapor condenses in low-pressure condenser 7, and the bulk of ammonia and carbon dioxide dissolves. The resulting solution is sent to scrubber 2. The final purification of gases emitted into the atmosphere is carried out by absorption methods.
The 70% urea solution leaving the bottom of the distillation column 8 is separated from the vapor-gas mixture and sent, after reducing the pressure to atmospheric pressure, first for evaporation and then for granulation. Before spraying the melt in the granulation tower 12, conditioning additives, for example, urea-formaldehyde resin, are added to it to obtain a non-caking fertilizer that does not deteriorate during storage.
When producing phosphate fertilizers, there is a high risk of air pollution with fluoride gases. The capture of fluoride compounds is important not only from a conservation point of view environment, but also because fluorine is a valuable raw material for the production of freons, fluoroplastic, fluorine rubber, etc. Fluorine compounds can get into wastewater at the stages of fertilizer washing and gas cleaning. To reduce the amount of such wastewater, it is advisable to create closed water circulation cycles in processes. To purify wastewater from fluoride compounds, methods of ion exchange, precipitation with iron and aluminum hydroxides, sorption on aluminum oxide, etc. can be used.
Wastewater from the production of nitrogen fertilizers containing ammonium nitrate and urea is sent for biological treatment, pre-mixed with other wastewater in such proportions that the concentration of urea does not exceed 700 mg/l, and ammonia - 65-70 mg/l.
An important task in the production of mineral fertilizers is the purification of gases from dust. The possibility of air pollution from fertilizer dust at the granulation stage is especially high. Therefore, the gas leaving the granulation towers must be subjected to dust cleaning using dry and wet methods.
A.M.
Kutepov and others.
General chemical technology: Textbook. for universities/A.M. Kutepov,
T.I. Bondareva, M.G. Berengarten - 3rd ed., revised. – M.: ICC “Akademkniga”. 2003. – 528 p.
I.P.
Mukhlenov, A.Ya. Averbukh, D.A Kuznetsov, E.S. Tumarkina,
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Mineral fertilizers are classified according to three main characteristics: agrochemical purpose, composition, properties and methods of production.
According to their agrochemical purpose, fertilizers are divided into direct, which are a source of nutrients for plants, and indirect, which serve to mobilize soil nutrients by improving its physical, chemical and biological properties. Indirect fertilizers include, for example, lime fertilizers used to neutralize acidic soils, structure-forming fertilizers that promote the aggregation of soil particles in heavy and loamy soils, etc.
Complex fertilizers contain two or three main nutrients. Based on the number of main nutrients, complex fertilizers are called double (for example, type NP or PK) and triple (NPK); the latter are also called complete. Fertilizers containing significant amounts of nutrients and few ballast substances are called concentrated.
Complex fertilizers are also divided into mixed and complex. Mixed are mechanical mixtures of fertilizers consisting of dissimilar particles obtained by simple fertilizer mixing. If a fertilizer containing several nutrients is obtained as a result of a chemical reaction in factory equipment, it is called complex.
Fertilizers intended to feed plants with elements that stimulate plant growth and are required in very small quantities are called microfertilizers, and the nutritional elements they contain are called microelements. Such fertilizers are applied to the soil in quantities measured in fractions of a kilogram or kilograms per hectare. These include salts containing boron, manganese, copper, zinc and other elements.
Based on their state of aggregation, fertilizers are divided into solid and liquid (for example, ammonia, aqueous solutions and suspensions).
2. Guided by physical chemical bases processes for producing simple and double superphosphates, justify the choice of technological mode. Give functional diagrams of production.
The essence of the production of simple superphosphate is the transformation of natural fluorine-apatite, insoluble in water and soil solutions, into soluble compounds, mainly monocalcium phosphate Ca(H 2 PO 4) 2. The decomposition process can be represented by the following summary equation:
In practice, during the production of simple superphosphate, decomposition occurs in two stages. In the first stage, about 70% of apatite reacts with sulfuric acid. In this case, phosphoric acid and calcium sulfate hemihydrate are formed:
Crystallized microcrystals of calcium sulfate form a structural network that retains a large amount of the liquid phase, and the superphosphate mass hardens. The first stage of the decomposition process begins immediately after mixing the reagents and ends within 20 - 40 minutes in superphosphate chambers.
After complete consumption of sulfuric acid, the second stage of decomposition begins, in which the remaining apatite (30%) is decomposed by phosphoric acid:
The main processes take place in the first three stages: mixing of raw materials, formation and hardening of superphosphate pulp, ripening of superphosphate in the warehouse.
Simple granular superphosphate is a cheap phosphate fertilizer. However, it has a significant drawback - low content of the main component (19 - 21% digestible) and a high proportion of ballast - calcium sulfate. It is produced, as a rule, in areas where fertilizers are consumed, since it is more economical to deliver concentrated phosphate raw materials to superphosphate plants than to transport low-concentrated simple superphosphate over long distances.
You can obtain concentrated phosphorus fertilizer by replacing sulfuric acid during the decomposition of phosphate raw materials with phosphoric acid. The production of double superphosphate is based on this principle.
Double superphosphate is a concentrated phosphorus fertilizer produced by the decomposition of natural phosphates with phosphoric acid. It contains 42 - 50% digestible, including 27 - 42% in water-soluble form, i.e. 2 - 3 times more than simple. By appearance and the phase composition of double superphosphate is similar to simple superphosphate. However, it contains almost no ballast - calcium sulfate.
Double superphosphate can be produced using a technological scheme similar to the scheme for producing simple superphosphate. This method of producing double superphosphate is called chamber method. Its disadvantages are the long-term ripening of the product, accompanied by inorganic releases of harmful fluoride compounds into the atmosphere, and the need to use concentrated phosphoric acid.
More progressive is flow method production of double superphosphate. It uses cheaper undiluted phosphoric acid. The method is completely continuous (there is no stage of long-term warehouse ripening of the product).
Simple and double superphosphates are contained in a form easily digestible by plants. However, in recent years, more attention has been paid to the production of fertilizers with an adjustable duration of action, in particular long-term ones. To obtain such fertilizers, superphosphate granules can be coated with a coating that regulates the release of nutrients. Another way is to mix double superphosphate with phosphate rock. This fertilizer contains 37 - 38%, including about half in a fast-acting water-soluble form and about half in a slow-acting form. The use of such fertilizer extends the period of its effective action in the soil.
3. Why does the technological process for producing simple superphosphate include a storage (ripening) stage in a warehouse?
The resulting monocalcium phosphate, unlike calcium sulfate, does not immediately precipitate. It gradually saturates the phosphoric acid solution and begins to crystallize as the solution becomes saturated. The reaction begins in superphosphate chambers and lasts for another 5–20 days of superphosphate storage in the warehouse. After ripening in the warehouse, the decomposition of fluorapatite is considered almost complete, although a small amount of undecomposed phosphate and free phosphoric acid still remains in the superphosphate.
4. Give a functional diagram for the production of complex NPK fertilizers.
5. Guided by the physico-chemical principles of ammonium nitrate production, justify the choice of technological mode and design of the ITN apparatus (use of neutralization heat.). Give a functional diagram of the production of ammonium nitrate.
The process of producing ammonium nitrate is based on a heterogeneous reaction between gaseous ammonia and a solution of nitric acid:
The chemical reaction occurs at high speed; in an industrial reactor it is limited by the dissolution of gas in liquid. To reduce diffusion inhibition of the process great importance has mixing of reagents.
The reaction is carried out in a continuously operating ITN apparatus (using the heat of neutralization). The reactor is a vertical cylindrical apparatus consisting of reaction and separation zones. In the reaction zone there is a glass 1, in the lower part of which there are holes for circulation of the solution. Slightly above the holes inside the glass there is a bubbler 2 for supplying ammonia gas,
above it there is a bubbler 3 for supplying nitric acid. The reaction vapor-liquid mixture exits from the top of the reaction glass. Part of the solution is removed from the ITN apparatus and enters the after-neutralizer, and the rest (circulation) goes again
down. The juice steam released from the para-liquid mixture is washed on cap plates 6 from splashes of ammonium nitrate solution and nitric acid vapor with a 20% solution of nitrate, and then with juice steam condensate. The heat of reaction is used to partially evaporate water from the reaction mixture (hence the name of the apparatus
ITN). Temperature difference in various parts the apparatus leads to more intense circulation of the reaction mixture.
The technological process for the production of ammonium nitrate includes, in addition to the stage of neutralization of nitric acid with ammonia, also the stages of evaporation of the nitrate solution, granulation of the nitrate alloy, cooling of the granules, treatment of the granules with surfactants, packaging, storage and loading of nitrate, purification of gas emissions and wastewater.
6. What measures are taken to reduce the caking of fertilizers?
An effective way to reduce caking is to treat the surface of the granules with surfactants. IN last years methods of creating various shells around granules have become widespread, which, on the one hand, protect the fertilizer from caking, on the other hand, make it possible to regulate the process of dissolution of nutrients in soil water over time, i.e., create long-term fertilizers.
7. What are the stages of the process of obtaining urea? Give a functional diagram of urea production.
Urea (urea) ranks second among nitrogen fertilizers in terms of production volume after ammonium nitrate. The growth in urea production is due to its wide range of applications in agriculture. It is more resistant to leaching compared to other nitrogen fertilizers, i.e. it is less susceptible to leaching from the soil, less hygroscopic, and can be used not only as a fertilizer, but also as an additive to cattle feed. Urea is also widely used for the production of complex fertilizers, time-controlled fertilizers, as well as for the production of plastics, adhesives, varnishes and coatings.
Urea is a white crystalline substance containing 46.6 wt. % nitrogen. His teachings are based on the reaction of ammonia with carbon dioxide:
Thus, the raw materials for the production of urea are ammonia and carbon dioxide obtained as a by-product in the production of process gas for ammonia synthesis. Therefore, the production of urea in chemical plants is usually combined with the production of ammonia.
The reaction is total; it occurs in two stages. At the first stage, urea synthesis occurs:
At the second stage, the endothermic process of water splitting off from the urea molecule occurs, as a result of which urea is formed:
The formation of ammonium carbamate is a reversible exothermic reaction that occurs with a decrease in volume. To shift the equilibrium towards the product, it must be carried out at elevated pressure. In order for the process to proceed at a sufficiently high speed, elevated temperatures are necessary. An increase in pressure compensates for the negative effect of high temperatures on shifting the equilibrium of the reaction in the opposite direction. In practice, urea synthesis occurs at temperatures of 150 – 190 0 C and pressure of 15 – 20 MPa. Under these conditions, the reaction proceeds at high speed and almost to completion.
The decomposition of ammonium urea is a reversible endothermic reaction that occurs intensively in the liquid phase. In order to prevent crystallization of solid products in the reactor, the process must be carried out at temperatures not lower than 98 0 C. Higher temperatures shift the equilibrium of the reaction to the right and increase its speed. The maximum degree of conversion of carbamide into urea is achieved at a temperature of 220 0 C. To shift the equilibrium of this reaction, the introduction of excess ammonia is also used, which, by binding reaction water, removes it from the reaction sphere. However, it is still not possible to completely convert carbamide into urea. The reaction mixture, in addition to the reaction products (urea and water), also contains ammonium carbonate and its decomposition products - ammonia and CO 2.
8. What are the main sources of environmental pollution during the production of mineral fertilizers? How to reduce gas emissions and harmful emissions from wastewater in the production of phosphate fertilizers, ammonium nitrate, and urea?
When producing phosphate fertilizers, there is a high risk of air pollution with fluoride gases. The capture of fluorine compounds is important not only from the point of view of environmental protection, but also because fluorine is a valuable raw material for the production of freons, fluoroplastics, fluorine rubber, etc. To absorb fluoride gases, absorption with water is used to form hydrofluorosilicic acid. Fluorine compounds can also enter wastewater at the stages of washing fertilizers and gas cleaning. To reduce the amount of such wastewater, it is advisable to create closed water circulation cycles in processes. To purify wastewater from fluoride compounds, methods of ion exchange, precipitation with iron and aluminum hydroxides, sorption on aluminum oxide, etc. can be used.
Wastewater from the production of nitrogen fertilizers containing ammonium nitrate and urea is sent for biological treatment, pre-mixed with other wastewater in such proportions that the concentration of urea does not exceed 700 mg/l, and ammonia - 65 - 70 mg/l.
An important task in the production of mineral fertilizers is the purification of waste gases from dust. The possibility of air pollution from fertilizer dust at the granulation stage is especially high. Therefore, the gas leaving the granulation towers must be subjected to dust cleaning using dry and wet methods.
The mineral fertilizer industry is one of the basic sectors of the Russian chemical complex. The production potential of the industry consists of over thirty specialized enterprises producing more than 13 million tons of nitrogen, potassium and phosphate fertilizers per year. Per share Russian Federation accounts for up to 6-7% of global fertilizer production. The industry produces more than 20% of the chemical complex's products in value terms, and its share in the structure of exports of the chemical industries exceeds a third. Compared to other sectors of the chemical complex, the mineral fertilizer industry looks the most prosperous. This is explained by a number of circumstances. Firstly, by the time radical economic transformations began in the country, many enterprises producing fertilizers were equipped with relatively advanced technology and equipment, which allowed them to produce products competitive on the international market. Secondly, the raw materials we have for the production of mineral fertilizers, primarily natural gas and potassium-containing ores, are distributed very contrastingly in the world: vast regions are simply deprived of them. Potash fertilizers are most in demand abroad, which provides them with a significant share (60-70%) in export volumes of fertilizer supplies. The main markets for Russian fertilizers are: Latin America and China. At the same time, the domestic demand for mineral fertilizers in our country has fallen sharply: from 1990 to 2002, the application of mineral fertilizers of all types in terms of 1 hectare of crops decreased by 40 times, but, in fairness, it should be noted that in recent years there has been a trend of some growth (for more details see Geography
No. 3/2005, p. 43-44).
The location of industry enterprises depends primarily on raw materials and consumer factors. Along with them, the distribution of nitrogen, phosphorus and potassium resources in soils plays a certain role. Nitrogen reserves in the soil increase from north to south to the forest-steppe zone, where they reach a maximum and then gradually decrease. In a similar way, soil phosphorus reserves change, with the only difference being that their maximum occurs in steppe zone. Potassium reserves in the soil are maximum in the forest zone and decrease to the south of it. At the same latitude, there are more nitrogen resources in the eastern regions than in the European part, and less phosphorus and potassium.
All mineral fertilizer production is characterized by high heat and energy intensity (the share of energy carriers in the cost of production ranges from 25 to 50%). Feedstock for production nitrogen fertilizers
(ammonium nitrate, carbamide, ammonium sulfate, etc.) - ammonia. Previously, ammonia was obtained from coke and coke oven gas, so previously the centers of its production coincided with metallurgical regions. To this day, some plants producing nitrogen fertilizers (usually small ones) are located within the country’s most important metallurgical bases: these are, first of all, Kemerovo, Cherepovets, Zarinsk, Novotroitsk, Chelyabinsk, Magnitogorsk, Lipetsk. In many of these cities there are not even specialized enterprises for the production of mineral fertilizers, and nitrogen fertilizers are produced by the metallurgical plants themselves as a by-product. IN Lately
The total operating capacity for ammonia production in Russia is about 9% of the world (the third figure in the world after China and the USA). However, the potential of enterprises is not fully used, and in terms of ammonia production, Russia ranks fourth in the world after China, the USA and India, producing approximately 6% of this type of product. The cost of produced nitrogen fertilizers depends on how efficiently ammonia production units operate. The less natural gas is consumed per ton of ammonia, the lower the costs and the higher the competitiveness.
Production phosphate fertilizers less sourcing-focused than the nitrogen subsector. Simple superphosphate (the most common phosphorus fertilizer) contains only about 2 times less soluble phosphorus compared to the feedstock. At the same time, some enterprises are located in close proximity to deposits of phosphorus raw materials - phosphorites (Voskresensk, Kingisepp). Some centers of non-ferrous metallurgy (in Russia - Krasnouralsk) are also engaged in the production of phosphate fertilizers, where the raw materials are waste gases from the metallurgical process, saturated with sulfur.
The main producers of phosphate raw materials in Russia are OJSC Apatit and Kovdorsky GOK. Both are located in the Murmansk region, beyond the Arctic Circle, which significantly increases transportation costs to fertilizer production centers, especially to Balakovo, Meleuz and Belorechensk. And if relatively high prices on the foreign market allow enterprises to carry out export activities with at least minimal profit, then for domestic consumers phosphate fertilizers are becoming less and less accessible due to high prices for ore raw materials, which today amount to 40-60% of the cost various groups fertilizers
The leaders in the production of phosphate fertilizers remain Ammophos OJSC (Cherepovets), Voskresensk Mineral Fertilizers OJSC and Acron OJSC ( Velikiy Novgorod). The level of capacity utilization in the production of phosphate fertilizers is even lower than in the production of nitrogen fertilizers. On average in Russia it barely exceeds 50%; only enterprises in Voskresensk and Veliky Novgorod operate at 80% of capacity.
Production potash fertilizers firmly tied to the only source of raw materials in Russia - the Verkhnekamsk potassium salt deposit, where two main enterprises operate: OJSC Uralkali (Berezniki) and OJSC Silvinit (Solikamsk). The main type of potash fertilizer is potassium chloride. The main part of the costs of producing enterprises falls on the extraction of potash ore, therefore, due to the very high material consumption, potash raw materials are processed on site. Unlike nitrogen and phosphorus fertilizers, the production of potash fertilizers has been steadily increasing in recent years, which is facilitated by a favorable situation on the foreign market.
A significant place in the production of fertilizers is occupied by complex mineral fertilizers (such as ammophos, diammophos, azofoska, etc.) containing two or three nutrients.
The mineral fertilizer industry is focused on producing products in granular form, convenient for transportation and consumption (base fertilizers are often mixed in different proportions before being applied to the soil).
| mineral fertilizers | Holding | Specialization |
|---|---|---|
| Enterprises within the holding | Agrokhimpromholding OJSC "Azot" (Novomoskovsk), OJSC "Minudobreniya" (Perm), OJSC "Azot" (Berezniki), JSC Kirovo-Chepetsk Chemical Plant, |
|
| JSC "Cherepovets Azot" | Phosagro Association OJSC "Apatit" (Kirovsk), JSC "Ammophos" (Cherepovets), JSC "Voskresenskie mineral fertilizers", JSC Balakovo Mineral fertilizers", |
|
| JSC "Minudobreniya" (Meleuz) | Interagroinvest | Production of potash fertilizers JSC "Silvinit" (Solikamsk), OJSC "Uralkali" (Berezniki), PA "Belaruskali" |
| (Soligorsk, Belarus) | Chemical company "Akron" | Production of nitrogen fertilizers JSC Acron (Velikiy Novgorod), JSC "Dorogobuzh" |
| (Verkhnedneprovsky) | Eurochem | Production of phosphate fertilizers JSC "Phosphorit" (Kingisepp), |
Kovdorsky GOK
| (in terms of 100% nutrients, thousand tons) | 1990 | 1995 | 1998 | 2000 | 2001 | 2002 | Region Place, Russian Federation, 2002 |
|---|---|---|---|---|---|---|---|
| Russian Federation | 15 979 | 9 639 | 9 380 | 12 213 | 13 026 | 13 562 | |
| Central Federal District | 3 363,8 | 1 487,0 | 1 391,5 | 1 968,5 | 2 138,6 | 2 227,7 | 3 |
| Belgorod region | – | – | 2,3 | 2,1 | – | – | |
| Bryansk region | 86,4 | 13,8 | 1,1 | 7,8 | 3,2 | 2,8 | 25 |
| Voronezh region | 334,3 | 190,7 | 291,9 | 518,9 | 577,5 | 591,5 | 6 |
| Kostroma region | – | – | 5,3 | 9,5 | 11,5 | 0,4 | 26 |
| Lipetsk region | 77,1 | 34,7 | 33,6 | 19,8 | 20,6 | 20,4 | 18 |
| Moscow region | 1 185,2 | 374,1 | 390,3 | 452,0 | 487,8 | 459,2 | 12 |
| Ryazan region | 19,6 | 0,4 | 0,1 | – | – | – | |
| Smolensk region | 483,2 | 368,4 | 243,4 | 369,9 | 388,4 | 475,3 | 11 |
| Tambov region | 208,4 | 21,2 | 1,2 | 23,3 | 16,8 | 0,1 | 27 |
| Tula region | 969,6 | 483,7 | 422,3 | 565,2 | 632,8 | 678,0 | 5 |
| Northwestern Federal District | 2 653,2 | 1 862,8 | 2 166,1 | 2 419,5 | 2 664,3 | 2 895,6 | 2 |
| Vologda region | 1 179,1 | 940,8 | 1 251,4 | 1 445,8 | 1 499,3 | 1 639,9 | 2 |
| Kaliningrad region | – | – | – | 36,4 | – | – | |
| Leningrad region. | 776,6 | 258,0 | 207,2 | 204,3 | 174,9 | 288,0 | 13 |
| Novgorod region | 697,5 | 664,0 | 707,5 | 733,0 | 990,1 | 967,7 | 3 |
| Southern federal district |
1 333,5 | 621,1 | 607,7 | 957,1 | 926,0 | 884,0 | 4 |
| The Republic of Dagestan | 52,6 | – | – | – | – | – | |
| Krasnodar region | 310,2 | 30,1 | 57,6 | 96,7 | 33,4 | 105,3 | 15 |
| Stavropol region | 970,7 | 591,0 | 550,1 | 860,4 | 892,6 | 778,7 | 4 |
| Volga Federal District | 7 394,5 | 4 901,5 | 4 953,1 | 6 344,9 | 6 740,8 | 6 918,1 | 1 |
| Republic of Bashkortostan | 574,7 | 287,9 | 59,5 | 353,7 | 312,4 | 223,5 | 14 |
| Republic of Tatarstan | 59,7 | 14,4 | 8,4 | 47,8 | 37,9 | 37,0 | 16 |
| Kirov region | 767,6 | 434,7 | 471,1 | 585,7 | 552,8 | 580,8 | 7 |
| Nizhny Novgorod region. | 176,2 | 28,2 | 5,9 | 10,6 | 13,1 | 11,4 | 22 |
| Orenburg region | 6,9 | 5,7 | 5,0 | 6,0 | 6,0 | 6,0 | 24 |
| Perm region | 4 269,2 | 3 254,0 | 3 940,5 | 4 359,6 | 4 888,5 | 5 093,4 | 1 |
| Samara region | 1 053,3 | 581,9 | 457,0 | 566,6 | 459,7 | 490,6 | 9 |
| Saratov region | 486,9 | 294,7 | 5,7 | 414,9 | 470,4 | 475,4 | 10 |
| Ural federal district | 398,1 | 42,7 | 42,4 | 25,3 | 26,0 | 30,9 | 6 |
| Sverdlovsk region. | 359,8 | 19,7 | 7,9 | 12,6 | 13,2 | 16,0 | 19 |
| Chelyabinsk region | 38,3 | 23,0 | 34,5 | 12,7 | 12,8 | 14,9 | 21 |
| Siberian Federal District | 835,7 | 724,3 | 219,0 | 498,0 | 530,2 | 606,1 | 5 |
| Altai region | 16,4 | 15,4 | 9,0 | 15,0 | 13,9 | 15,4 | 20 |
| Krasnoyarsk region | 22,9 | 10,0 | 16,9 | 22,1 | 15,8 | 21,6 | 17 |
| Irkutsk region | 259,0 | 288,8 | 8,1 | 10,6 | 9,1 | 6,1 | 23 |
| Kemerovo region | 537,4 | 410,1 | 185,0 | 450,3 | 491,4 | 563,0 | 8 |
According to the State Statistics Committee of the Russian Federation
