Chemical Process Technology II (Maam Kehkashan)

2012

Nitrogen Fertilizers
Nitrogen (N) is a key nutrient in manipulating plant growth. Most nursery/floral producers use large quantities of N fertilizers. Plants require N in relatively large quantities and in forms that are readily available. When N is deficient in plants restricted growth of tops and roots and especially lateral shoots may occur. Then we need Nitrogen fertilizers for the better growth of the plants. Nitrogen fertilizer is available in different forms: liquid, which must be injected into the ground, or dry pellets, which can be applied to the surface of the soil by hand or by machine.

Importance of Nitrogen Fertilizers:

Fertilizers are used to maintain the correct level of nitrogen in the soil, ensuring strong, green plants with a healthy growth rate. Nitrogen fertilizers can be used on a wide range of flora, from the household garden to commercial crops. They are currently used in one-third of the world's total crop production, including species such as maize, barley and soybean. Nitrogen fertilizers are also extensively used on commercial lawns, including a large proportion of the world's golf courses.

Types of Nitrogen Fertilizers

The types of Nitrogen Fertilizer are divided into different groups according to the manner in which the nitrogen combines with other elements.

Ammonium Nitrate

Introduction:
Ammonium nitrate is very important nitrogenous fertilizer because of its high nitrogen content (33%) and Cheapness of its manufacturing. It is Soluble in water, alcohol and NH 3. It is an explosive when mixed with combustible materials or exposed to high temperature. Ammonium nitrate is marketed in several forms, depending upon its use. Liquid ammonium nitrate may be sold as a fertilizer, generally in combination with urea. Solid ammonium nitrate may be produced in the form of prills, grains, granules, or crystals. Prills can

Prepared by: Syed Saad Ahmed | B.E 3rd Year Chemical Engineering

Chemical Process Technology II (Maam Kehkashan)

2012

be produced in either high or low density form, depending on the concentration of the melt. High density prills, granules, and crystals are used as fertilizer on the other hand grains are used solely in explosives.

Raw Material:
Following are the raw material we use in the synthesis of the ammonium nitrate: 57-60% HNO3 from oxidation-absorption tower Liquid NH3 Clay, for coating on end product to avoid explosions.

Ammonium Nitrate Synthesis:

The process of production of Ammonium Nitrate is based on the reaction of nitric acid and ammonia with principal variations in methods of producing the product in solid form as pellets, crystals or flakes. Process: Ammonium nitrate is made by reacting nitric acid (made by oxidizing ammonia) with ammonia in a stainless steel reaction vessel with agitation. NH3(g) + HNO3(aq) NH4NO3

The production process comprises three main unit operations: Neutralization Evaporation Solidification (prilling and granulation) If properly proportioned and preheated, the reaction can be run continuously to produce molten ammonium nitrate containing very little water (1-5%). Ammonium Nitrate is formed in to small spheres by dropping the reaction product through a shot tower or in to flakes by cooling it on belts or drums. The solidified spherical pellets or prills are about 1.5 mm in diameter and must be screened and dried before coating with clay. Fines and oversized material are re-dissolved and sent to the neutralizing for recycle.

Prepared by: Syed Saad Ahmed | B.E 3rd Year Chemical Engineering

Chemical Process Technology II (Maam Kehkashan)

2012

Advatanges of Ammonium Nitrate Fertilizers:

Dissociation into these the form of Ammonium (NH4+) and nitrate (NO3-) is very easy. The immediate availability of nitrate ions. Ammonium Nitrate fertilizer can be sued at any time of the year. Alterations on the soils PH are minimal. During seasons like summer, it is very applicable to use since it evaporates much slowly than other types. Storage of this fertilizer is also easy. It is relatively cheap to produce. It is not subject to losses due to volatilization.

Prepared by: Syed Saad Ahmed | B.E 3rd Year Chemical Engineering

Chemical Process Technology II (Maam Kehkashan) Disadvantages of Ammonium Nitrate Fertilizers:

2012

Ammonium nitrate is also an explosive agent. This explosive is used by mixing it with several oxidizers and fuels. It is easily available in the markets as it is a cheapest crop nourishing fertilizer so it can be misuse in mass destructive weapons. If it comes in contact with fire or high temperature level, it can explode on its own. Although decomposition point of ammonium nitrate is 400 degree Fahrenheit, it can significantly lower when it comes in contact with organic and/or inorganic impurities

Ammonium Sulfate
Introduction:
This fertilizer type comes in a white crystalline salt form. When alkaline substances are added to it ammonia is liberated. It has a weakly acid reaction. The application of ammonium sulfate fertilizer can be done before sowing, at sowing time, or even as a top-dressing to the growing crop.

Raw Material:
The raw materials for the manufacture of Ammonium Sulphate from gypsum are: Ammonia Carbon dioxide Gypsum Water

Ammonium Sulfate Synthesis:

The process converts gypsum to calcium carbonate and ammonium sulfate by allowing it to react with CO. This process contains four major units: 1) Absorption tower 2) Gypsum converter 3) Concentrator-crystallizer 4) Solid handling system In an absorption tower, ammonium carbonate, a major reactant, is formed by reacting carbon dioxide and ammonia in aqueous solution. The ammonium carbonate solution is then mixed with gypsum (CaSO4.2H20) and delivered to a gypsum conversion unit.

Prepared by: Syed Saad Ahmed | B.E 3rd Year Chemical Engineering

Chemical Process Technology II (Maam Kehkashan)

2012

In the gypsum converter, the mixture is converted to ammonium sulfate solution and calcium carbonate by the following reaction: (NH4)2CO3 + CaS04.2H20 (NH4)2SO4 + CaCO3 + 2H20 The overflow from the gypsum converter, containing all of the (NH4)2SO4 produced, will give a solution of 35% ammonium sulfate. The solution will be concentrated from 35 to about 42 to 45%. The ammonium sulfate solution should be supersaturated within a Meta stable field during the process of crystallization, in order to produce the larger crystals (particle size 1.2 to 3.3 millimeters) required for fertilizer application. The slurry with crystals from the crystallizer is centrifuged and the crystals are washed with dilute aqueous ammonia. The (NH4)2SO4 crystals are first dried then cooled in rotary type equipment. Suitable size crystals (1.2 to 3.3mm) are delivered to bulk storage.

Advantage of Ammonium Sulfate Fertilizer:

It is easy to handle It can be stored well under dry conditions. Though this fertilizer type is soluble in water, its nitrogen is not readily lost in drainage, because the ammonium ion is retained by the soil particles.

Disadvantage of Ammonium Sulfate Fertilizer:

Hardens during prolonged storage During the rainy season, it sometimes forms lumps. Ammonium sulfate may have an acidic effect on garden soil. Over time, the longcontinued use of this type of fertilizer will increase soil acidity and thus lower the yield.

Prepared by: Syed Saad Ahmed | B.E 3rd Year Chemical Engineering

Chemical Process Technology II (Maam Kehkashan)

2012

Prepared by: Syed Saad Ahmed | B.E 3rd Year Chemical Engineering

Chemical Process Technology II (Maam Kehkashan)

2012

Ammonium Sulfate Nitrate:

This fertilizer type is available as a mixture of ammonium nitrate and ammonium sulfate. It is recognizable as a white crystal or as dirty-white granules. This fertilizer contains 26% nitrogen, three-fourths of it in the ammonium form and the remainder (i.e. 6.5%) as nitrate nitrogen. Ammonium sulfate nitrate is non-explosive, readily soluble in water and is very quick-acting. Because this type of fertilizer keeps well, it is very useful for all crops. Though it can also render garden soil acidic, the acidifying effect is only one-half of that of ammonium sulfate on garden soil. Application of this fertilizer type can be done before sowing, at sowing time or as a topdressing, but it should not be applied along the seed.

Urea
Introduction:
Urea is an organic compound with the chemical formula (NH2)2CO. It is of great importance to the agriculture industry as a nitrogen-rich fertilizer. Synthetic urea: It was the first organic compound to be artificially synthesized from inorganic starting materials, in 1828 by Friedrich Whler, who prepared it by the reaction of potassium cyanate with ammonium sulfate. In past urea was not considered as a chemical for agricultural and industrial use. Within the 20th century it was found to be a by far the best nitrogenic fertilizer for the plants and became widely used as a fertilizer. Urea can be produced as prills, granules, flakes, pellets, crystals, and solutions. Urea has the highest nitrogen content of all solid nitrogenous fertilizers. It is highly soluble in water.

Raw Material:
Urea is commercially produced from two raw materials, ammonia, and carbon dioxide. Large quantities of carbon dioxide are produced during the manufacture of ammonia from coal or from hydrocarbons such as natural gas and petroleum-derived raw materials. Ammonia: Ammonia (NH3) is a comparatively stable, colourless gas at ordinary temperatures. Ammonia gas is lighter than air. Ammonia can be highly toxic to a wide range of organisms. In humans, the greatest risk is from inhalation of ammonia vapour, with effects including irritation and corrosive damage to skin, eyes and respiratory tracts. Ammonia is highly soluble in water, although solubility decreases rapidly with increased temperature. Ammonia reacts with water in a reversible reaction to produce ammonium (NH4) + and hydroxide (OH)- ions. Ammonia is a

Prepared by: Syed Saad Ahmed | B.E 3rd Year Chemical Engineering

Chemical Process Technology II (Maam Kehkashan)

2012

weak base. The formation of hydroxide ions in this reaction increases the pH of the water, forming an alkaline solution. About 85% of the ammonia produced worldwide is used for nitrogen fertilizers. Carbon Dioxide: CO2 is an odourless and colourless gas which contains 0.03% in the atmosphere. It is emitted as a pollutant from number of industries. CO2 can be obtained from ammonia production process as a byproduct.

Urea Synthesis:
Urea is made from ammonia and carbon dioxide. The production of Urea takes place in an equilibrium reaction, with incomplete conversion of the reactants. Unconverted reactants can be used for the manufacture of other products, for example ammonium nitrate or sulfate, or they can be recycled for complete conversion to urea in a total recycle process. Process: The ammonia and carbon dioxide are fed into the reactor at high pressure and temperature, and the urea is formed in a two step reaction. The first reaction is exothermic: 2NH3 + CO2 NH2COONH4 (ammonium carbamate)

Whereas the second reaction is endothermic: NH2COONH4 H2O + NH2CONH2 (urea)

Both reactions combined are exothermic. The urea contains unreacted NH3 and CO2 and ammonium carbamate. As the pressure is reduced and heat applied the NH2COONH4 decomposes to NH3 and CO2. The ammonia and carbon dioxide are recycled. The urea solution is then concentrated to give 99.6% w/w molten urea, and granulated for use as fertilizer and chemical feedstock. Urea is used as a nitrogen-release fertilizer, as it hydrolyses back to ammonia and carbon dioxide. In the past decade urea has surpassed and nearly replaced ammonium nitrate as a fertilizer.

Prepared by: Syed Saad Ahmed | B.E 3rd Year Chemical Engineering

Chemical Process Technology II (Maam Kehkashan)

2012

Advantages of Urea Fertilizer:

Urea production cost is relatively low. Urea can be applied to soil as a solid or solution or to certain crops as a foliar spray. Urea usage involves little or no fire or explosion hazard. Urea's high analysis, 46% N, helps reduce handling, storage and transportation costs over other dry N forms. Urea manufacture releases few pollutants to the environment. Urea, when properly applied, results in crop yield increases equal to other forms of nitrogen.

Disadvantages of Urea Fertilizer:

Urea Fertilizer releases harmful pollutants (several poisonous gasses) during its manufacturing process. It exerts higher concentrations of ammonia in the soil making it even more acidic and thus retards the soil of its natural fertility. Urea contains impurities more than 2%, it cannot be used as a fertilizer, since the impurities are toxic to certain crops, particularly citrus. Urea is very soluble in water, and hygroscopic water; hygroscopic water creates a thin layer surrounding individual soil particles, which makes water unavailable to plants, and hence requires better packaging quality.

Prepared by: Syed Saad Ahmed | B.E 3rd Year Chemical Engineering

Chemical Process Technology II (Maam Kehkashan)

2012

Ammonia:
This fertilizer type is a gas that is made up of about 80% of nitrogen and comes in a liquid form as well because under the right conditions of temperature and pressure, ammonia becomes liquid (anhydrous ammonia). Another form, aqueous ammonia, results from the absorption of ammonia gas into water, in which it is soluble. Ammonia is used as a fertilizer in both forms. The anhydrous liquid form of ammonia can be applied by introducing it into irrigation water, or directly into the soil from special containers.

Sodium Nitrate:
Sodium nitrates are also known as Chilean Nitrate. The nitrogen contained in sodium nitrate is refined to 16%. This means that the nitrogen is immediately available to plants and is a valuable source of nitrogen in this type of fertilizer. When one makes a soil amendment using sodium nitrates as a type of fertilizer in the garden, it is usually as a top- and side-dressing. Particularly when nursing young plants and garden vegetables. Sodium nitrate is quite useful as a type of fertilizer in an acidic soil. However, the excess use of sodium nitrate may cause de-flocculation.

Ammonium Chloride:
This fertilizer type comes in a white crystalline compound, which has a good physical condition and 26% ammoniac nitrogen. It is not recommended to use this type of fertilizer on crops such as tomatoes because the chlorine may harm the crop.

Prepared by: Syed Saad Ahmed | B.E 3rd Year Chemical Engineering