CHAPTER I

INTRODUCTION

Urea is an oraganic compound with the chemical formula (NH 2)2CO. Urea is
also known by the International Nonproprietary Name (INN) carbamide, as
established by the World Health Organization. Other names include
carbamide resin, isourea, carbonyl diamide, and carbonyldiamine.

Synthetic urea
It was the first organic compound to be artificially synthesized from
inorganic starting materials, in 1828 by Friedrich Wöhler, who prepared it by
the reaction of potassium cyanate with ammonium sulfate. Although Wöhler
was attempting to prepare ammonium cyanate, by forming urea, he
inadvertently discredited vitalism, the theory that the chemicals of living
organisms are fundamentally different from inanimate matter, thus starting the
discipline of organic chemistry. This artificial urea synthesis was mainly relevant
to human health because of urea cycle in human beings. Urea was discovered;
synthesis in human liver in order to expel excess nitrogen from the body. So 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 was the leading
nitrogen fertilizer worldwide in the 1990s.Apart from that urea is being utilized in
many other industries. Urea is produced on a scale of some 100,000,000 tons per
year worldwide. For use in industry, urea is produced from synthetic ammonia
and carbon dioxide. Urea can be produced as prills, granules, flakes, pellets,
crystals, and solutions.More than 90% of world production is destined for use
as a fertilizer. Urea has the highest nitrogen content of all solid nitrogenous
fertilizers in common use (46.7%). Therefore, it has the lowest transportation
costs per unit of nitrogen nutrient.
Commercial production of urea
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. This allows direct synthesis of urea from these raw
materials. The production of urea from ammonia and carbon dioxide takes place
in an equilibrium reaction, with incomplete conversion of the reactants. The
various urea processes are characterized by the conditions under which urea
formation takes place and the way in which unconverted reactants are
further processed. 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. Two principal
reactions take place in the formation of urea from ammonia and carbon dioxide.
The first reaction is exothermic:
2 NH3 + CO2 ↔ H2N-COONH4 (ammonium carbamate)
Whereas the second reaction is endothermic:
H2N-COONH4 ↔ (NH2)2CO + H2O
Both reactions combined are exothermic.
Properties of urea
Mol. Formula - NH2CO N
Melting Point - 132.60C
Sp. Gravity - 1.335@200C
Heat of Fusion - 57.08 Cal/gm
Heat of Combustion - 2531 Cal/gm
Crystal Form - Tetragonal
Nitrogen Content - 46.6%
Boiling Point - Decompose on boiling
Colour -White
 Bulk Density - 740 to 750 kg/m3
Angle of Repose - 23 to 300C
Viscosity - 2.58@132.70C
Triple point - 1020C
Dielectric Constant - 3.52 to 0.2
Sp. Heat - 0.42Kcal/cm2
Raw materials of urea manufacturing
1. Ammonia
Ammonia, NH3, is a comparatively stable, colorless gas at ordinary temperatures,
with a boiling point of -33 C. Ammonia gas is lighter than air, with a density of
approximately 0.6 times that of air at the same temperature. 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, as shown in
equation. Ammonia is a weak base, and at room temperature only about 1 in 200
molecules are present in the ammonium form (NH4)+. The formation of
hydroxide ions in this reaction increases the pH of the water, forming an alkaline
solution.
NH3 + H2O (NH4)+ + OH-
.

Ammonia Production
Essentially all the processes employed for ammonia synthesis are variations of
the Haber-Bosch process, developed in Germany from 1904-1913. This
process involves the reaction of hydrogen and nitrogen under high temperatures
and pressures with an iron based
catalyst.
N2 +3 H2 2 NH3
The source of nitrogen is always air. Hydrogen can be derived from a number of
raw materials including water, hydrocarbons from crude oil refining, coal, and
most commonly natural gas. Hydrogen rich reformer off-gases from oil refineries
have also been used as a source of hydrogen. Steam reforming is generally
employed for the production of hydrogen from these raw materials. This process
also generates carbon dioxide, which can then be used as a raw material in the
production of urea.
Ammonia storage
Anhydrous ammonia is usually stored as a liquid in refrigerated tanks at -33.3 C
and atmospheric pressure, often in doubled-walled tanks with the capacity for
hundreds or thousands of tonnes. The low temperature is usually maintained by
the venting of ammonia gas.
2. Carbon Dioxide
CO2 is a odorless and colorless gas which contain 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 by product.
Applications of urea
1. Agricultural use
More than 90% of world production is destined for use as a fertilizer. Urea is used
as a nitrogen-release fertilizer, as it hydrolyses back to ammonia and carbon
dioxide, but its most common impurity, biuret, must be present at less than 2%,
as it impairs plant growth. Urea has the highest nitrogen content of all solid
nitrogeneous fertilizers in common use (46.4%N.) It therefore has the lowest
transportation costs per unit of nitrogen nutrient. In the past decade urea has
surpassed and nearly replaced ammonium nitrate as a fertilizer . The ammonium
form is better retained in the soil by the clay materials than the nitrate form and is
therefore less subject to leaching. Urea is highly soluble in water and is therefore
also very suitable for use in fertilizer solutions, e.g. in “foliar feed‟ fertilizers.
2. Industrial use
Urea has the ability to form 'loose compounds', called clathrates, with many
organic compounds. The organic compounds are held in channels formed by
interpenetrating helices comprising of hydrogen-bonded urea molecules. This
behaviour can be used to separate mixtures, and has been used in the
production of aviation fuel and lubricating oils. As the helices are interconnected,
all helices in a crystal must have the same 'handedness'. This is determined
when the crystal is nucleated and can thus be forced by seeding. This property
has been used to separate racemic mixtures.
3. Medical use
Urea is used in topical dermatological products to promote rehydration of the
skin. If covered by an occlusive dressing, 40% urea preparations may also be
used for nonsurgical debridement of nails. This drug is also used as an earwax
removal aid. Like saline, urea injection is used to perform abortions. It is also the
main component of an alternative medicinal treatment referred to as urine
therapy.
4. Textile use
Urea is a raw material for urea-formaldehyde resins production in the adhesives
and textile industries. A significant portion of urea production is used in the
preparation of urea- formaldehyde resins. These synthetic resins are used in the
manufacture of adhesives, moulding powders, varnishes and foams. They are
also used for impregnating paper, textiles and leather. In textile laboratories they
are frequently used both in dyeing and printing as an important auxiliary, which
provides solubility to the bath and retains some moisture required for the dyeing
or printing process.
 CHAPTER II
REVIEW OF RELATED LITERATURE

The agricultural industry widely uses urea, a white crystalline solid containing 46
percent nitrogen as an animal feed additive and fertilizer. Here, we’ll focus on its
role as a nitrogen fertilizer.
In the past decade, urea has surpassed and nearly replaced ammonium nitrate
as a fertilizer. This has brought up new questions about urea and how to use it.
Fertilizers
Fertilizers are substances containing the chemical elements that improve growth
and productivity of plants. It is derived from a plant or animal residue or byproduct
or natural material deposit which has been processed in such a way that its
content of plant nutrients has not been materially changed except by purification
and concentration, , defines fertilizers as inorganic or organic plant food in solid or
liquid forms that can be applied to soil in order to improve the quality and/or
quantity of crops produced. They enhance soil fertility thus the ability of the soil to
provide plant nutrients and resources that support growth, by increasing plant
nutrients during the cycle. Crooke, (1972), pointed out that fertilizers have the
ability to reduce the cost of production since they can raise yield with marginal
increase in total cost per hectare.
Although fertilizers provide nutrients to crops, they can contain elements, such as
heavy metals, that are potentially harmful for the environment. They can be a
major source of non-point pollution in soil and water. Eutrophication, NO3
contamination of ground water, and the accumulation of heavy metals in soil and
their release to waters, together with their potential bioaccumulation in the food
chain, are among the main problems mentioned by (Shokeri, 2008).
Due to increasing concern regarding environmental problems related to
fertilizers, previous agricultural production research aimed at optimizing fertilizer
Kinds and nutrient composition of fertilizer
There are two broad groups of fertilizers: (1) inorganic fertilizers and (2) organic
fertilizers. And the nutrients in fertilizers can be grouped into two categories.
These are the macro- and micronutrients. These nutrients promote plant growth
(Bary, Cogger, & Sullivan, 2004).
Macronutrients
Nitrogen (N) promotes rapid growth, increase leaf size and encourages shoots
growth. It is a component of chlorophyll, and gives plant their greenness. If there
is too little nitrogen, plants become stunted and pale. If plants are overdosed with
nitrogen, they will grow too fast and become soft and sappy - an invitation to
pests. Phosphorus (P) or phosphate encourages seed germination and early
growth, stimulates blooming, enhances bud set, aids in seed formation and
hastens maturity. Only small quantities are needed. A deficiency in phosphate
shows as stunted growth. Potassium (K) or potash is associated with the size and
quality of fruit and flowers. It toughens up plants and protects them from pests
and diseases and its deficiency shows as small flowers and fruits and yellowing
or browning of the leaves. Magnesium (Mg) is another greening agent and an
activator of many plant enzyme required in growth processes. A deficiency shows
as chlorosis, which is yellowing of the leaves starting between the veins. It is
easily remedied by adding organic matter to the soil.

Calcium (Ca) is a structural nutrient, it is an essential part in cell walls and

membranes and helps to manufacture protein. Sulphur (S) is necessary for
protein synthesis and also helps to form chlorophyll. Lack of sulphur is unusual
where the soil is rich in organic matter (Jokella, Magdoff, Bartlett, Bosworth, &
Ross, 2004).
Micronutrients
Micronutrients are mostly needed in minute quantities. Manganese (Mn) helps
make chlorophyll and protein and acts as an activator for enzymes in plant growth
process. A deficiency in Mn shows as stunting and yellowing of new leaves. Iron
(Fe) serves as an activator for biological processes, such as respiration,
photosynthesis, and symbiotic nitrogen fixation. Only the tiniest quantities of iron
are needed. Iron deficiencies are most likely happen on chalky soils. Symptoms
of lack of iron are pale leaves with brown edges and margins. Zinc (Zn) controls
the synthesis of indole acetic acid, an important plant growth regulator. Copper
(Cu) aids in the activation of numerous plant enzymes and plays a role in the
development of plant pigments that influence color. Boron (B) is an important
element for growing plant tissues. A lack of boron could cause ‘corkiness’ in fruit
and vegetables. Molybdenum (Mb) is required by plants for the utilization of
nitrogen. Oxygen, carbon and hydrogen are taken up from sunlight, air and water
.
Inorganic fertilizer: Definition, advantages and disadvantages
Inorganic fertilizers are fertilizers made artificially by chemical reactions. It is a
fertilizer material which does not have carbon as the essential component of its
basic chemical structure (Meister, 2002). They are specifically designed to feed a
plant a certain amount of specific nutrients. Listed in Table 2.1 are common
inorganic fertilizers. These fertilizers are extensively consumed by most of the
farmers because it is widely available in the market.
Integrated use of organic and inorganic fertilizers for nutrient management
Because inorganic fertilizer used in intensive agriculture is not sustainable and
utilization of organic fertilizer alone is not enough in maintaining high yield,
technological options are needed according to Rola, (2004). Hence, farmers often
apply organic and inorganic fertilizer in combined (Law-Ogbomo, Remison, &
Jombo, 2011).
Integrated nutrient management or the combined use of organic and inorganic
fertilizer has been proven to be a sound soil fertility management strategy and
found to be promising in maintaining stability in crop production in certain soils
(Rola, 2004). Several researchers have demonstrated the beneficial effect of
combined use of chemical and organic fertilizers to mitigate the deficiency of
many secondary and micronutrients in fields that continuously received only N, P,
and K fertilizers for a few years, without any micronutrient or organic fertilizer.
Hernandez, Chocano, Moreno, & Garcia, (2014) also added that the combined
use of compost and inorganic fertilizer, however produced higher yields and
better fruit quality than soils that underwent the respective inorganic treatment
when used alone. The conjunctive use of compost and inorganic fertilizer made it
possible to reduce inorganic fertilization by about 40% while obtaining similar fruit
quality and amounts in addition to improving soil characteristics. Thus, Cuevas,
(1989) recommended a combined use of one-half organic and one-half inorganic
fertilize