o Fertilizers are compounds given to plants to promote growth; they are usually applied

either via the soil or by foliar feeding.

o It can be organic or inorganic, it can be naturally occurring or manufactured through

natural process or chemical process.

o Fertilizers are used in the agriculture industry to improve the yield or the amount of
crop the farmers received from the acreage of land.
Early 1650’s: “philosophical dung” was produced by Johann
Glauber.

1659: Ammonium Nitrate was first discovered in Germany.

1773: Urea was developed by Friedrich Wohler.

1809: Chile saltpeter (Sodium Nitrate) deposit was discovered.

1842: John Lawes of England discovered the production of

single superphosphate (SSP)

1910: Large scale synthesis of NH3 was made possible by Fritz

Haber and Carl Bosch.

1928: Synthetic Sodium Nitrate was produced in US.

 Contributors In The Development Of
FERTILIZER INDUSTRY
❑ Justus von Liebig –contributed greatly to the enlightenment about plant nutrition and practically
boosted the practice of fertilizer application
❑ Friedrich Wohler – he discovered the urea in attempt to synthesize ammonium cyanate.
❑ Sir John Bennet Lawes – produced practical superphosphates, from the phosphates of rock and
coprolites, through experimentation.
❑ Jean Baptiste Boussingault – pointed out that the amount of nitrogen in various kind of
fertilizers are important.
❑ Carl Bosch and Fritz Haber – developed the process that enabled nitrogen to be cheaply
synthesized into ammonia.
 ROLE OF FERTILIZER

Fertilizers play an essential role in replenishing nutrients in the soil that are
used by plants each growing season.

It can increase food grain production, release marginal lands from

production; reduce environmental degradation; and reduce the risk and
uncertainty associated with the production of agricultural commodities.

It is the vital ingredient in feeding a growing global population.

 Others

35%
China
America

11% 33%
Russia
India

9% 11% Pakistan

1%
5 to 15% methane on dry weight basis
74 % hydrogen, 24 % nitrogen,
0.8% methane and O.3% argon,
on a dry weight basis.
UREA --

(NH 2 ) 2 CO
 HISTORY
Urea was the first organic
compound to be
Antoine Francois, comte de
artificially synthesized
Fourcroy and Louis
from inorganic starting
Vauquelin discovered nitrated
materials by Friedrich
crystal that are identical to
Wöhler .
Rouelle’s substance and
invented the term “urea” AgNCO + NH 4Cl → (NH 2 ) 2 CO + AgCl

1773 1817 1922

1799 1828
Urea was first discovered
in urine by the French William Prout succeeded Commercial production
chemist Hilaire Rouelle. in obtaining and started in Germany and
He obtained crystals determining the chemical then USA and UK in early
containing urea by composition of the 1930’s
evaporating it and treating substance.
it with alcohol in
successive filtrations.
A. Product Description

1. PROPERTIES OF UREA

Molecular formula (NH 2 ) 2 CO

Molecular weight 60.05 g/mol

Appearance Colorless crystal

Melting Point 132.7 ᵒC

Solubility Fairly soluble in water

Density 1323 kg/m3

 2. USES
FERTILIZER is the most common end use of urea either in solid form or in
liquid form

i. Solid urea are combined with other fertilizer materials to make

multicomponent (N-P-K) mixed fertilizer.

ii. Liquid urea can used as direct application fertilizer or mixed with other
liquid fertilizer materials.

➢ The most common direct application fertilizer is a mixture of liquid urea

and ammonium nitrate with total nitrogen content of 32%
➢ Other fertilizers containing urea are mixtures of various proportions of
urea, ammonium nitrate, ammonia with total available nitrogen content of
37-49%
B. Urea Process Chemistry

1. Formation of Ammonium Carbamate

2 NH 3 + CO 2 ⇔NH 2CO 2 NH 4
This reaction is exothermic and spontaneous, liberating 152.1 KJ/mol of heat NH 2CO 2 NH 4
at Cv or 158 to 159.5 KJ/mol at Cp.

2. Formation of Urea from Ammonium carbamate

NH2CO2 NH4 ⇔CO( NH2 )2 + H2O
The water formed in the reaction limits the formation of urea solutions to a maximum
of 76-93%
3. Effects of process variables (Temperature)

1 Dry urea is more stable

3
especially below 130ᵒC.
Decomposition product of
urea include ammonia,
biuret, cyuniric acid, and
Urea decomposes at 60ᵒC in carbon dioxide. Biuret is formed when the
an aqueous solution and the solid urea is heated above
decomposition rate 130ᵒC at atmospheric
accelerate as the pressure.
temperature rises.
2CO( NH2 )2 ⇔H2 NCONHCONH2 + NH3
C. Process Description

Figure 1. Block diagram of urea production process

 Once-Through Process
1
Partial Recycle Process
SOLUTION
PRODUCTION Total Recycle Process
• Basic gas recycle process
• Basic liquid recycle process
• Basic gas/liquid recycle process
Solution concentration

2 •
•
Crystallization and Dewatering
Evaporation
Solid Formation
SOLID UREA • Prilling
• Granulation
PRODUCTION a) Pan granulation
b) Drum granulation
Final Product Preparation
• Cooling
• Screening
• Coating
SOLUTION PRODUCTION

Figure 2. Once-through Process

SOLUTION PRODUCTION

Figure 3. Partial recycle process

SOLUTION PRODUCTION

TOTAL RECYCLE PROCESS

Three variations of the total recycle process are:

1. Decomposed carbamate process are separated

and recycled in their pure state.
2. Carbamate solution is recycled to the reactor.
3. A combination of gas/liquid recycle may occur.
SOLUTION PRODUCTION
SOLUTION PRODUCTION

Figure 4. Inventa gas recycle urea process

SOLUTION PRODUCTION
SOLUTION PRODUCTION

Figure 5. Stamicarbon CO2 Stripping urea process

SOLUTION PRODUCTION
SOLUTION PRODUCTION

Figure 6. SNAM PROGETTI Ammonia Stripping urea process

SOLID UREA PRODUCTION

The formation of urea requires critical balance

between temperature, retention time, and air
flow due to several physical characteristics;
namely, melting point, heat of crystallization,
and decomposition properties. These factors
lead to careful control and at times adaptation
of established techniques depending upon the
environment in which the material is
produced.
SOLID UREA PRODUCTION

Figure 7. Solidification of urea

Figure 8. Sketch of Pan Granulator
Figure 9. Cross section of Spherodizer
 PHYSICAL FORMS OF UREA

Prilled form Granular form

• Total nitrogen 46% min • Total nitrogen 46% min
• Biuret content 1% max • Biuret content <1%
• Moisture 0.5% max • Moisture <0.5%
• Particle size 1-2.8 mm • Particle size 2-4 mm
AMMONIUM
SULPHATE
Ammonium Sulphate is an inorganic chemical compound
which contains 21% Nitrogen in the form of ammonium
ion and 24% sulfur as sulfate ion.

It occurs naturally as the rare mineral mascagnite in

volcanic fumaroles and due to coal fires on some dumps.
 First produce as by product of the manufacture of coal in
1815 England and later from coke-oven battery gas.

1893 It’s production became important in USA.

It was first produced in India (at Jamshedpur in Jharkhand) as

1933 a by-product of the steel industry.
 It is produced using sulfuric acid as raw materials at
1941
Belagula in Karnataka (India).

Produced using gypsum as raw material at

1947
Ugyogamandal, Kerala (India).

Produced as a by product of the polymer

1974
(caprolactam) Industry at Vadodara in Gujarat (India).
PROPERTIES OF AMMONIUM SULPHATE
MOLECULAR FORMULA (NH4)2SO4

MOLECULAR WEIGHT 132.14 gm/ mole

APPEARANCE Fine white hygroscopic crystals

MELTING POINT >280°C

SOLUBILITY Soluble in water but insoluble in

alcohol, ether, acetone

DENSITY 720-1040 kg/m3

 It is used in
preparation
U of other
ammonium

S sulphate

E Used as an
Ammonium
S sulfate is used
largely as an
agricultural spray
adjuvant for water
soluble
artificial
OF insecticides,
fertilizer for
AMMONIUM herbicides, and
alkaline soil.
SULFATE fungicides.
 FOUR MANUFACTURING
PROCESSES

BY-PRODUCT GYPSUM
OF PROCESS
CAPROLACTAM

DIRECT OR
RECOVERY OF
SYNTHETIC
COKE OVEN
PROCESS
 Fertilizer manufacturing The Tennessee Valley Authority
facilities were relatively and the land grant colleges The ammoniated
small and produced changed the way fertilizers phosphate fertilizer
were produced and began to
fertilizers tailored to the promote higher analysis
products allow
soil needs of area fertilizers so that more farmers to apply more
farmers, commonly phosphate could be delivered fertilizer in one pass
within a 100-mile radius. to farmers at lower costs.

1950s
Present

1960s
Ammonium Phosphate
Molecular formula NH4H2PO4
Molecular wt 115.03 g/mole
Appearance White crystal
Melting point 190 0C
Solubility Moderately soluble in water
Density 1.803 g/mL
Two major types:
1. Monoammonium phosphate
2. Diammonium phosphate
1. Monoammonium Phosphate
Anhydrous ammonia added to liquid phosphoric
acid gives monoammonium phosphate (MAP). It
is a fertilizer or fertilizer intermediate with high
P2O5 content of about 55% and nitrogen content
11-12%.
2. Diammonium Phosphate
With more ammonia, technical grade
diammonium phosphate (DAP) containing 16 to
18% nitrogen and 20 to 21 % phosphorus (46%
P2O5) is formed.
Manufacturing Process
Uses of Ammonium Phosphate
Ammonium phosphate may be used…
… in flame-proofing, plant nutrient
solutions.
… in manufacturing of yeast, vinegar, yeast
foods, and bread improvers.
Uses of Ammonium Phosphate
Ammonium phosphate may be used…
… in buffer solutions and in analytical
chemistry
… as a fermentation agent, nourishment
agent for food grade.
Uses of Ammonium Phosphate
Ammonium phosphate may be used…
… as a fire prevention agent for fabric,
timber and paper, as well as a fire
prevention coating, and dry powder for fire
extinguisher.
Ammonium Nitrate
Molecular formula NH4NO3
Molecular wt 80.043 g/mole
Appearance White/grey crystal
Melting point 169.9 0C
Solubility Soluble in water
Density 1.725 g/mL
Ammonium Nitrate
• An inorganic compound.
• It is manufactured by a chemical reaction of
Ammonia and nitric acid under controlled
environment.
• It is manufactured and marketed in both solid
and liquid form.
History
• The first batch of ammonium
nitrate was synthesized by
German chemist Johann R.
Glauber in 1659.
• The synthesis process can be as
simple as mixing together ammonia
and nitric acid.
History
World War I
• The true explosive capabilities of ammonium nitrate were not
discovered until WWI.
• Throughout the war, ammonia synthesis plants in Germany were
converted from fertilizer production plants into plants that
created materials for bombs. They supplied the Axis country
with explosives.
• These plants used the Haber-Bosch process to form their
ammonia.
• In this process hydrogen and nitrogen were combined under
extremely high pressure to form ammonia.
Manufacturing Process
Uses
• Used as a key ingredient in the explosives for Mines,
Quarries and Infrastructure.
• Used in production of Nitrous Gases for Anesthesia
Purpose in Hospitals.
• Dyes and Chemicals.
• Metal Cladding in the engineering industry.
• Fertilizer companies use it as an interim product to
manufacturer complex fertilizers.
Other Uses
• Used in instant cold packs.
• Used in the treatment of some titanium ores.
• Used in the preparation of nitrous oxide.
• Used in survival kits mixed with zinc dust and
ammonium chloride.
• Products of AN reactions are used in air bags
used in cars.