FERTILIZERS

Assistant Professor : Dr. Muhammad Salman

Institute of Chemistry

University of Punjab
 PLANT NUTRIENTS
 Plants, like human beings and animals require food for their and
development.
 The food of plants is composed of certain chemical elements known as
plant nutrients or plant food elements.
 About 35 elements such as C, O, H, P, K, Ca, Mg, S, Mn, Mo, Cu, B, Zn,
Fe, Cl, Na, Si, Al, Co, I, Rb, Sr, Ni, Cr, As, Br, Ga, La, Li, Pb, V, Y, Zr and Se
have been regarded for nutrition of plants.
 Out of these, 17 elements have considered essential for plant growth
and development.

MAJOR PLANT NUTRIENTS:

 The primary and secondary nutrient elements are collectively known as
major plant nutrients.

MICRO-NUTRIENTS OR MINOR PLANT NUTRIENTS:

 The nutrients which are used by plants in small quantities are known as
micro-nutrients or minor plant nutrients.
 They are also known as trace elements because they are required in
trace quantities.
 e.g.; Mn, Mo, Cu, B, Zn, Fe, Cl

SOURCE OF ELEMENTS:
 The air and the soil are the sources of plant nutrients.
 From air, plants take up the principle part of its Carbon in the form of
CO2 by photosynthesis.
 From soil it derives water and various minerals. A part of CO2 is also
obtained from soil through plant roots.
 Out of 17 elements, Carbon, Hydrogen and Oxygen are provided by air
and water and remaining 14 elements are provided by soil.
 The macro-nutrients provided by soil include N, P, K, Ca, Mg and S.
 The micro-nutrients provided by soil include Mn, Mo, Cu, B, Zn, Fe, Cl.
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  About 60 elements are found in the composition of plants.
 Primarily C, O, H make up the principle part of plant matter.

IMPORTANCE OF ELEMENTS:
 N, P and K containing minerals are especially important for plant life.
These elements stimulate process of metabolism in plant cells, growth of
plants. Also increase the valuable plant contents such as starch of
potatoes, sugars of beets and proteins of grains. It also increases
resistance to Frost, Drought and diseases.

FUNCTIONS OF NITROGEN
The most important function of Nitrogen are

1. Nitrogen tends primarily to encourage above ground vegetative growth

and it imparts dark green color to the plants.
2. Nitrogen regulate the utilization of Potassium, Phosphorus and other
constituents to a considerable extent.
3. Nitrogen promotes vegetative growth and improves the quality of the
produced including Fodder, Leafy Vegetable and Food Crop.
4. Nitrogen increases the Tillering of cereal crop

ADVERSE EFFECTS OF NITROGEN

Abundant supply of Nitrogen may, however, cause some adverse effects which
include

1. In case of cereal crops the straw becomes weak and the crop very often
lodges and, straw and grain ratio is increased.
2. Excess nitrogen deteriorates the quality of some crops such as potato,
Barley and sugarcane.
3. It delays reproductive growth and may adversely affect fruit and grain
quality.

DEFICIENCY OF NITROGEN
The deficiency of Nitrogen may also cause some adverse effects which includes

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 1. The plant become yellowish or light green and remains stunted.
2. The leaves and young fruits tend to drop prematurely.
3. Nitrogen deficient plant ripens prematurely and crop gives poor yield.
4. Root growth is severely affected.
5. It delays reproductive growth, but increase profuse vegetative growth.
6. The flower bud often turns pale and shed prematurely.

FUNCTIONS OF PHOSPHORUS
The main functions if phosphorus include

1. It stimulates root development and growth in the Seedling stage hence

help to establish the Seedling quickly.
2. It enhances leaf development and encourages greater growth of shoots
and roots.
3. It enhances the development of reproductive parts and thus brings
about early maturity of crops particularly the cereals and it counteracts
the effect of excess nitrogen.
4. It develops resistance to certain diseases.

ADVERSE EFFECTS
EXCESS:
Excessive Phosphorus however may cause some adverse effects which include

1. Profuse root growth, particularly to the lateral and fibrous rootlets.

2. It develops normal growth having green leaf color.
3. It may cause trace element deficiency in some cases, particularly those
of iron and Zinc.
4. Unlike nitrogen, excess of phosphorus is not harmful.

DEFICIENCY:
A deficiency of phosphorus may cause the following important adverse effects

1. Roots and shoot growth is restricted and plant become thin and spindly.
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 2. Leaves may shed prematurely and there may be considerable delaying in
flowering and fruiting.
3. The leaves of cereal crops become dull green in color.
4. The deficiency is shown by slow growth and low yield
5. Potato tubers show rusty brown Lesions.

POTASSIUM
FUNCTIONS OF POTASSIUM
The important functions of potassium are given below

1. It is an essential element for the development of chlorophyll.

2. It increases the crop resistance to certain diseases and counteract the
adverse effects of excess nitrogen.
3. Potassium is very necessary for the production of best quality grains and
fruits.
4. Potash plays an important role in the production of quality vegetables.
5. Potassium increases the plumpness and boldness of grains and seeds.
6. Potassium acts as an enzyme activator.

ADVERSE EFFECTS
The potassium deficiency may cause the following important effects

1. Deficiency of potassium may cause chlorosis that is yellowing of leaves

and leaf scorch in the case of fruit trees.
2. Potassium deficient plants show a decreased rate of photosynthesis.
3. Potato plant shows an abnormal dark green color of foliage followed by
brownish.
4. Deficiency of Potash results in blackening of tubers and damage in
shortage and transit.

NEED FOR FERTILIZERS

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  After repeated cultivation, a stage is, however, reached when the soil
becomes less productive, if supply of nutrients is not provided.
 Thus in order to make up this deficiency, certain elements in the form of
their compounds is added to the soil to make it reproductive.
 These substances are known as fertilizer thus fertilizers are defined as

“Fertilizers are those substances which must be added to the soil in order

to remove the deficiency of Essential elements required for plant growth.”

CLASSIFICATION OF FERTILIZERS
Fertilizers are classified as

1. Direct fertilizers or indirect fertilizers

2. Simple fertilizers or double/triple fertilizers
3. Mixed fertilizers or Complex fertilizers
4. Water soluble fertilizers or water in soluble fertilizers

1. DIRECT FERTILIZER
“Those which contain the nutrient elements in the form of compounds and are
directly assimilated by plants.”

For example: Phosphatic, Nitrogenous, Potash Fertilizers

2. INDIRECT FERTILIZERS
“Those substances which are added to the soil in order to improve its chemical,
mechanical or biological properties.”

For example:

i. Ground dolomite and limestone used to decrease soil acidity.

ii. Gypsum used to improve the properties of soils with the high salt
content.

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3. SIMPLE FERTILIZERS
“Those fertilizers which contain only one nutrient element are called simple
fertilizers.”

4. DOUBLE OR TRIPLE FERTILIZERS

“The fertilizers containing two or three elements are called double or triple
fertilizers respectively.”

The triple fertilizers are also called as complete fertilizers.

5% and 6% of Nitrogen respectively.

AMMONIUM NITRATE
 Ammonium Nitrate is the most important nitrogenous fertilizers.
 Ammonium Nitrate plants are found in most of the fertilizer producing
countries of the world.
 Worldwide more than 80% of the Ammonium Nitrate is used as Fertilizer
and its minor amount is used for other purposes like for industrial
explosives.

RAW MATERIALS
All Ammonium Nitrate plants are operated in conjugation with an ammonium
plant and nitric acid plant, thus the raw materials for Ammonium Nitrate are
Ammonia and nitric acid and both of these are usually produced at the same
installation.

METHOD OF PRODUCTION
There are three important methods of producing Ammonium Nitrate these are

1. Crystallization
2. Flaking
3. Prilling

The latest and the most important method is Prilling. This method was
developed in 1940.
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 PRILLING METHOD
OPERATIONS IN PRILLING:

A modern Ammonium Nitrate Prilling plant consists of the following operations

1. NEUTRALIZATION
 Heated Ammonia vapors (obtained by Haber’s process) and 60 to 80%
nitric acid (prepared by the oxidation of ammonia) are introduced at
the base of a neutralizer tower operating under a pressure of 3-5 atm
and through which neutralized solution is recycled.
 The neutralization reaction is exothermic indicating a high yield to be
subjected to
i. Use of nitric acid of nearly 60 to 80% strength.
ii. Preheating the reactants before heating.
iii. Efficient utilization of heat of reaction for concentration
purpose.

HNO3 + NH3 NH4NO3

(83%)

∆H= -20.6 KCal

 In some plants in which low-cost steam from other sources is available
atmospheric neutralization is used.
2. EVAPORATION
 Solution obtained from the neutralizer contains about 83%
Ammonium Nitrate.
 This solution is allowed to pass through a heater supplied with
steam.
 The heated solution from the heater is then passed to a vacuum
evaporator where its concentration is increased to about 95%. 83%
solution (if left) is drawn off at this point and used in making
solution.
3. PRILLING
 The concentrated solution is now sprayed into Prilling Tower.
 The falling solution in the tower is cooled by an ascending current of air.

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  The Prilling tower are quite high up to 180 feet.
 The solution is separated through spray nozzles in such a manner that
the liquid breaks up into drops of uniform and adequate size.
 The prills solidify sufficiently as they reach the bottom of the tower.
 They must be handled carefully until they are dried.
4. DRYING AND FINISHING
 It is very difficult to dry the prills of Ammonium Nitrate because it is
deliquescent in nature.
 The drying temperature must be low to avoid melting.

METHODS OF DRYIG

Various methods of drying are available

1. 1ST METHOD:
 In this method the material is cool to below 90℉ and the remaining
moisture is removed in a second dryer. (temp.??)

UREA
 Urea or carbamide is the high quality and most valuable nitrogen
fertilizer with a 46% nitrogen content.
 It is easily assimilated by plants and can also be used directly like
nitrogen addition in livestock feeds or animal food.
 Urea is synthesized from Ammonia and carbon dioxide in 2 stages
1. The formation of Ammonium carbamate.
2NH3 + CO2 NH2COONH4
+159.1KJ

2. Dehydration of the carbamate to form a melt of urea.

NH2COONH4 NH2CONH2 +
H2O -285KJ

 The overall production of Urea is a gas liquid heterogeneous process

occurring in kinetically controlled region.

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  IN GENERAL THE MANUFACTURE INVOLVES THE FOLLOWING
STAGES
1. Chemical reaction between Ammonia and carbon dioxide.
2. Distillation of the synthesis product.
3. Processing the urea solution obtained in the distillation
operation into the end point.
 The rate of overall reaction is determined by dehydration of Ammonium
carbamate in the melt, the slowest stage.
 The equilibrium ratio and rate of Urea synthesis depends on the
temperature, pressure and chemical composition of the system.
 The rate of reaction and actual urea yield also grows rapidly with the
pressure because of increase driving forces of the process.
 In industry urea synthesis is carried out without using a catalyst at 180-
200 atm pressure and 180 to 200 ℃temperatures.
 Higher temperatures cannot be employed because they increase
corrosion of the Apparatus. 100% excess ammonia is used.
 The raw materials are the expansion gases obtained in the process of
manufacturing Ammonia (contain up to 90% carbon dioxide) and liquid
Ammonia used in 100 to 125% excess over the Stoichiometric amount.
 When using 100% carbon dioxide and absolutely pure Ammonia the urea
yield (relative to carbon dioxide) under the optimum conditions is 60 to
70% and the molten mass obtained by dehydration of carbamide
contains about 35% urea.
 Good Economics of the process and low cost of Urea can only be
achieved by using the parts of the reactants ammonia and carbon
dioxide which do not take part in the reaction.
 Thus unreacted Ammonia and carbon dioxide are generally used for
manufacturing other products.

SYNTHESIS
 Synthesis take place in a tower made of alloy steel.
 The inner cylinder of the tower acts to protect the walls of the high
Pressure Vessel against corrosion by the reaction mixture.

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  Liquid ammonia is fed to the annular spaces between the tower wall and
the inner cylinders by a pump.
 It flows along the walls, protecting them from corrosion.
 Ammonia reacts with carbon dioxide which is fed to the inside of the
cylinder at the bottom of the tower, which operates in plug flow.
 The molten urea is removed from the upper part of the tower, throttled
to atmospheric pressure and transferred to the distillation Tower, where
excess of ammonia and products of a decomposition of Ammonium
carbamate salts are stripped from the urea solution.
 The solution is concentrated in an evaporator and urea is produced
either in the form of crystals or it is granulated in prilling Tower.
 The gases discharged from the distillation Tower are regenerated.

ACTION OF UREA AS FERTILIZER

 Urea is first hydrolyzed by soil water to ammonia and carbon dioxide.
 Then nitrosification of ammonia takes place by the help of nitrosomonas
and nitrosococcus bacteria and nitrites are formed.
 Nitrification of nitrites is brought about by nitro bacteria to form nitrates
utilized by the

POTASSIUM FERTILIZERS
Potassium containing fertilizers are

1. potassium nitrate
2. Potassium Chloride
3. Potassium Sulfate

POTASSIUM CHLORIDE
 Potassium chloride is obtained by the evaporation of Olead sea Brine by
solar energy.
 During the process of evaporation, the concentration increases from
1.2% in the brine to 23% in liquid which crystallizes in the pan.
 After refining about 97% Potassium Chloride can be obtained, potassium
chloride contains about 63.17% potassium peroxide and about 52.44%
potassium Content.
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  Potassium chloride is most common potassium fertilizer having Potash in
Chloride form.
 It is sold in the market as a Muriate of potash.
 It is cheaper than all other potassium fertilizers and so it is extensively
used by the farmers and cultivators throughout the world.
 It can also be prepared by ore such as carnallite, kainite by crystallization
and floatation method.

NORMAL SUPERPHOSPHATE
 Phosphate manure can be taken up by the plants in soluble form.
 When tricalcium phosphate in the form of bone meal or Rock phosphate
powder (main source of phosphorus pentaoxide) is applied to the soil,
tricalcium phosphate is slowly converted into calcium superphosphate in
the soil and then the soluble phosphate is taken up by the plants. I
 n order to avoid the slow transformation, Rock phosphate is transferred
quickly into soluble phosphate, which is then applied to the soil.
 This artificially prepared monocalcium phosphate is known as super
phosphate, commercial superphosphate is a mixture of monocalcium
phosphate and crystalline calcium phosphate.
 It contains about 16% Phosphorus pentoxide. The soluble calcium
phosphate prepared by treating Rock phosphate with sulfuric acid is called
superphosphate.

Ca3(PO4)2 + 2H2SO4 + 2H2O Ca(H2PO4)2 +

2CaSO4.2H2O

 Also prepared from calcium Fluor-apatite with sulfuric acid.

2Ca5F(PO4)3 + 7H2SO4 + 3H2O

3Ca(H2PO4)2.3H2O + 7CaSO4 + 2HF + Heat

RAW MATERIALS
 A fairly high grade of phosphate rock is required to make superphosphate
that contains 20% available Phosphorus pentoxide.
 Rock containing 33.5% or more Phosphorus pentoxide is normally used.
Strong sulfuric acid (93-98%) is used in most plants.
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IMPORTANT POINTS
 In the manufacture of normal superphosphate, the ground phosphate
rock is fed by a weigh feeder into a double conical mixer, where it is
thoroughly mixed with calculated amount of sulfuric acid. The later is
diluted with water in the cone to the concentration of 51 Be. The heat
of dilution is utilized in heating the sulfuric acid to proper reaction
temperature and excess heat is dissipated by evaporation of extra water
added. In order to control the product moisture, the rate of water
addition and acid concentration may be varied.
 The acid and water are fed into the cone mixer tangentially in order to
provide complete mixing with the phosphate rock. The fresh
superphosphate discharges from the cone mixer to a pug mill, where
additional mixing take place and reaction starts.
 From pug mill the super phosphate drops on to the Den conveyor for
solidifying before reaching the cutter. The cutter slices the solid mass of
crude product so that it may be conveyed to pile storage for cutting or
completion of chemical reaction, which takes 10 to 20 days to reach an
acceptable Phosphorus pentoxide availability as plant food. The fumes
from the continuous Diu are Scrubed with water sprayers to remove
acid and fluoride before being exhausted to the atmosphere.
 The scrubber water is discharge to a limestone to neutralize the acid.

PROPERTIES OF SUPERPHOSPHATE
1. Superphosphate normally contains 5 to 8% moisture after curing. Low
moisture contents help in reaching the general objectives of 20%
available Phosphorus pentoxide contents.
2. Hygroscopicity is quite low; the critical relative humidity at 86 ℉ is 94%.
3. Bulk density for non-granular material ranges from about 50 to 70
pounds per cubic feet respectively.

TRIPLE SUPERPHOSPHATE

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  Triple superphosphate or concentrated super phosphate contains about 44-
47% Phosphorus pentoxide content, Which is nearly three times as high as
in normal superphosphate.
 It can be manufactured by the action of 78% phosphoric acid on finely
powdered calcium phosphate or phosphate Rock containing about 32.5 to
33% Phosphorus pentoxide content.
 The manufacturing procedure is quite similar to that of normal
superphosphate.
 The reaction mixture is allowed to stand for 3 months to make the reaction
complete.
 Then grey solid mass thus obtained is crushed to powder.

Ca3(PO4)2 + 4H3PO4
3Ca(H2PO4)2

 Triple superphosphate is essentially an impure monocalcium phosphate,

made by the following reaction

Ca10(PO4)6F2 + 14H3PO4 + 10H2O

10CaH4(PO4)2.10H2O + 2HF

“The properties of triple superphosphate depend upon the type of Rock and
acid used for production and on the granular or non granular nature of the
product.”

PREPARATION OF GRANULAR TRIPLE SUPERPHOSPHATE

Granular triple superphosphate is usually prepared by the following methods

1. WET AND DRY METHOD

 In wet and dry method, granulation is carried out by treating the crude
product with water and steam in a Rotary drum, followed by drying and
screening.
2. SLURRY GRANULATION METHOD
 In slurry granulation method, rock is mixed with relatively weak acid (38-
40% Phosphorus pentoxide) in a series of tanks.

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  The resulting slurry is then mixed with excess of dried recycled granules in
a paddle mixer called “Blunger.”
 The coated granules thus obtained are dried and screened.
3. GRANULATION METHOD
 In granulation process acid as well as granulation are carried out
simultaneously in a Rotary drum.
 Preheated acid, phosphate Rock and recycled fines are mixed in the drum
and then granulated with steam.
 The resulting product is cooled, screened and cured.

“ Properties of granular triple superphosphate depend on the type of

process by which it is manufactured.”

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