Introduction to

fertiliser
Rushil Bhatt
• A fertilizer is a material that furnishes one or more of the
chemical elements necessary for the proper development
and growth of plants.
• The most important fertilizers are fertilizer products (also
called chemical or mineral fertilizers), manures, and plant
residues.
• A fertilizer product is a material produced by industrial
processes with the specific purpose of being used as a
fertilizer.
• Fertilizers are essential in today’s agricultural system to
replace the elements extracted from the soil in the form of
food and other agricultural products.
• Plant Nutrients: Chemical elements that are essential for
the proper development and growth of plants are typically
referred to as plant nutrients.
• Many countries express quantities or percentages of the
primary nutrients in terms of elemental nitrogen (N),
phosphorus pen oxide (P2O5), and potassium oxide (K2O2).
• Secondary nutrients and micronutrients usually are
expressed on an elemental basis although calcium and
magnesium sometimes are expressed in the oxide form.
• However, several countries express all plant nutrients on an
elemental basis.
1.Macronutrients: used in large quantities by the plant
1. Structural nutrients: C, H, O
2. Primary nutrients: N, P, K
3. Secondary nutrients: Ca, Mg, S
2.Micronutrients: used in small quantities by the plant
1. Fe, B, Cu, Cl, Mn, Mo, Zn, Co, Ni
• Some of these elements are utilized within the physical plant structure,
namely carbon (C), hydrogen (H), and oxygen (O).
• These elements, obtained from the air (CO2) and water (H2O), are the basis for
carbohydrates such as sugars and starch, which provide the strength of cell walls,
stems, and leaves, and are also sources of energy for the plant and organisms that
consume the plant.
• Elements used in large quantities by the plant are termed macronutrients, which can
be further defined as primary or secondary.
• The primary nutrients include nitrogen (N), phosphorus (P), and potassium (K).
These elements contribute to plant nutrient content, function of plant enzymes and
biochemical processes, and integrity of plant cells. Deficiency of these nutrients
contributes to reduced plant growth, health, and yield; thus they are the three most
important nutrients supplied by fertilizers.
• The secondary nutrients include calcium (Ca), magnesium (Mg), and sulfur (S).
• The final essential elements are used in small quantities by the plant, but
nevertheless are necessary for plant survival. These micronutrients include iron
(Fe), boron (B), copper (Cu), chlorine (Cl), Manganese (Mn), molybdenum (Mo), zinc
(Zn), cobalt (Co), and nickel (Ni).
 Terminology and Definitions
• The below specified definitions are those given by International
Association for Standardization (ISO) and Association of
American Plant Food Control Officials (AAPFCO)
• Fertilizer Material- A fertilizer that meets any of the following
conditions (AAPFCO):
• 1. Contains important quantities of no more than one of the
primary plant nutrients (nitrogen, phosphorus, or potassium).
• 2. Has 85% or more of its plant nutrient content present in the
form of a single chemical compound
• 3. Is derived from a plant or animal residue or by product 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.
• Soil Conditioner – Material added to soils, the main function of which is
to improve their physical and/ or chemical properties and/ or their
biological activity.
• Liming Material – An inorganic soil conditioner containing one or both of
the elements calcium and magnesium, generally in the form of an oxide,
hydroxide, or carbonate, principally intended to maintain or raise the pH
of soil.
• Straight Fertilizer: A qualification generally given to a nitrogenous,
phosphatic, or potassic fertilizer having a declarable content of only one
of the primary plant nutrients, i.e. nitrogen, phosphorus, or potassium.
• Compound Fertilizer: A fertilizer that has a declarable content of at
least two of the plant nutrients nitrogen, phosphorus and potassium,
obtained chemically or by blending or both.
• Granular Fertilizer:– Solid material that is formed into particles of a
predetermined mean size. (%N, P2O5,K2O) eg: 5-10-5
• Coated Fertilizer – Granular fertilizer that is covered with a thin of a
different material in order to improve the behavior and/ or modify the
characteristics of the fertilizer.
• Coated Slow-Release Fertilizer- A product containing
sources of watersoluble nutrients, release of which in the soil
is controlled by a coating applied to the fertilizer.
• Polymer-Coated Fertilizer -A coated slow-release fertilizer
consisting of fertilizer particles coated with a polymer (plastic)
resin. It is a source of slowly available plant nutrients.
• Controlled-Release Fertilizers- Fertilizers in which one or
more of the nutrients have limited solubility in the soil
solution, so that they become available to thea growing plant
over a controlled period.
• Nitrogen Stabilizer - A substance added to a fertilizer to
extend the time that the nitrogen component of the fertilizer
remains in the soil in the ammonia cal form.
• Liquid Fertilizer – A term used for fertilizers in suspension or
solution and for liquefied ammonia
• Solution Fertilizers– Liquid fertilizer free of solid particles.
• Suspension Fertilizer– A two-phase fertilizer in which solid
particles are maintained in suspension in the aqueous phase.
– A fluid containing dissolved and undissolved plant nutrients. The
suspension of the undissolved plant nutrients may be inherent
with the materials or produced with the aid of a suspending agent
of nonfertilizer properties. Mechanical agitation may be necessary
in some cases to facilitate uniform suspension of undissolved plant
nutrients.
– A liquid (fluid) fertilizer containing solids held in suspension, for
example, by the addition of a small amount of clay. The solids may
be water-soluble in a saturated solution, or they may be insoluble,
or both.
Slurry Fertilizer -A fluid mixture that contains dissolved and
undissolved plant nutrient materials and requires continuous
mechanical agitation to assure homogeneity
 Fundamentals of N, P and K
• Soil factors that affect the plant availability of the primary or
fertilizer nutrients (N, P and K) are quite complex, and
different from one another.
• The available forms, mechanisms of becoming plant available,
forms of stored nutrients in soils, and timing of plant uptake
are different not only between the nutrients but also for
individual fertilizer sources of each nutrient.
• A basic understanding of the reaction of nutrients in soils and
the factors that affect the response of crops to fertilizers is
essential for people in the fertilizer industry so that they can
make informed production and marketing decisions based on
what can increase the profit from using fertilizers.
 NE
Soil Nitrogen
• Nitrogen is a component of amino acids, which make up proteins, chlorophyll
(the molecule that captures the sun’s energy), enzymes, and the genetic
material, nucleic acids.
• Therefore, this nutrient is needed in large amounts by all plants.
• Plants that do not have adequate N are yellowish, have yellowing and
browning older leaves, are stunted and have poor root systems.
• Without additions of N, the nutrients are practically uniformly deficient for all
grasses and cultivated crops.
• The only exceptions are leguminous crops that have symbiotic bacterial
colonies growing within the plant, which have the ability to meet N needs
through fixation of atmospheric N2
• Excess N can cause excessive vegetative growth, delayed maturity, and stalk
breakage in small grains.
• The other macronutrients do not have direct detrimental effects
when applied to excess.
• The availability of N to plants is largely controlled by soil
microbial processes. NE
• The N cycle in soils is complex, and under certain conditions
large amounts of plant available N can be lost from the soil
in drainage water or to the atmosphere.
• In this way, N is different from the other nutrients,
which are not as readily lost from soils.
• The rates of conversion between forms of N and the direction
(immobilization and mineralization) depend principally on
the growth conditions of the microorganisms, i.e.,
temperature, moisture, oxygen availability and composition
of organic substrates etc, rather than simply abiotic
reactions
• Nitrogen uptake depends on the relatively small amount of available N
forms in soil solution the soil’s ability to replenish the available forms, and
the growth conditions for the plant. NE
• Of course, any condition that inhibits plant growth such as other nutrient
deficiencies, poor rooting conditions, poor weather, etc., will reduces N
uptake.
• Nitrate (NO3-) is the main form of N available to upland crops, whereas
ammonium (NH4+) is the main form taken up by plants growing under
flooded conditions, notably rice.
• Nitrate moves through soils with the soil water, since soils have little anion-
absorbing capacity.
• Therefore, NO3- can move with water to plant roots for uptake.
• Nitrate is also eligible for leaching into groundwater.
• To reduce NO3- pollution, it is therefore important that the amount of NO3-
stored in the soil be minimized during periods in which water percolates
through the soil.
• Fertilizer N applications can be made more efficient by applying the N
before it is needed by the crop
• Nitrate-N is also subject to loss from the soil through microbial
processes when soils become highly anaerobic due to water
saturation, which inhibits oxygen movement. NE
• When soils become anaerobic, certain microbes use NO3- as a
terminal election acceptor, and the NO3- is converted to N2 and
N2o, forms of N that cannot be used by plants.
• This loss of plant available N, called denitrification, therefore
precludes NO3- use in flooded rice culture.
• When soils are flooded to grow rice, the NO3- accumulated from
organic matter transformations during the period of dry season
fallow is lost through denitrification.
• Upland soils, which become very wet for a week or more because of
poor internal drainage or weather conditions, can lose NO3- through
denitrification, particularly if there is readily degradable organic
material in the soil.
• The organic material causes O2 to be consumed more rapidly and
provides growth substances for the denitrification organisms.
• While the denitrification process is lamented by agronomists
as a loss of plant available N from the soil system, it is the
only way that N is recycled back to the atmosphere as N2.
• Without this process, lower soil layers and ground waters
would become large reservoirs of NO3- and the oxygen-
enriched atmosphere would support continual conflagrations
and thus, make life difficult.
• Therefore, the N cycle is just as important as the carbon and
the hydrologic cycles to the life support system of the earth.
NE
NE
• Ammonium N is a plant available from in addition to NO3-, but
in normal upland soils it is converted fairly rapidly to NO3- by a
series of microbial reactions collectively called nitrification.
• Most NH4+ fertilizers are converted to NO3- within a few
weeks, but this period can vary with soil temperature, moisture,
O2 availability, soil pH, and the manner in which NH4+ or NH3
was applied.
• Soils of less than 5.0 nitrify more slowly than more neutral soils.
• Concentrated zones of NH4+ can also reduce the rate of its
conversion to NO3- As a cation, NH4+ can be absorbed onto
cation exchange sites and is therefore normally not subject to
leaching as is NO3-.
• In addition, NH4+ can move into the interior of clay lattice
structures and be protected NEfrom nitrification or plant uptake;
this is called ammonium fixation.
• N in organic forms is the major storehouse of N in soils and
since the biological conversions occur fairly rapidly, plants
rely mainly on N derived from organic material to meet their
N needs.
• When NH4+ and NO3- are added to soils, the soil
microorganisms make the major decisions as to what
happens to the N, that is, whether the N is put into the
organic N pool by their assimilation of the N or is converted
to other forms of N either usable or unusable by plants.
• When a carbonaceous material, for instance straw, is added
to soils, NO3- or NH4+ (termed mineral N) will be used by
the microbes to utilize the carbon energy source, and there
will be bet immobilization or incorporation of the plant
available N into unavailable
NE organic forms.
• This organic N can then be converted back to NH4+ and then
to NH3- after only a few weeks and becomes available to the
crop.
• This organic pool of N is therefore the most important aspect
of N nutrition, and 70% - 80% of the N taken up by crops is
normally from this pool rather than directly from mineral
fertilizer additions.
• Synthesized fertilizer N sources not only increase the
available mineral N status of soil but also temporarily
increase the amount of N in soilNE
organic matter as well
 NE
Soil phosphorus
• Phosphorus compound are important in energy transfer and
storage reactions since electrons are moved via adenosine
di- and triphosphate in most biochemical reactions.
• Phosphorus is also a constituent of nucleic acids, which
make up genetic encoded strands of DNA and RNA used for
protein synthesis.
• Flowering, fruiting, seed formation, and early plant
development therefore rely heavily on P supplies, as do root
development and several other processes.
NE
NE
 NE

• Even though the P content of plant tissues is about

0.1% - 0.4%, which is about one-half of the amount of N
or K, P is a critical component of particular basic to life.
• Phosphorus is fairly mobile in plants and is therefore
moved to the youngest tissues of plants are P deficient.
• Deficiencies of P are not as readily observed as those of
N, or even K, through the effects on growth and yield
are often dramatic.
• Some plant species exhibit a purple or red coloration
when they are deficient in P all will show overall
stunting.
• The orthophosphate form H2PO4 predominates as the form of P taken up
by plants although there are also a few organic compounds that have
been shown to be taken up directly plants. NE
• The solubility of orthophosphate compounds in the soil solution may vary
from 0.05 to 3 ppm.
• Unlike N, which is supplied as NO3- by mass flow of water to plant roots,
only a fraction of the P needed by plants is supplied by mass flow with
soil water.
• Diffusion is a much more important mechanism by which plant roots are
supplied with P, and the amounts of P in solution and its replenishment
are determined by the dissolution of relatively insoluble P compounds or
minerals.
• However, plant roots are not totally passive sinks for P; the exudation of
organic materials provides substrates for microbial populations, which
produce various acids that help to dissolve P compounds in soils.
• Zones around plant roots, called the rhizosphere, support colonies of
microorganisms that are essential to the growth of many species of
plants.
Nitrogen Fertilisers
• Ammonia
• Urea
• Ammonium Nitrate
• Ammonium Sulphate
• Calcium Nitrate
• Ammonium Chloride
• Sodium Nitrate
 Ammonia: Production and Storage
• Ammonia or azane is a compound of nitrogen and hydrogen
with the formula NH3.
• Colourless gas with a characteristic pungent smell.
• Ammonia, either directly or indirectly, is also a building-block
for the synthesis of many fertilizers, pharmaceuticals and is
used in many commercial cleaning products.
• Both caustic and hazardous.
• Worldwide production was estimated at 146.5 million tonnes.
• Ammonia, as used commercially, is often called anhydrous
ammonia.
• This term emphasizes the absence of water in the material.
• Because NH3 boils at −33.34 °C (−28.012 °F) at a pressure of
1 atmosphere, the liquid must be stored under high pressure or
at low temperature.
• “Household ammonia” or “ammonium hydroxide” is a solution
of NH3 in water.
• The concentration of such solutions is measured in units of the
Baumé scale (density), with 26 degrees baumé (about 30%
w/w ammonia at 15.5 °C) being the typical high-concentration
commercial product.
• Household ammonia ranges in concentration from 5 to 10
weight percent ammonia
• Approximately 90% of ammonia is used as fertilizers either
as its salts or as solutions.
• When applied to soil, it helps provide increased yields of
crops such as corn and wheat.
• Consuming more than 1% of all man-made power, the
production of ammonia is a significant component of the
world energy budget.
 Production of Ammonia
• Ammonia is produced in a process known as the Haber
process,
• Nitrogen and hydrogen react in the presence of an iron
catalyst to form ammonia.
• The hydrogen is formed by reacting natural gas and steam
at high temperatures and the nitrogen is supplied from the
air.
• Other gases (such as water and carbon dioxide) are
removed from the gas stream and the nitrogen and
hydrogen passed over an iron catalyst at high temperature
and pressure to form the ammonia
 Step 1 - Hydrogen production
• Hydrogen is produced by the reaction of methane with water.
• However, before this can be carried out, all sulfurous
compounds must be removed from the natural gas to prevent
catalyst poisoning.
• These are removed by heating the gas to 400 C and reacting
it with zinc oxide:
• ZnO + H2S → ZnS + H2O
• Following this, the gas is sent to the primary reformer for
steam reforming, where superheated steam is fed into the
reformer with the methane.
• The gas mixture heated with natural gas and purge gas to
770 C in the presence of a nickel catalyst.
• At this temperature the following equilibrium reactions are
driven to the right, converting the methane to hydrogen,
carbon dioxide and small quantities of carbon monoxide:
• CH4 + H2O →3H2 + CO
• CH4 + 2H2O → 4H2 + CO2
• CO + H2O → H2 + CO2
• This gaseous mixture is known as synthesis gas
 Step 2 - Nitrogen addition
• The synthesis gas is cooled slightly to 735 C.
• It then flows to the secondary reformer where it is mixed with a
calculated amount of air.
• The highly exothermic reaction between oxygen and methane
produces more hydrogen. Important reactions are:
• CO + H2O → CO2 + H2
• O2 + 2CH4 → 2CO + 4H2
• O2 + CH4 → CO2 + 2H2
• 2O2 + CH4 → 2H2O + CO2
• The necessary nitrogen is added in the secondary reformer.
• As the catalyst that is used to form the ammonia is pure iron, water,
carbon dioxide and carbon monoxide must be removed from the gas
stream to prevent oxidation of the iron.
Step 3 - Removal of carbon
monoxide
• Here the carbon monoxide is converted to carbon
dioxide (which is used later in the synthesis of urea) in a
reaction known as the water gas shift reaction:
• CO + H2O → CO2 + H2
• This is achieved in two steps.
• Firstly, the gas stream is passed over a Cr/Fe3O4
catalyst at 360 C and then over a Cu/ZnO/Cr catalyst
at 210 C.
• The same reaction occurs in both steps, but using the
two steps maximises conversion.
Step 4 - Water removal
• The gas mixture is further cooled to 40o C, at which
temperature the water condenses out and is removed.
 Step 5 - Removal of carbon oxides
• The gases are then pumped up through a counter-current of UCARSOL
solution (an MDEA solution)
• Carbon dioxide is highly soluble in UCARSOL, and more than 99.9% of
the CO2 in the mixture dissolves in it.
• The remaining CO2 (as well as any CO that was not converted to CO2 in
Step 3) is converted to methane (methanation) using a Ni/Al2O3
catalyst at 325 C:
• 2CO + 3H2→CH4 + H2O
• CO2 + 4H2→ CH4 + 2H2O
• The water which is produced in these reactions is removed by
condensation at 40 C as above.
• The carbon dioxide is stripped from the UCARSOL and used in urea
manufacture.
• The UCARSOL is cooled and reused for carbon dioxide removal.
 Step 6 - Synthesis of ammonia
• The gas mixture is now cooled, compressed and fed into the
ammonia synthesis loop
• A mixture of ammonia and unreacted gases which have already been
around the loop are mixed with the incoming gas stream and cooled
to 5 C.
• The ammonia present is removed and the unreacted gases heated to
400 C at a pressure of 330 barg and passed over an iron catalyst.
• Under these conditions 26% of the hydrogen and nitrogen are
converted to ammonia.
• The outlet gas from the ammonia converter is cooled from 220C to
30oC.
• This cooling process condenses more the half the ammonia, which is
then separated out.
• The remaining gas is mixed with more cooled, compressed incoming
gas.
• The reaction occuring in the ammonia converter is:
• N2 + 3H2 → 2NH3
• The ammonia is rapidly decompressed to 24 barg.
• At this pressure, impurities such as methane and hydrogen become
gases.
• The gas mixture above the liquid ammonia (which also contains
significant levels of ammonia) is removed and sent to the ammonia
recovery unit.
• This is an absorber-stripper system using water as solvent.
• The remaining gas (purge gas) is used as fuel for the heating of the
primary reformer.
• The pure ammonia remaining is mixed with the pure ammonia from
the initial condensation above and is ready for use in urea
production, for storage or for direct sale.
DESCRIPTION OF STORAGE AND
TRANSFER EQUIPMENT
• Ammonia is usually stored by using one or other of
three methods:-
• Fully refrigerated storage in large tanks with a typical
capacity of 10,000 to 30,000 tonnes (up to 50,000)
• Pressurised storage spheres or cylinders up to about
1,700 tonnes
• Semi-refrigerated tanks
• Anhydrous ammonia is stored in three types of tank as
outlined above:-
• Fully refrigerated at a temperature of about –33°C, these
tanks are provided with refrigeration equipment
• Semi-refrigerated spheres : Refrigerated storage is preferred
for storage of large quantities of liquid ammonia.
• The initial release of ammonia in the case of a line or tank
failure is much slower than with pressurized ammonia
 Urea
• Urea or carbamide is an organic compound with the chemical
formula CO(NH2)2.
• The molecule has two —NH2 groups joined by a carbonyl
(C=O) functional group.
• Urea serves an important role in the metabolism of nitrogen-
containing compounds by animals
• It is solid, colourless, and odorless (although the ammonia
that it gives off in the presence of water, including water
vapor in the air, has a strong odor).
• It is highly soluble in water and practically non-toxic (LD50 is
15 g/kg for rat).
• Dissolved in water, it is neither acidic nor alkaline.
• The body uses it in many processes, the most notable one
being nitrogen excretion.
• Urea is widely used in fertilizers as a convenient source of
nitrogen.
• Urea is also an important raw material for the chemical
industry.
• The synthesis of this organic compound by Friedrich
Wöhler in 1828 from an inorganic precursor was an
important milestone in the development of organic
chemistry, as it showed for the first time that a molecule
found in living organisms could be synthesized in the lab
without biological starting materials
• More than 90% of world production of urea is destined for
use as a nitrogen-release fertilizer.
• Urea has the highest nitrogen content of all solid
nitrogenous fertilizers in common use.
• Therefore, it has the lowest transportation costs per unit of
nitrogen nutrient.
• The standard crop-nutrient rating of urea is 46-0-0.
• Many soil bacteria possess the enzyme urease, which
catalyzes the conversion of the urea molecule to two
ammonia molecules and one carbon dioxide molecule, thus
urea fertilizers are very rapidly transformed to the
ammonium form in soils.
• Urea is also used in many multi-component solid fertilizer
formulations.
• Urea is highly soluble in water and is, therefore, also very
suitable for use in fertilizer solutions (in combination with
ammonium nitrate: UAN), e.g., in 'foliar feed' fertilizers.
• For fertilizer use, granules are preferred over prills because
of their narrower particle size distribution, which is an
advantage for mechanical application.
• The most common impurity of synthetic urea is biuret,
which impairs plant growth.
Urea (NH2CONH2)
UREA PRODUCTION
• The commercial synthesis of urea involves the
combination of ammonia and carbon dioxide at high
pressure to form ammonium carbamate which is
subsequently dehydrated by the application of heat to
form urea and water.
• Reaction 1 is fast and exothermic and essentially goes to
completion under the reaction conditions used industrially.
• Reaction 2 is slower and endothermic and does not go to
completion.
• The conversion (on a CO2 basis) is usually in the order of 50-
80%.
• The conversion increases with increasing temperature and
NH3/CO2 ratio and decreases with increasing H2O/CO2 ratio.
• The design of commercial processes has involved the
consideration of how to separate the urea from the other
constituents, how to recover excess NH3 and decompose the
carbamate for recycle.
• Attention was also devoted to developing materials to
withstand the corrosive carbamate solution and to optimise
the heat and energy balances.
• NH3 and CO2 are converted to urea via ammonium carbamate at a pressure of
approximately 140bar and a temperature of 180-185°C.
• The molar NH3/CO2 ratio applied in the reactor is 2.95.
• This results in a CO2 conversion of about 60% and an NH3 conversion of 41%.
• The reactor effluent, containing unconverted NH3 and CO2 is subjected to a
stripping operation at essentially reactor pressure, using CO2 as stripping agent.
• The stripped off NH3 and CO2 are then partially condensed and recycled to the
reactor.
• The heat evolving from this condensation is used to produce 4.5bar steam some
of which can be used for heating purposes in the downstream sections of the
plant.
• The NH3 and CO2 in the stripper effluent are vaporised in a 4bar decomposition
stage and subsequently condensed to form a carbamate solution, which is
recycled to the 140bar synthesis section.
• Further concentration of the urea solution leaving the 4bar decomposition stage
takes place in the evaporation section, where a 99.7% urea melt is produced.