18CHT45 - CHEMICAL PROCESS INDUSTRIES

Unit – III Fertilizer Industries:

Manufacture of ammonia, urea, ammonium phosphate,
ammonium nitrate, ammonium sulphate
Single and triple super phosphate
Potassium nitrate, potassium sulphate and potassium chloride
Compound fertilizers of N-P-K.
 Fertilizer industry
Fertilizers are substances that supply one or more of the
chemicals required for plant growth.
The primary objective of this fertilizer industry is to ensure
the inflow of both primary and secondary elements required
for crop production in the desirable quantities.
The success of the agricultural sector in India is largely
dependent on the fertilizer industry.
 Nitrogen Based Fertilizer
Ammonia 82 % ( N2 % Content)
Urea 46%
Ammonium Nitrate 36%
Ammonium Sulfate 21%
Di Ammonium Phosphate 18 %
Mono Ammonium Phosphate 12%
Manufacture of Ammonia and Urea
PROPERTIES

Molecular formula : NH3

Molecular weight : 17.031gm/mole
Appearance : Colourless gas
Odour : Strong pungent
Boiling point : -33.34 C
Melting point : -77.73 C
Density : 681.9kg/m3 at −33.3 °C (liquid)
Solubility : Soluble in water
 Properties of Ammonia

Ammonia is a colorless gas with characteristic pungent odour.

It is lighter than air.
Boiling point of ammonia: –33.5° C
Freezing point of ammonia: – 77.7° C
It is highly soluble in water.
Ammonia makes eyes tearful.
NH3 gas can be liquefied, however, due to its extremely low
boiling point, liquid ammonia must be stored at low temperature
and high pressure.

At high concentrations, exposure to ammonia gas can cause

permanent lung damage and death.

It has a high latent heat of vaporization (1370 J per gram) and is

therefore used in refrigeration plants of ice making machines.
 Properties of Ammonia
Dissociation of ammonia:
Can dissociate to form nitrogen and hydrogen when passed
through a red-hot tube or electric spark.
2NH3 ⇔N2 + 3H2
Oxidation of ammonia:
Ammonia reacts with oxygen when heated in the presence of
platinum at 800° C to yield nitric oxide.
4NH3 + 5O2 → 4NO + 6H2O + heat energy
2NO + O2 → 2NO2
 Sources of raw material
Nitrogen

Nitrogen is taken from air.

Hydrogen

Hydrogen can be synthesized from any feed stock listed in the table.
 Process Description
The method was first developed by Haber and Bosch therefore
known as Haber and Bosch Process.
The manufacture of ammonia is carried out by passing mixture of
pure hydrogen and nitrogen in the proportion of 3:1 by volume under
pressure (100-1000atm depending on conversion required).
Both the gases are sent through filter to remove compression oil and
additionally through the high temperature guard converter in which
CO and CO2 are converted to CH4 , and also removal of traces of
H2O, H2S, P and As.
The relatively cool gas is added along the outside of converter tube walls
to provide cooling.

Carbon steel is used as material of construction for pressure vessel and

internal tubes.

The preheated gas flows next through the inside of the tube which
contains promoted iron catalyst at 500-550 C.

The NH3 product, with 8-30% conversion depending on a process

conditions, is removed by condensation, first with water cooling and then
NH3 refrigeration.

The unconverted N2 –H2 mixture is recirculated to allow an 85-90% yield.

 Catalyst development
Iron oxide promoted by alkali is widely used as catalyst or
nonferrous metal oxides such as K2O (1-2%) and Al2O3 (2-5%).

The iron oxide is fused in an electric furnace and the promoters

added. The solidified mass is ground to desired particle size.

The iron oxide is reduced to porous iron in the start-up phases of

operation in the synthesis reactor.

There is a maximum operating temperature of about 620 C, above

which the catalyst fuses.
 USES
Ammonia is major raw material for fertilizer industries

It is used during the manufacture of Nitro compounds,

Fertilizers e.g. urea, ammonium sulfate, ammonium phosphate
etc.

It is also used in manufacture of Nitric acid, Hydroxylamine,

Hydrazine, Amines and amides, and in many other organic
compounds

It is also used in heat treating, paper pulping, explosives and

refrigerants
Manufacturing of Urea
 PROPERTIES
Molecular formula : CH4N2O

Molecular weight : 60.06gm/mole

Appearance : White granules

Odour : Odourless

Bulk density : 673-721kg/m3

Melting point : 132-135 C

Density : 1.32gm/ml

Solubility : Solubility in water, ethanol, glycerol

Moisture : 1% by wt. (Max.)

Urea is high moisture absorbent therefore it should be stored in sealed and well enclosed bags .
 Sources of raw material
 Ammonia can be synthesized by Haber – Bosch or Modern

process

 CO2
Side Reaction
Biuret
 2NH2 CO NH2 NH2 CO NH CO NH2 + NH3

Ammonium Carbamate

Urea
 Major Engineering problems
Autoclave variables

Carbamate decomposition and recycle

Production of granular urea (Prilling)

Heat dissipation in the autoclave

Corrosion
 Autoclave variables
The objective of autoclave reaction is to produce the optimum economic yield.
The conditions which affects rate of reactions are temperature, pressure, NH3 /
CO2 ratio and feed rate. The urea production rate can be varied as follows

Increase with increasing pressure .

Increase with temperature to maximum at 175-180 C, then falls of sharply. The

operating pressure should be above the dissociation pressure (dissociation
pressure is 180atm at 190°C) for the carbamate.

Use no excess ammonia.

Reasons for not operating at maximum temperature and
pressure without excess ammonia.

Increased pressure increases capital and operating cost of

compression and reaction equipment.

At higher temperature urea decomposed to biuret, which is

detrimental to germinating seeds and toxic to animals.

The above process conditions enhance corrosion rates to

machinery.
Production of granular urea (Prilling)

Problem again is biuret formation. Vacuum drying of 80% urea to > 99% and spraying
to air cooled and solidify must be done just above the melting point of urea and with a
minimum residence time.

Heat dissipation in the autoclave

The exothermic heat of reaction can be removed by coils, wall cooling

Corrosion

It can be minimized by use of the corrosion resistant metals and maintaining the
proper reaction conditions. High cost silver or tantalum liners are used in the
autoclaves with titanium, stainless (321SS) and aluminum alloys used in other parts of
the plant..
 USES
As a fertilizer

As a protein food supplements for plants

As an ingredient in the manufacture of resins, plastics, adhesive, coatings

Textiles anti-shrink agents and ion exchange resins

In melamine production

It is an intermediate in the manufacture of ammonium sulfamate, sulfamic

acid and pthalocyanines.
 AMMONIUM NITRATE(NH4NO3)
Ammonium nitrate is a colorless crystalline substance

Melting point 169.6 °C [337.3 °F].

It is highly soluble in water; heating of the water solution decomposes the salt to
nitrous oxide (laughing gas).

it dissolves the solid in an endothermic reaction

Due to its powerful oxidizing properties is used with proper additives as

commercial explosive.

Solid ammonium nitrate can undergo explosive decomposition when heated in a

confined space, government regulations have been imposed on its shipment and
storage.
 AMMONIUM NITRATE(NH4NO3)

Ammonium Nitrate is in the first place a nitrogenous fertilizer representing

more than 10% of the total nitrogen consumption worldwide.

It is more readily available to crops than urea.

In the second place, It is applied as a straight material or in combination with

calcium carbonate (or) limestone (or) dolomite.

The combination is called calcium ammonium nitrate (CAN) or Nitrolime or

various trade names and in compound fertilizers including nitro-phosphates.

It is also a principal ingredient of most liquid nitrogen fertilizers.

 PROPERTIES
Molecular weight : 80

Melting point : 170oC

Boiling point : Decomposes above 200 oC

Soluble : In water, alcohol and ammonia

N2 content : 33.5%

Explosive when mixed with combustable materials or exposed to

higher temperature.
 Calcium Ammonium Nitrate
Calcium ammonium nitrate or CAN, also known as nitro-limestone or
nitrochalk and Mostly used as a fertilizer.

Fertilizer grade CAN contains roughly 8% calcium and 21-27% nitrogen. CAN
is preferred for use on acid soils,[as it acidifies soil less than many common
nitrogen fertilizers.

Calcium ammonium nitrate is made by adding powdered limestone to

ammonium nitrate;another, fully water-soluble version, is a mixture of calcium
nitrate and ammonium nitrate, which crystallizes as a hydrated double salt:
5Ca(NO3)2•NH4NO3•10H2O.

Unlike ammonium nitrate, these calcium containing formulations are not

classified as oxidizers
 Manufacture of Ammonium Nitrate and Nitrolime
All processes are 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.

Raw Material
◦ 57-60% HNO3
◦ Liquid Ammonia
◦ Clay (for coating on end product to avoid explosion)

Chemical Reaction:

NH3 + HNO3 NH4NO3

 STEPS INVOLVED
Reaction of preheated ammonia with nitric acid in neutralizer.

Evaporation

Formation of prills in prilling tower.

Screening

Drying

Coating of NH4NO3 with clay.

 Process Description
Prilling Process

Neutralizer

The stoichiometric quantities of nitric acid and gaseous ammonia are

introduced by an automatic ratio controller to a neutralizer.
The ammonia vapor is reacted with aqueous nitric acid in a stainless steel
reaction vessel with agitation.
The neutralizer can be carried out at atmospheric pressure and temperature
does not exceed 105 C.
The pH and the temperature must both be strictly controlled to limit the
losses from the neutralizer.
The heat of reaction causes water to boil off and the final salt solution is 78%
and 140 C.
 Process Description
Evaporation to concentrate the AN

The ammonium nitrate solution from neutralizer fed to vacuum evaporator

for concentration. The solution is concentrated to 95% solids and
temperature 130 C.

Prilling

The hot concentrated melt is either granulated or prilled.

The hot liquor is sprayed from the top of the prilling tower (60 – 75 m high)
counter current to conditioned air flow.

Air is drawn upward by fans at the bottom of the tower.

The solidified spherical pellets or prills are about 1.5 mm in diameter and
must be screened and dried before coating with clay.
 Process Description
Screening:
The prills are removed from the bottom of the tower and passed to screens.
Fines and oversized material are redissolved and sent to the neutralizing
reactor for recycle.
Dryer:
The screened materials are cooled in a steam heated conveyor dryer.
Coating or Mixing the filling material:
In order to reduce the nitrogen content of A.N from 35% to 33.5%, the proper
filling material is added (about 4% by weight of powdered limestone or
dolomite or even kaolin)
Usually the prills are coated with clay to increase their flow.
The finished product contains 33.5% nitrogen are sent for bagging.
 STENGEL Process Description
It involves vapor phase reaction in a packed stainless steel reactor.
Ammonia vapor is preheated to 140-150 C in a single stage heat exchanger.
60% HNO3 is preheated first to 95 C in a stainless steel unit and then to 160 C
in a tantalum unit to avoid high temperature HNO3 corrosion.
The molten Ammonium nitrate and water vapor at 200 C are passed to cyclone
separator where air aids in removal of steam from the molten salt.
Molten salt is removed at the bottom and solidified on a water-cooled
stainless steel belt.
The solids are crushed, ground to flake size and screened.
Oversize is reground and the fines are dissolved and returned to HNO3
preheater stream.
The product flakes are coated with clay, and bagged and shipped.
 Modification to produce Nitrolime (CAN):

The same process which produced a 95% melt for prilling can be utilized for
the production of nitrolime.
The melt flows from a storage tank to a pug mill which is a screw mixer
consisting of two sets of mixing blades rotating in opposite direction.
Pulverized lime stone powder (325 mesh) is admixed herewith some heat of
reaction evolved.

The product flows to a rotary drum granulator, then to a co-current direct

heated flue gas dryer where product moisture is reduced to 0.5 – 0.6% H2O.
The dried Nitrolime is size reduced in crushing rolls.

Screen separates 2-4mm particles which move on to a coating drum where

fine limestone dust is added to yield a free-flowing product.

Oversize material (> 4 mm) is recycled to crushing rolls.

Undersize (< 2 mm) is returned to the pug mill.
 Major Engineering Problems
Corrosion

- Carbon steel used in NH3 storage and feed system.

- Stainless steel is used for HNO3.

- Stengel process- Tantalum metal is needed.

Decomposition

Temp. 525 C and 1.5 atm.

Conditioned air requirements

Both AN and CAN are hygroscopic so that humidity and temperature requirements
of the air in the materials handling area are critical.
 Uses
Ammonium nitrate is most commonly used in fertilizers (as an
excellent and inexpensive nitrogen source)
It is used to produce Calcium Ammonium Nitrate (CAN),
Ammonium Sulphate Nitrate (ASN) fertilizers.
Calcium ammonium nitrate or ammonium nitrate is used in some
instant cold packs for first aid on sport injuries
It is also used to manufacture explosives as it acts as a strong
oxidizing agent.
In particular, ammonium nitrate is used to prepare an industrial
explosive called ANFO (ammonium nitrate fuel oil), which is
composed of 94% ammonium nitrate and 6% fuel oil.
Amatol is a highly explosive material made from a mixture of TNT
and ammonium nitrate
 Instant Cold Pack
An instant cold pack is a device that consists of
two bags; one containing water, inside a bag
containing ammonium nitrate, calcium
ammonium nitrate or urea.

When the inner bag of water is broken by

squeezing the package, it dissolves the solid in an
endothermic reaction.

This reaction absorbs heat from the surroundings,

quickly lowering the pack's temperature.
 AMMONIUM PHOSPHATE
Ammonium phosphate also known as ammonium orthophosphate
is the salt of ammonia and phosphoric acid.

It consists of ammonium cations and phosphate anion.

There are two major types of ammonium phosphate which are

◦ Monoammonium phosphate (MAP)

◦ Diammonium phosphate (DAP)

Mono ammonium phosphate (MAP)
Anhydrous ammonia added to liquid phosphoric acid gives
mono ammonium phosphate (MAP).

It is a fertilizer or fertilizer intermediate with high P2O5 content

of about 67% and nitrogen content 11-12%.

Solid monoammonium phosphate can be considered stable in

practice for temperatures up to 200 °C, when it decomposes into
gaseous ammonia NH3 and molten phosphoric acid H3PO4.

Mono-ammonium phosphate is manufacture by reacting

ammonia with phosphoric acid, centrifuging and drying in a
rotary dryer.
 Di ammonium phosphate (DAP)
With more ammonia, technical grade di ammonium phosphate
(DAP) containing 16 to 18% nitrogen and 46% P2O5 is formed.

DAP requires two-stage reactor system in order to prevent loss of

ammonia.

The granulation process followed by neutralization is completed

in rotary dryer, which is heated by a furnace using fuel.
 Di ammonium phosphate (DAP)
"Hazardous Decomposition Products: Gradually loses
ammonia when exposed to air at room temperature.
Decomposes to ammonia and monoammonium phosphate at
around 70°C (158°F). At 155°C (311°F), DAP emits
phosphorus oxides, nitrogen oxides and ammonia."
 PROPERTIES
MAP DAP
Mol. Wt. : 115 132

M.P : 190 C 155 C

Density : 1.8 gm/cc 1.62 gm/cc

Odour : Odourless Odourless

pH :4 - 4.5 7–8

Solubility : Water Water

 MANUFACTURE OF MAP & DAP
Raw Materials

Ammonia

Phosphoric acid

Sources of raw material

Ammonia can be synthesized by Haber – Bosch or Modern process

Phosphoric can be manufacture by electric arc furnace, blast furnace or wet process.

Reactions

NH3 + H3PO4 NH4H2PO4

NH3 + NH4H2PO4 (NH4)2HPO4

 PROCESS DESCRIPTION
The two principal steps are

Neutralization

Granulation

Neutralization

Quantities of phosphoric acid and ammonia in the neutralization step are different form
mono ammonium phosphate (MAP) and diammonium phosphate (DAP).

To manufacture mono ammonium phosphate, ammonia to phosphoric acid ratio is 0.6:1

in the neutralizer.

While for diammonium phosphate, ammonia to phosphoric acid ratio is 1.4:1 in the
neutralizer.
 PROCESS DESCRIPTION
Phosphoric and ammonia are added to the first of three continuous mixed
reactors, anhydrous ammonia is added beneath the slurry level in the first
neutralizer in an amount equivalent to 80% neutralization.

Further ammonia is added in the 2nd and 3rd tanks to obtain conversion to the
di ammonium salt if a higher nitrogen containing fertilizer is needed.

The exothermic reaction heats the slurry nearly to the boiling point (130°C).
Unreacted and excess NH3 vapor is collected from the top of each tank and
recharged below the liquid level for reducing NH3 losses (less than 3%).

The hot slurry containing about 16 to 20% water is pumped into the
granulator, where more ammonia is added to increase the molar ratio to
approximately 2.0.
 PROCESS DESCRIPTION
Granulation

Slurry from the third neutralized is mixed with KCl and absorbed in a bed of dry recycle
fertilizer moving through a rotating drum granulator.

This provides a tumbling action to cool recycle material with a slurry film.

A rotary adiabatic drier reduces the moisture to less than 1%, with 10 minute contact
time with air initially at 150 C.

Dried product is separated into three fractions on a double deck screen.

After screening the fertilizer granules are coated with specific material in order to
regulate its dissolving process in the soil when used.

A portion of the product from the deck of the lower screen is sent to bagging
operations. The balance, together with pulverized oversize and fines, is returned to the
granulator.
 PROCESS DESCRIPTION
Major engineering problem

Ammonia losses
◦ Ammonia loss should be kept below 3%.

◦ It can be achieved by using multistage reactors along with efficient recycling

mechanism of collecting the vapor of ammonia from top of the neutralization tower
and recycle back to the process.

Corrosion
◦ Use of corrosion resistance material like SS-316 for hot acid and fumes ducts, carbon
steel for granulation, drying and screening.
 USES
The largest use of monoammonium phosphate as fertilizers.

It supplies soil with the elements nitrogen and phosphorus in a form usable
by plants. Its NPK label is 12-61-0 (12-27-0), meaning that it contains 12% by
weight of elemental nitrogen and (nominally) 61% of phosphorus pentoxide
P2O5, or 27% of elemental phosphorus.

Monoammonium phosphate crystals are piezoelectric, a property required in

some active sonar transducers

Used in buffer solutions and in analytical chemistry.

For food grade, DAP is also used as a yeast nutrient in winemaking and mead-
making
 Uses
MAP (or) DAP can be used as a fire retardant .

[Phosphate salts containing a thermally volatile cation are most effective for fire
retarding cellulosic fuels. As the treated fuel is heated, the cation is released and the
residual phosphoric acid then reacts with the cellulose molecule producing an ester.
The phosphate ester subsequently thermally degrades via dehydration resulting in
the release of water vapor and the deposition of graphite-like carbon that is not
flammable in atmospheric conditions. ]

Monoammonium phosphate is a widely used crystal in the field of optics due to its
birefractive properties.

[Birefringence (or) birefractive is the optical property of a material having a

refractive index that depends on the polarization and propagation direction of light.]
 Ammonium sulfate
Ammonium sulfate, also called di-ammonium sulfate or sulfuric acid di-
ammonium salt, Fine white hygroscopic granules or crystals with no smell &
salty taste.

The compound dissolves easily in water but will insoluble in acetone, alcohol
and ether.

It readily absorbs water, so if it's exposed to moist air, it will “scab” on the damp
surfaces.

When ammonium sulfate reacts with alkaline substances, it gives off ammonia
gas.

The most common use is as a soil fertilizer since the chemical contains 21%
(w/w) nitrogen and 24% (w/w) sulfur.
 Ammonium sulfate
Ammonium sulfate decomposes upon heating above 250 °C, first forming
ammonium bisulfate. Heating at higher temperatures results in
decomposition into ammonia, nitrogen, sulfur dioxide, and water.

As a salt of a strong acid (H2SO4) and weak base (NH3), its solution is acidic;
 MANUFACTURE
Direct neutralization

Gypsum process

As by-product from caprolactam

Recovery from cock oven

 Direct neutralization or
Synthetic Manufacture
Ammonium sulphate is produced by the direct reaction of concentrated
sulphuric acid and gaseous ammonia.

Raw materials
◦ Ammonia

◦ Sulfuric acid

Sources of raw material

◦ Ammonia can be synthesized by Haber – Bosch or Modern process.

◦ Sulfuric acid can be obtained by contact process.

Reaction

2NH3 + H2SO4 (NH4)2SO4

 Gypsum Process
Raw materials

Ammonia

CO2

Gypsum

Sources of raw material

Ammonia can be synthesized by Haber – Bosch or Modern process

Ammonium sulfate also is
manufactured from gypsum.
Ammonia is absorbed in water to form ammonium hydroxide.

Ammonium hydroxide is carbonated at the pressure of about 2.1kg/cm2 in

towers packed with aluminum rings.

CO2 absorbed in NH3 to form ammonium carbonate in absorption tower.

Finely divided gypsum is added to a solution of ammonium carbonate

causing calcium carbonate precipitates as a solid, leaving ammonium
sulfate in the solution:
(NH4)2CO3+CaSO4 → (NH4 )2SO4+CaCO3
 PROCESS DESCRIPTION
Reactions of ammonium carbonate and gypsum solutions are carried out in a
series of wooden vessels or mild steel vessels having steam coils and agitators to
give a total retention time of 4 to 6 hours.

The slurry produced is filtered and the calcium carbonate cake washed and
dewatered in a vacuum filter.

CaCO3 obtained as by product is used as a raw material for the manufacture of

cement.

25% Ammonium sulphate solution is concentrated in triple effect evaporating

crystallizers and the crystals are centrifuged and dried in a rotary drier at 120 C.
 PROCESS DESCRIPTION
Handling and storage

Crystalline ammonium sulfate is free flowing and does not normally pose
any problem in handling and storage.

However, it generally contains some powdered material which causes

caking, especially under high humidity.

Due to its susceptibility to caking and slight acidity, ammonium sulfate is

normally bagged in polyethylene lined gunny bags or high density
polyethylene (HDPE) woven sacks.
 USES
Ammonium sulfate is used most commonly as an artificial fertilizer for alkaline soils.
When introduced into damp soil, an ammonium ion is released. This creates a small
amount of acid, which lowers the pH balance of the soil.

In the treatment of drinking water, ammonium sulfate is used in combination with

chlorine to generate chloramines for disinfection. It's also in flame retardant materials
because it lowers the combustion temperature and increases the production of residues
or chars.

Ammonium sulfate activates yeast, so it helps to get industrially produced bread to rise,
and it's also a general-purpose food additive.

It plays an important role in developing vaccines during the purification process.

It is also used as an agricultural spray adjuvant for water-soluble insecticides, herbicides,

and fungicides.
Single and triple super phosphate, potassium
nitrate, potassium sulphate and potassium
chloride
 Calcium Phosphates

Large tonnages of low-grade calcium phosphates are made as fertilizers.

There are two distinct grades possible based on the method of production
from phosphate rock.

 Superphosphate

 Triple superphosphate
 Superphosphate
 It made by reacting phosphate rock with with sulphuric acid; contains
16-20% P2O5.

 Superphosphate, Ca(H2PO4)2 , also referred as single superphosphate

(SSP).

 Chemically, SSP contains mono calcium phosphate and calcium sulfate.

 Single superphosphate has a low phosphorus content (16 to 22 % P2O5),

and 6 to 10% moisture content.
 PROPERTIES
Molecular formula : Ca(H2PO4)2

Molecular weight : 234.05gm/mole

Elemental analysis : 16% P2O5 (7%P), 12% S, 21% Ca, 4% phosphoric acid

Appearance : White, Gray or brown granular

Odour : Odourless

Boiling point : 203 C

Melting point : 109 C

Solubility : Solubility in water, HNO3 and HCl

 Superphosphate
Made by reacting phosphate rock with sulphuric acid

Raw Material Required

◦ Phosphate rock
◦ Sulphuric Acid

Chemical Reaction

[Ca3(PO4)2]3 CaF2 + 7H2SO4 3CaH4(PO4)2 . 7CaSO4 + 2HF

SiO2 Impurities Removal

4HF + SiO2 SiF4 + 2H2O

3SiF4 + 2H2O 2H 2SiF6 + SiO2

H2SiF6 + NaCl Na2SiF6 + 2HCl

 Major Equipment's Used
Crusher

Ring roll mill

Continuous Blender

Den or Silo

Rotary Granular

Rotary Dryer
 Process Description
Phosphate rock lumps are crushed in a jaw crusher and grounded to -100
mesh in a hammer or ring roll mill.

After size reduction passed to continuous blender with (65-70%) sulfuric

acid continuously.

Where the reaction take place.

With proper grinding and acid control, the reaction is effectively complete
and can be sent directly to a granular or otherwise store in silo for 24 hrs to
complete the reaction.

The SiF4 and HF fumes along with CO2 are scrubbed in water and the silica
is removed by NaCl.
 Process Description
The porous , crumbly material from the den is mixed with rock dust from

the grinding section of the plant and fed to sloping rotary drum.

Water is sprayed on tumbling solids to form free flowing granules

The product is dried in a rotary dryer.

In the process, provision can be made to produce a chemical mixed

fertilizer containing N-P by adding excess H2SO4 and neutralizing with NH3

in the granulator.
 USES
It is the principal carrier of phosphate, the form of phosphorus usable by
plants, and is one of the world's most important fertilizers.

it is low cost source of phosphorous in a wide range of pasture and cropping

situations

Generally mixed with sulfate of ammonia and potash, and also blended with
other fertilizers
 Triple Superphosphate
Triple superphosphate (TSP) is the more concentrated fertilizer than
ordinary superphosphate, containing from 44 to 51% of available P2O5 or
nearly three times the amount in the regular superphosphate.

TSP is manufactured by adding phosphoric acid to rock phosphate,

producing mainly water-soluble mono calcium phosphate with no calcium
sulfate.

Its concentrated form is cheaper to transport, store and apply when

compared with the dilute form.
 PROPERTIES
Molecular formula : Ca(H2PO4)2

Molecular weight : 234.07gm/mole

Appearance : White or gray granules

Solubility : water soluble

pH : 2.5-3.0 (aqueous solution)

P2O5 (water soluble) : 42.5% minimum

Free phosphoric acid : 3% by wt. (Max.)

Density : 800-881kg/m3

Moisture : 12.0% by wt. (Max.)

 Triple Superphosphate
Made by reacting phosphate rock with phosphoric acid

Raw Material Required

◦ Phosphate rock

◦ Phosphoric Acid

Chemical Reaction

[3Ca3(PO4)2]3 CaF2 + 14H3PO4 10CaH4(PO4)2 + 2HF

 Major Equipment's Used
Crusher

Ring roll ill

Continuous Belt Reactor

Rotary Granular

Rotary Dryer
 Process Description
Phosphate rock lumps are crushed in a jaw crusher and grounded to -100
mesh in a hammer or ring roll mill.

After size reduction passed to continuous belt reactor with (65-70%)

sulfuric acid continuously.

Where the reaction take place.

With proper grinding and acid control, the reaction is effectively completed
with in 15 to 20 minutes and can be sent directly to a granular or
otherwise store in silo for 24 hrs to complete the reaction.

The SiF4 and HF fumes along with CO2 are scrubbed in water and the silica
is removed by NaCl.
 Process Description
The porous , crumbly material from the den is mixed with rock dust from

the grinding section of the plant and fed to sloping rotary drum.

Water is sprayed on tumbling solids to form free flowing granules

The product is dried in a rotary dryer.

In the process, provision can be made to produce a chemical mixed

fertilizer containing N-P by adding excess H3PO4 and neutralizing with NH3

in the granulator.
 USES
TSP can be used in wastewater treatment to reduce lead levels.

As a low cost source of phosphorus, TSP is the main substitute for single
superphosphate in cropping blends.

It is used mainly in blends with DAP and MAP

Source of phosphorus in situations where no nitrogen is required

In horticultural blends where the phosphorus content needs boosting.

Potassium Based Fertilizer
Potassium Chloride

Potassium Nitrate

Potassium Phosphate

Potassium Sulfate
 POTASSIUM CHLORIDE
 Potassium chloride (KCl) is a metal halide salt composed of

potassium and chlorine.

 Potassium chloride crystals are face centered cubic.

 "Muriate of potash" is name which is occasionally association

with its use as a fertilizer containing 60% plant food as K2O.
 Potash varies in colour from pink or red to white depending on
the mining and recovery process used.

 White potash or soluble potash is usually higher in analysis and

is used primarily for making liquid starter fertilizers.

 It occurs naturally as the mineral sylvite and in combination

with sodium chloride as sylvinite.

 PROPERTIES
Molecular formula : KCl

Molecular weight : 74.55 gm/mole

Appearance : white crystalline solid

Odour : Odourless

Boiling point : 1420 °C

Melting point : 770 °C

Density : 1.984gm/ml

Solubility : Soluble in glycerol and water, slightly

soluble in alcohol, insoluble in ether

Moisture : 0.5% by wt. (Max.)

 METHODS OF MANUFACTURE
Potassium chloride is obtained by following methods

1. Leaching process

2. Flotation process
 RAW MATERIALS
◦ Sylvinite

◦ Utilities

◦ Steam

◦ Water

◦ Electricity

Potash mineral or brine

Potash mineral or sylvinite contain potassium chloride and sodium

chloride.
 LEACHING PROCESS

The solubility of potassium chloride and sodium chloride increases as the

temperature increases.
Individually both are much more soluble in hot water than in cold water.
But in solutions saturated with both sodium and potassium chloride, the
concentration of NaCl diminishes as temperature rises, while the
concentration of potassium chloride increases.

These solubility characteristics are used to extract potassium chloride from

sylvinite.

Crushed ore is mixed with sufficient quantity of recycle brine which is

already saturated with NaCl and heated almost to dissolve KCl.
The KCl rich brine on clarification and then cooling by vacuum evaporation
produces KCl crystals which are centrifuged, washed, dried and packed.
 FLOTATION PROCESS
Floatation process for extraction of potassium chloride is much cheaper than
leaching process and hence is used more extensively in the industry.

In the process the ore is crushed to 10 mesh size then washed to remove clay
slimes.

To render it inert to amines, washed crushed ore is treated first with starch gums
and then with an amine acetate which selectively coats KCl particles.

Air is then bubbled through the slurry.

The air bubbles attach themselves to the coated particles and float them to the
surface while the uncoated particles sink.

The floated KCl is centrifuged, dried and packed.

 HANDLING AND STORAGE
The crystalline potassium chloride is free flowing and does not normally pose any
problem in handling and storage.

Potassium chloride is imported as bulk cargo and transported to NPK fertilizer and
mixing plants in open trucks or in bags.

It is stored in bulk in closed storage yards.

Caking occurs in presence of impurities when humidity is high and the mass tends
to become like rock.

Retrieval from such storage may pose problems and sometimes explosives may
have to be used.
 USES
As a fertilizer .

Used as thickeners, stabilizer, mineral salts, gelling agents and acidity regulator
in food .

Used as a salt replacer in foods, for recovery of potassium in the human body.

It's used in brewing, as a salt substitute (as salt free, sodium free, and low
sodium products), gelling agent, and in reduced sodium breads.

Used in various pharmaceutical preparations to correct potassium deficiency.

It used as a substitute for table salt in the diet of people with cardiovascular
disorders, in administration of the potassium ion, and as a constituent of
Ringer's solution (contains sodium chloride, potassium chloride, calcium chloride
and sodium bicarbonate).
 Potassium Nitrate
It is also called as nitre or saltpeter.
It is an alkali metal nitrate because it is an ionic salt of potassium
ions K+ ions and nitrate ions NO3−.
White crystalline powder.
Potassium nitrate is soluble in hot water.
This compound releases oxygen when heated or decomposed. It is a
strong oxidizing agent.
Boiling Point 400 °C .
Melting Point 334 °C.
Potassium nitrate is a water-soluble NK fertilizer containing 13.7%
nitrate nitrogen and 46% potassium oxide (38.4%).
 POTASSIUM NITRATE (KNO3)
The third most widely used potassium salt in agriculture is potassium nitrate.
 PROPERTIES

Molecular weight: 101.103

White crystalline powder or Crystals

High solubility

Low chlorine level

Free flowing

Low moisture content

Slightly acidic pH
 METHODS OF MANUFACTURE
Potassium nitrate is manufactured in two ways:

By reacting nitric acid with potassium chloride with a chlorine by product and

Reacting sodium nitrate with potassium chloride and crystallizing out the salt.

NITRIC ACID WITH POTASSIUM CHLORIDE

Nitric acid reacts with potassium chloride at low temperature according to the
equation;

CHEMICAL REACTION

KCl + HNO3 KNO3 + HCl

 PROCESS DESCRIPTION

KCl is dry-screened with the separation of two equal coarse and fine fractions.

Fines are directly sent to reactor.

Coarse KCl is passed to dissolving tank and dissolved by recycled HNO3.

The reaction then takes place between the KCl with the nitric acid having a
60% concentration at ambient temperature between 15° and 30° C., using molar
proportion of 0.9 to 1 mole (KCl:HNO3) in the reactor.

When the reaction is completed, crystallization takes place by cooling the

stream to a temperature between 0° and -30° C. in a cooling crystallizer.
 PROCESS DESCRIPTION
Followed by the separation of the potassium nitrate crystals from the resultant
brine (HCl + HNO3) at an approximate temperature of 20° C in centrifuge filter,
washing with water and drying, leading to KNO3 as the end product.

It can be sold in the powder form or melted and prilled.

The brine obtained in the previous stage as a filtrate is processed by extraction

using solvents in order to obtain a brine containing HCl (15-20%) which is free
from HNO3.

Solvent: Polyalkylene glycols

Solvent extract is washed with water to recover the solvent and HNO3 is
recirculate for dissolving of KCl in dissolving tank.
 USES
Fertilizer

Detergents and soaps

Glass and ceramics

Textiles and dyes

Chemicals and drugs

Gunpowder, also known as black powder, is the earliest known chemical

explosive. It is a mixture of sulfur, charcoal, and potassium nitrate (saltpeter).
The sulfur and charcoal act as fuels, and the saltpeter is an oxidizer.

Rocket propellants and fireworks

Leather processing Industries

Solar power plants

 Other Applications
CHEMICAL INDUSTRY:
Potassium nitrate is used in a wide variety of applications including glass
manufacturing, explosives for mining and civil works, metal treatment and
fireworks.
FOOD INDUSTRY:
Potassium nitrate is a well-known ingredient in the food industry, as a mean to
cure and preserve meats against microbial agents and to maintain the
desirable color of meats and hard cheeses.
PHARMACEUTICALS:
Potassium nitrate is a well-known product to de-sensitize sore teeth. It is
therefore, a common ingredient in sophisticated toothpastes focusing on the
treatment of sensitive teeth.
POWER PLANTS:
Mixtures of potassium nitrate and sodium nitrate salts are increasingly
used as means to significantly enhance the efficiency of Concentrating Solar
Power (CSP) plants. This salt mixture, due to its high latent heat capacity, is
very effective in storing thermal energy for up to several days.
 POTASSIUM PHOSPHATE
Potassium Phosphates are excellent fertilizers, and their very high
analysis is an advantage that has stimulated much research in an
effort to find an economical production process.

However, no process has been developed that is economical enough

to result in widespread production; therefore, present use is limited
to special purposes for which the high cost can be justified.
 ALTERNATE SALTS OF POTASSIUM PHOSPHATES

Phosphate Potassium Salts Compound Formula

Monopotassium phosphate KH2PO4

Dipotassium phosphate K2HPO4

Tripotassium phosphate K3PO4

Potassium metaphosphate KPO3

 Mono potassium phosphate
It is also potassium di hydrogen phosphate, KDP, or monobasic potassium
phosphate, KH2PO4.

Monopotassium phosphate can exist in several polymorphs.

At room temperature it forms paraelectric crystals with tetragonal symmetry.

Upon cooling to −150 °C (−238 °F) it transforms to a ferroelectric phase of

orthorhombic symmetry, and the transition temperature shifts up to −50 °C (−58 °F)
to when hydrogen is replaced by deuterium.

Heating to 190 °C (374 °F) changes its structure to monoclinic. When heated further,
MKP decomposes, by loss of water, to potassium metaphosphate, KPO3, at 400 °C
(752 °F).
Composition Content

Water soluble Phosphates (as P2O5 ),per cent by weight ,

52.00
minimum

Water soluble Potash (as K2O ),per cent by weight ,

34.00
minimum
 Tripotassium phosphate
Tripotassium phosphate can be colorless to white and be found
as either crystals, lumps or powder form.

it has a very high melting point of 1380 °C which allows it to

be heated to remove water without decomposing the salt.

It is slightly hygroscopic.

Tripotassium phosphate is a strong inorganic base with a pH of

11.5－12.5.[

It is a water-soluble ionic salt which has the chemical formula

K3PO4
 PROPERTIES
Odor : odorless

Density : 2.388 g/cm3

Available in the form of : dry powder, liquid, pellets and large crystals

Soluble in water and slightly soluble in ethanol

Boiling point : 400 C

Melting point : 252.6 C

 Manufacturing process
RAW MATERIAL

Conc.Phosphoric acid (85%)

Conc.Potassium hydroxide (40-45%)

Potassium hydroxide and phosphoric acid react to form potassium phosphate

and water according to the reaction

KOH (aq) + H3PO4 (aq) KH2PO4 (aq) + H2O(l)

Flow Sheet
 PROCESS DESCRIPTION
The reactants involved in the production of potassium phosphate are phosphoric
acid and potassium hydroxide.

The reagents may be pumped into the reaction vessel or manually added.

Water may be added to dilute the reaction mixture and to maintain a slurry.

Once both reagents are added, the reaction mixture usually is mixed for a period
of time, usually about 1 hour.

One common method of mixing is to use agitators present within the reaction
vessel.

The reaction is exothermic and temperature rises more than 60 C.

Usually, the reaction mixture is cooled to about 55° C. or 50° C. or lower.

 PROCESS DESCRIPTION
The reaction mixture may be cooled by any means of refrigeration.

Once the reaction mixture has been cooled it then may be homogenized.

This reduces the particle size within the cooled reaction mixture/slurry.

The reaction mixture may be pumped into the homogenizer (A homogenizer is

a machine that takes a substance and makes it a uniform consistency and
helps reduce separation) set at about a 25 micron clearance between the rotor
and stator.

After the reaction mixture is homogenized, pump may be used to move the
homogenized slurry to a spray dryer.
 PROCESS DESCRIPTION

Spray drying involves the atomization of a liquid into a spray followed by the

drying of droplets in a drying chamber.

When the moisture evaporates from droplets, dry particles are formed and

these particles are released from a drying chamber for collection.

The particle size range of about 75-100 microns.

Spray dryers usually have a feed pump, an atomizer, an air heater, an air

disperser, a drying chamber and systems for exhaust air cleaning and powder

recovery.
 USES
Used as a fertilizer,

Food additive and a fungicide.

Pesticides

It is a source of phosphorus and potassium.

It is also a buffering agent.

Fertilizer-grade MKP powder contains the equivalent of 52% P 2O5 and 34% K2O

Potassium phosphate and sodium phosphate is a combination medicine used to

make the urine more acid to help prevent kidney stones.

When used in fertilizer mixtures with urea and ammonium phosphates, it minimizes
escape of ammonia by keeping the acidity relatively low level.
 Potassium Sulphate
Properties

Its colour is white

It is readily soluble in water

It contains 41.6 – 44.1% K (Or 50 – 53% K2O). It is usually 90

– 95% K2SO4.

It is a neutral salt and neutral fertilizer.

Raw Material
◦ KCl
◦ Sulphuric Acid
Reaction
 Process Description
The potassium chloride reacts during slow mixing in the heated Mannheim
furnace with sulfuric acid, producing gaseous HCl and K2SO4.

The furnace is heated by natural gas or fuel oil. The product K2SO4 is
cooled in a cooling drum. Lump material from the cooler is crushed and
finished or can be compacted and granulated as with KCl.

The HCl gas is cooled in a graphite in a graphite heat exchanger and

absorbed in water in two stages to produce 30% hydrochloride acid as a
byproduct.

The process gives an excellent quality that contains over 50% K2O and less
than 1% chlorine. Emissions are well controlled.
 Primary Nutrition in fertilizer
Nitrogen %N
Urea 45
Ammonium sulphate 21
Prilled ammonium nitrate 34
Ammonium nitrate/calcium carbonate 21-26
Anhydrous ammonia 81
Liquid fertilisers containing 20-40
ammonium
nitrate, ammonia and urea
Phosphorus %P2O5
Superphosphate 18-21
Triple superphosphate 45-47
Ground mineral phosphate 29-33
Basic slag 8-22
Potassium %k2O
Potassium chloride (muriate of 60
potash)
Potassium sulphate 50
 Contd…

What is straight fertilizer?

Straight fertilizer is a fertilizer that contribute single nutrient to the
crops.
Few examples of straight fertilizer are urea, rock phosphate,
ammonia, ammonium sulfate and muriate of potash.
 STRAIGHT FERTILIZER

The straight fertilizers are those fertilizers which supply only one primary plant
nutrient, either N or P or K.

On this basis, the fertilizers can be straight nitrogenous, straight Phosphatic or

straight Potash fertilizers.

Examples of straight nitrogenous fertilisers include Ammonium Sulphate (AS),

Calcium Ammonium Nitrate (CAN), Ammonium Chloride and Urea.

Examples of straight Phosphatic fertilizers include Single Super Phosphate (SSP)

and Triple Super Phosphate (TSP)

Example of straight Potash fertilizer is Potassium Chloride.

STRAIGHT FERTILIZER
 COMPOUND/COMPLEX FERTILIZER
Fertilizers containing two or all three of the three basic plant nutrients—N, P2Os,
and K2O—as well as microelements, such as B, Mn, Cu, Zn, and Mo. These
combination (compound or complex) fertilizers can offer advantages of
convenience in the field, economic savings, and ease in meeting crop nutritional
needs.
COMPOUND FERTILIZER
PRODUCTION

Compound fertilizers are made using basic fertilizer materials, such as

NH3, ammonium phosphate, urea, S, and K salts. Compound fertilizer
contains multiple nutrients in each individual granule.

There are many methods used for making these fertilizers, with the
specific manufacturing processes determined by the available basic
components and the desired nutrient content of the finished product.
Here are four brief examples.

Compaction methods (agglomeration) involve binding small fertilizer particles

together using compaction, a cementing agent, or a chemical bond.

Accretion-based fertilizers are made by repeatedly adding a thin film of

nutrient slurry which is continually dried, building up multiple layers until the
desired granule size is reached.

Pipe-cross reactors are used to chemically melt NH3, acids containing S or P,

and other Nutrients such as K sources and micronutrients into a solid fertilizer
with the desired nutrient content.

The nitrophosphate process involves reacting phosphate rock with nitric acid
to form a mixture of compounds containing N and P. If a K source is added
during the process, a solid fertilizer with N, P, and K will result.
TYPES OF COMPOUND FERTILIZERS
AMMONIUM PHOSPHATE SULPHATE

AMMONIUM PHOSPHATES

NITROPHOSPHATES

UREA AMMONIUM PHOSPHATES (UAP)

NPK COMPLEX FERTILIZERS

COMPOUND FERTILIZER
MIXED FERTILIZER
A mixture of two more straight fertilizer materials is referred to as fertilizer
mixture. Sometimes, complex fertilizers containing two plant nutrients are also
used in formulating fertilizer mixtures.
Complete fertilizer refers to the fertilizers containing three major plant nutrients,
N, P2O5 and K2O.
Mixed fertilizers are also called "Blended fertilizer“, meaning a fertilizer obtained
by dry mixing of several fertilizers, with no chemical reaction. The ingredients
used in fertilizer mixtures vary widely in their physical and chemical
characteristics.
When such widely varying materials in physical and chemical properties are
mixed together, naturally many changes are expected to take place during or after
the mixing.
Some changes will be of physical nature and some will be of chemical nature.
Mixed fertilizers are made by thoroughly mixing the ingredients either
mechanically or manually.
The best mixed fertilizers are obtained when granulated components are mixed.
NPK COMPLEX / COMPOUND FERTILIZER
 PROPERTIES
Colour- uncoated condition(Gray), Coated (white or Cream)

Sp. gravity : 1.54

Relative humidity : 60-65

Required raw materials are

Phosphoric acid
Ammonia
Potash and Urea
Fillers (sand, dolomite, etc.)
Coating agents (clay, soapstone, etc.)
 NH3 H3PO4 UREA

PRENEUTRALISATION

AMMONIATION
POTASH GRANULATION

DRYING

SCREENING

COOLING

COATING

NPK
COMPLEX
 METHODS OF MANUFACTURE
Ammonia and phosphoric acid in the required proportions are metered to the pre
neutraliser and the resultant slurry is pumped to the granulator which can be a
rotating drum.

Here the nitrogen content is increased by adding more ammonia and feeding in
urea whenever necessary.

Filler and potash are also added to make up the required product formulation.

The granulator discharge is then dried, screened, cooled and coated with a coating
agent to improve the storage properties.
 Handling storage and Packing
Granular NPK complex fertilizers are free flowing and do not normally pose any

problem during handling and storage.

Coating agents are used to make the resistant to caking.

However, exposure long periods in regions of high humidity can cause caking.

NPK complex fertilizers are, therefore, bagged in polyethylene lined HDPE bags

to prevent any possible seepage of moisture from the atmosphere which tends to

promote caking.
THANK YOU
 BIO-FERTILIZERS
INTRODUCTION

'Biofertilizer' is a substance which contains living microorganism

It is stimulating plant growth through the synthesis of growth promoting

substances

Microorganisms could readily and safely convert complex organic material into
simple compounds, so that they are easily taken up by the plants.

Bio-fertilizer is technically living, it can symbiotically associate with plant roots.

It maintains the natural habitat of the soil. It increases crop yield by 20-30%,
replaces chemical nitrogen and phosphorus by 30%, and stimulates plant
growth.
 Importance of Bio-fertilizers
They increase the yield of plants by 15-35%.

Bio-fertilizers are effective even under semi-arid conditions,

Farmers can prepare the inoculum themselves,

They improve soil texture,

Bio-fertilizers do not allow pathogens to flourish,

They produce vitamins and growth promoting bio-chemical’s,

They are non-polluting.

 TYPES OF BIO-FERTILIZERS
Nitrogen fixing Biofertilizers

1.Rhizobium

A soil habitat bacterium able to colonize the legume roots

Fixes atmospheric elemental nitrogen symbiotically into plant usable form.

Fixes 50-100 kg/ha/year of nitrogen, most useful in concern with amount of

N2 fixed.

It is especially important for legumes and oilseeds

 TYPES OF BIO-FERTILIZERS
2. Azotobacter

A free living bacteria mostly found in neutral to alkaline soils.

Fixes the atmospheric nitrogen by converting into ammonia

Produces abundant slime which helps in soil aggregation.

 TYPES OF BIO-FERTILIZERS
3. Azospirillum

Proliferates under both anaerobic and aerobic condition.

Nitrogen fixing ability of 20-40 kg/ha

Disease resistance and drought tolerance are some of the additional benefits
 TYPES OF BIO-FERTILIZERS
4. Cyanobacteria

Both free-living as well as symbiotic cyanobacteria (blue green algae) have been
harnessed in rice cultivation.

The benefits due to algalization could be to the extent of 20-30 kg/ha.

Add growth-promoting substances & vitamin B12

Improve the soil’s aeration, water holding capacity and add to bio mass when
decomposed after life cycle
 TYPES OF BIO-FERTILIZERS
5. Azolla
A free-floating water fern used as Biofertilizer for wetland rice
Fixes atmospheric nitrogen in association with nitrogen fixing blue green algae
Anabaena azollae
Known to contribute 40-60 kg /ha per rice crop
Constraints in Bio fertilizer Technology
Technological constraints
◦ Use of improper, less efficient strains for production.

◦ Lack of qualified technical personnel in production units.

◦ Production of poor quality inoculants without understanding the basic

microbiological techniques

◦ Short shelf life of inoculants.

Environmental constraints
◦ Seasonal demand for biofertilizers

◦ Simultaneous cropping operations and short span of sowing/planting in a particular

locality

◦ Soil characteristics like salinity, acidity, drought, water logging, etc.

Infrastructural constraints

◦ Non-availability of suitable facilities for production

◦ Lack of essential equipments, power supply, etc.

◦ Space availability for laboratory, production, storage, etc.

◦ Lack of facility for cold storage of inoculant packets

Financial constraints

◦ Non-availability of sufficient funds and problems in getting bank loans

◦ Less return by sale of products in smaller production units.

Human resources and quality constraints

Lack of technically qualified staff in the production units.

Lack of suitable training on the production techniques.

Ignorance on the quality of the product by the manufacturer

Non-availability of quality specifications and quick quality control methods

No regulation or act on the quality of the products

Awareness on the technology

Unawareness on the benefits of the technology

Problem in the adoption of the technology by the farmers due to different

methods of inoculation.

No visual difference in the crop growth immediately as that of inorganic

fertilizers.