NITROGENO
US
FERTILIZER
18BCH013 Devam Shah
GROUP
18BCH056 III
Grishma Savani
18BCH057 Sejal Jain
18BCH060 Shrey Patel
INTRODUCTION
Fertilizer is any material of natural or
synthetic origin added to the soil to supply
one or more plant nutrients.
The nitrogenous fertilizer industry
includes the production of synthetic
ammonia, nitric acid, ammonium
nitrate, and urea. Synthetic
ammonia and nitric acid are used
primarily as intermediates in the
production of ammonium nitrate
and urea fertilizers.
The nitrogenous fertilizers market was
valued at USD 110.55 billion in 2016.
It is projected to grow at a CAGR of
2.33% from 2017, to reach USD
126.96 billion by 2022.
TABLE OF CONTENTS
01 02 03 04
UREA NITRIC ACID AMMONIUM AMMONIUM
NITRATE SULPHATE
01
UREA
INTRODUCTION
TO UREA
● It is the most important nitrogenous
fertilizer because of its high Nitrogen
Content (46%)
● It is a white crystalline solid which is
widely used in the agricultural industry
INTRODUCTION TO
UREA
• Urea has surpassed and nearly
replaced Ammonium Nitrate as a
fertilizer
• Urea is manufactured as granules as
granules are resistant to moisture and
hence is suitable to fertilizer blends.
INTRODUCTION TO
UREA
• Besides its use in crops, it is also used as
cattle feed supplement to replace the
protein requirements.
• It is also used for the production of
plastics.
• At present day neem coated fertilizer is
used in India.
PROPERTIES OF UREA
Molecular
Mol. Wt. Melting point
Formula
60 NH2CONH2 132℃
Specific gravity
Solubility Density
1.335
119 gm/cc 1.32 gm/cm3
Technical Specifications of Neem Coated
Urea Fertilizer
Parameter Quantity Present
Moisture % by weight, maximum 1.0
Total N % by weight (on dry basis) 46.0
minimum
Biuret % by weight, maximum 1.5
Neem oil content soluble in 0.035
Benzene, % by weight, minimum
Particle size Minimum 90% of the material be
retained on 1 mm and 2.8 mm IS
sieve.
Factors Affecting Synthesis of Urea
production
NH3/CO2 Temper-
Pressure Feed rate
ratio ature
Ideal NH3/CO2 The increase in Urea production rate The ideal Feed rate
ratio is 5:1 i.e., 5 temp also increase with increase as stated before is
moles of Urea and 1 increases the in pressure. The 5:1 i.e. 5 moles of
mole of CO2 production of operating pressure NH3 and 1 mole of
urea up to 175- should be above CO2.
180 0 C. Beyond dissociation pressure
this temp, it falls for the Carbamate
of sharply
How Urea Works as a
Fertilizer?
CO (NH2)2 + H2O CO2 + 2NH3
(Hydrolysed)
2NH3 + 3O2 2NO2 2H2O + 2H + Energy
(Nitrosomos, Nitrosocous)
2NO2 + O2 2NO3 + Energy
The urea is first hydrolyzed by soil water to produce CO 2 &
NH3
How Urea Works as a
Fertilizer?
● The ammonia which is produced in the presence
of O2 & bacteria nitrosomos & nitrosocous under
goes nitrification process and produce nitrates &
liberates some amount of energy.
● The nitrates which are produce under goes
oxidation process in the presence of same
bacteria to produce nitrates which each be easily
taken by plant for there growth It is also produce
energy.
Manufacturing of Urea
Manufacturing
Total recycle Process Stamicarbon Or CO2 Snaprogetli process
Or Ammonium Or NH3 Stripping
stripping process
bicarbonate process
decomposition
Carbon Dioxide
(CO2)
TOTAL RECYCLE
PROCESS
Ammonia
(NH3)
RAW MATERIALS
CHEMICAL REACTIONS
DESIRABLE REACTIONS
1. NH3 + CO2 NH4 COO NH2
(Ammonium carbamate)
2. NH4 COO NH2 NH2CONH2 + H2O
(Ammonium carbonate) Urea
UNDESIRABLE REACTIONS
2NH2 CONH2 NH2 CO NHCONH2 + NH3
(Urea) (Biuret)
Process Flow Diagram
Stamicarbon
Stripping Process
Urea is synthesized at 140 bar and 170-185 ℃
with molar NH3/CO2 ratio of 2.95 to 3.0 in
the reactor. In this the CO2 conversion is
58-60%.
The unreacted ammonia and Carbon
dioxide in the form of liquid ammonium
carbamate, is decomposed using the feed
CO2 as stripping agent.
Stamicarbon Stripping Process
The carbamate decomposition is
slow process and endothermic in The mixture of unreacted
nature reagents and carbamate flows to
the decomposer
The ammonium carbamate will Further concentration of the urea
under goes decomposition to solution leaving the 3-bar
produce urea. decomposition stage takes place in the
evaporation section.
Process Description
1 3
The Stoichiometry ratio of CO2/NH3 for
Over all 99% of CO2 & NH3 are
conversion to urea is essentially above 55% but by
converted into urea in this process.
using excess of CO2 are NH3 the equilibrium can
be achieved 85%
2 4
The urea produce is passed through
A concentrated product of
evaporator to increase the concentration
urea is obtained after
& the passed to the prilling tower to
evaporation
produce urea crystals.
Video on Stamicarbon Process
NH3 stripping process Or Snaprogetli process
● The liquid ammonia & CO2 which is compressed 182-200 atm are passed into synthetic
tower
● The synthetic tower also contains reaction chamber.
● The NH3 reacts with CO2 to from ammonium carbamate, NH3, CO2, & H2O
● The ammonium carbamate which is form under goes decomposition in reaction chamber to
produce urea.
● The mixture of this gases are passed into distillation tower where excess NH3, CO2 & water
are remove from the top of the distillation column.
● The urea solution produce from distillation tower is condense and passed through
evaporator.
NH3 stripping process Or Snaprogetli process
● In evaporator the concentrate of urea increases up to 99%
● The solution form of urea is passed through passing tower to form crystals of urea by
passing cooling air.
Differences in the 3 Processes
Recycling of the reacted NH3
NH3 & CO2 are NH3 & CO2 are NH3 & CO2 are absorb
absorb in water & separated by selective by using light oil and
then recycle as a absorption & then then recycle as slurry
solution of recycle separately in the of ammonium
ammonium form of liquid NH3 & carbamate.
carbamate CO2
Differences in the 3 Processes
Portion of unreacted ammonia recycle
Once through recycle Total recycle Water recycle
Conditions for Good Yield of Urea
● Various Conditions are:
The NH3, CO2 ratio where is
widely ranging from 10% excess
The CO2 should be free from O2 NH3 over the Stochiometric
& H2 to avoid corrosion amount the larger excess gives
better result preheating of NH3
are essential for better result.
Preheating of NH3 is essential
Reaction temp should be high.
for better result
Uses of Urea
1 2 3 4
Urea pills are Urea is used the It is also used as
It is one of the
used as high preparation of urea softening agent
important Nitrogen
protein material formaldehyde and other which is added to
fertilizer is contain
for cattle feed plastics. the product based
46% of Nitrogen
on cellulose.
Advantages of Urea
You can apply urea to soil as a Usage involves little or no fire
solid, solution or, for certain Urea’s high analysis – 46 percent N – helps
or explosion hazard. reduce handling, storage and transportation
crops, a foliar spray.
. costs over other dry N forms
Urea manufacturing releases When properly applied, it results in
Cost of Production is
few pollutants to the crop yield increases equal to other
relatively low compared to
environment. forms of nitrogen
other nitrogenous fertilizers
Why are Inhibitors used in Urea
Fertilizers?
● Urea cannot be applied to bare soil because of significant loss of ammonia by volatilization
because of rapid hydrolysis to ammonium carbonate.
● This hydrolysis can be prevented by the use of compounds called urease inhibitors.
● These inhibitors inactivate the enzyme and thereby prevent the rapid hydrolysis of urea
when it is added to soil.
● This rapid hydrolysis also causes ammonia injury to the seedlings if large quantities of this
fertilizer is placed near the seeds.
● This is the reason why urea fertilizer cannot be mixed with other fertilizer before its
application.
Urea do’s and don'ts
2
1
Store separately from ammonium Don’t use small, fast-moving
nitrate. augers to move the urea.
3 4
Don’t exceed a spreading width of Don’t place urea in direct contact
50 feet when urea is applied. with corn seed.
Urea do’s and don'ts
5 6 7
Keep rates of nitrogen applied Apply urea on seed crops When broadcasting urea on
together with small grain in drill when atmosphere temperature soils of high pH (above 7.5),
to 10 pounds on dry soils and 20 is below 60 degrees incorporate the material into
pounds when soil is moist. Fahrenheit. the soil as soon as possible.
02
NITRIC ACID
PROPERTIES
● Aqua fortis
● Spirit of Niter
Chemical formula HNO3
Molar mass 63.012 gm/mol
Appearance Colorless, yellow or red fuming liquid
Melting point −42 °C (−44 °F; 231 K)
Boiling point 83 °C (181 °F; 356 K) 68% solution
boils at 121 °C (250 °F; 394 K)
Solubility Completely soluble
CHARACTERISTICS
A strong acid
A strong oxidizing agent
Decomposes when exposes to the
sunlight
Nitric acid is a colorless liquid that is used in the
manufacture of inorganic and organic nitrates and
nitro compounds for fertilizers, dye intermediates,
explosives, and many different organic
USES OF NITRIC ACID chemicals.
USES OF NITRIC
●
ACID
To produce TNT, TNG explosives.
● Important chemical
● Get dissolved metals
● To produce fertilizers
● To produce metal nitrates:
○ AgNO3: photographic films and paper
○ KNO3: Gun powder
○ NaNO3: preservation for meat, manufacture of sausages
PREPARATION OF NITRIC ACID
● Concentrated sulfuric acid and sodium nitrate reaction
● Add concentrated H2SO4 acid to the solid NaNO3(s) and distill the mixture
● Ostwald process :In industrial production of HNO3
● Ostwald process is used in industry to production of nitric acid. Ammonia and oxygen are used as raw
materials in the presence of Pt / Rh catalyst. Higher temperatures and pressure are applied in the production
to get a successful yield.
OSTWALD PROCESS
The process converts ammonia to nitric acid in two steps.
During the first step ammonia is oxidized to form nitric oxide (NO) and
nitrogen dioxide (NO2).
During the second step, the nitrogen dioxide that was formed is absorbed
in water. This, in turn, forms nitric acid.
During this process NOx, NH3 and N2O emissions are produced.
ENVIRONMENTAL POLLUTION DUE TO NITRIC ACID MANUFACTURING
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SAFETY
● Nitric acid is a corrosive acid and a powerful oxidizing agent. The major hazard posed by it is
chemical burns, as it carries out acid hydrolysis with proteins (amide) and fats (ester), which
consequently decomposes living tissue (e.g. skin and flesh).
● Concentrated nitric acid stains human skin yellow due to its reaction with the keratin. These
yellow stains turn orange when neutralized. Systemic effects are unlikely, however, and the
substance is not considered a carcinogen or mutagen.
● The standard first-aid treatment for acid spills on the skin is, as for other corrosive agents,
irrigation with large quantities of water. Washing is continued for at least 10–15 minutes to cool
the tissue surrounding the acid burn and to prevent secondary damage.
● Contaminated clothing is removed immediately and the underlying skin washed thoroughly.
● Being a strong oxidizing agent, nitric acid can react with compounds such as cyanides, carbides,
or metallic powders explosively and with many organic compounds, such as turpentine, violently
and hypergolically (i.e. self-igniting). Hence, it should be stored away from bases and organics.
03
AMMONIUM
NITRATE
PROPERTIES
Molecular formula: NH4NO3 (contains 33% N)
Molecular weight: 80.043 gm/mol
Appearance: Odorless and colorless crystal
Meting point: 179.6 C
Boiling point: 210 C
Solubility: Soluble in water, alcohol and NH3
Stable under ordinary conditions of use and storage but emit nitrous
Decomposition: oxide when heated to decompose
Nature: Hygroscopic
METHODS OF PRODUCTION
NH4NO3
Crystallization
Priling Process Stengel Process
Process
Haber-Bosch
Process
Ammonia
Nitric Acid
Ammonia
Oxidation
Process
RAW MATERIALS
CHEMICAL REACTION
STENGEL PROCESS
MAJOR ENGINEERING PROBLEMS
Safety
Corrosion
Crystallization
Conditioned air requirements
USES
● Fertilizer
● Industrial Explosive
STORAGE & PACKING
● Prevent contamination of Ammonium Nitrate with organic materials such as
grease or other hydrocarbon, chlorates, nitrates, and metal salts to avoid fire.
● Ammonium Nitrate is stored in polyethylene lined jute bags
PLANTS PRODUCING
AMMONIUM NITRATE
● Fertilizer Corporation of India Ltd.
● Deepak Nitrate Ltd.
● ICI Ltd.
04
AMMONIUM
SULPHATE
AMMONIUM
SULPHATE
● It is one of the most important nitrogenous
fertilizer because of its moderately high
Nitrogen Content (21%)
● It is a white crystalline solid which is
widely used in the agricultural industry
AMMONIUM SULPHATE
• The primary use of ammonium sulfate
is as a fertilizer for alkaline soils. In the
soil the ammonium ion is released and
forms a small amount of acid, lowering
the pH balance of the soil, while
contributing essential nitrogen for plant
growth.
AMMONIUM SULPHATE
• (NH4)2 SO4 is used to maintain alkalinity
of soil.
• It is used as a fertilizer or crops paddy,
potato and tea.
• At present day neem coated fertilizer is
used in India.
PROPERTIES OF AMMONIUM SULPHATE
Molecular
Mol. Wt. Melting point
Formula
132.14 (NH4)2SO4 513℃
Specific gravity
Solubility Density
1.76
74.4 gm/cc 1.77 gm/cm3
Manufacturing of Ammonium Sulphate
Manufacturing
Using Ammonia,
Using Ammonia and From Coke Oven
Carbon Dioxide and
Sulphuric Acid Gas
Gypsum
Carbon Dioxide
(CO2)
PRODUCTION
OF AMMONIUM
SULPHATE
Ammonia Gypsum
(NH3)
RAW MATERIALS
CHEMICAL REACTIONS
DESIRABLE REACTIONS
1. NH3 + CO2 NH4 COO NH2
(Ammonium carbamate)
2. NH4 COO NH2 + + CaSO4.2H2O (NH4)2SO4 + CaCO3 +2H2O
(Ammonium (Gypsum)
Carbamate)
Process Flow Diagram
The Process
The ammonia & CO2 are passed into
absorption tower in absorption tower This ammonium carbonate solution
the NH3, CO2 and water reacts to is pass into reactor in which finally
1 2
produce ammonium carbonate crushed gypsum is added
In this reactor the ammonium
The (NH4)2 SO2 is completely soluble in
carbonate react with gypsum to
produce a mixture of ammonium water where as calcium carbonate is in
3 4 soluble in water.
sulphate calcium carbonate and water.
This type of reactor are used in series
around 8
Process Description
By using this properties the CaCO3 From vacuum filter 25%
carbonate is separated from (NH4)2 SO4 6 ammonium sulphate is obtain. 8
This mixture is passed through vacuum Then it is passed to a
filter Ammonium separated sulphate crystal evaporator in
from CaCO3 carbonate by passing 7
5 which the temp. maintain
water and by filtration process. is around 109◦C
Process Description
By using this evaporator the concentration of
ammonium sulphate is increase such that it And finally white crystal of
10 ammonium sulphate are 12
contains 2% moisture
obtained.
Finally it passed into Rotary dryer The crystals are then
where the moisture content to reduce 11 either dispatched or stored
9 1% at a temp of 130◦C in sacks.
Conditions for Good Yield of Ammonium
Sulphate
● Various Conditions are:
Reactions of ammonium
carbonate and gypsum solutions
are carried out in a series of CO2 and NH3 are passed until all
wooden vessels or mild steel the gypsum is converted into
vessels having steam coils and CaCO3.
agitators to give a total retention
time of 4 to 6 hours
The slurry produced is filtered
and the calcium carbonate cake
CaCO3 obtained as by product
washed and dewatered. The
is used as a raw material for the
solution is evaporated and the
manufacture of cement.
crystals are centrifuged and
dried in a rotary drier at 120◦C.
Uses of Ammonium Sulphate
1 2 3 4
It is one of the It is used to Used as Fertilizer for Ammonium sulfate
important Nitrogen maintain crops like paddy, potato to bread products as
fertilizer is contain Alkalinity of the and tea. a dough conditioner.
A component in fire
20-21% of soil due to its
extinguisher powder.
Nitrogen pH.
REFERENCES
● https://www.essentialchemicalindustry.org/chemi
cals/nitric-acid.html
● https://www.worldofchemicals.com/449/chemistr
y-articles/manufacturing-of-nitric-acid-by-ostwal
d-process.html
● https://www.tandfonline.com/doi/pdf/10.1080/00
022470.1964.10468252
● https://www3.epa.gov/ttnchie1/old/ap42/ch08/s0
8/final/c08s08_feb1998.pdf
● https://byjus.com/jee/ostwald-process/
● https://www.chemistryscl.com/advancedlevel/ind
ustry/nitric/main.html
● https://youtu.be/QTRXdaWBP2s
THANK YOU
