Chapter II

Nitrogen Industries
 Outline
 Introduction to Nitrogen industry
 Production of the following chemicals
 Ammonia, NH3
 Nitric Acid, HNO3
 Urea, NH2(CO)2
 Ammonium Nitrate, NH4NO3
 other chemicals
 Ammonium sulftae, Ammonium phosphate, Sodium Nitrate,
Potassium Nitrate, cyanamide, ammonium chloride
Introduction

 N2 is abundant in air can be fixed to ammonia by reacting with

hydrogen
 This is used for low-cost chemical supply
 Mostly as nitrogen fertilizers
 Nitric acid and other chemicals
 As Ethiopian economy is based on agriculture and agriculture is
based on fertilizers, nitrogen industry plays important role in it
Ammonia
Properties

 Molecular weight = 17.03

 MP = -77.7 °C
 BP = -33.4 °C
 Solubility in water = Very soluble
 Grades:
 Anhydrous or liquefied NH3, stored at 80° F with pressure of 175
psig
 Aqueous grade (28 wt % NH3)
Consumption Pattern

The end uses for ammonia worldwide:

 Direct application as fertilizer 25%
 Urea (fertilizer & plastic) 21%
 Ammonium phosphate 16%
 Nitric acid 12%
 Miscellaneous 12%
 Ammonium nitrate 8%
 Ammonium sulfate 3%
 Acrylonitrile 3%
Nitrogen consumption in fertilizer

 Mixed fertilizers: Principal elements are NPK

 The composition is expressed as wt% of total N, available P2O5
and soluble K2O
 e.g. 5-10-5 is 5 wt% N, 10 wt% of P2O5, 5wt% K2O
 Generally in granular solids
Manufacturing Processes

 Ammonia gas is synthesised in the chemical industry by reacting

nitrogen gas with hydrogen gas in what is known as the Haber-
Bosch Process
 where do we get these raw materials (N2 and H2) from?
 N2 can be obtained from fractional distillation of liquefied air
 The hydrogen is made by (i) reacting methane (natural gas)
and water or (ii) from cracking hydrocarbons (both reactions are
done at high temperature with a catalyst).
Cont.…

 (i) methane + water (steam) ==> hydrogen + carbon monoxide

CH4 + H2O ====> 3H2 + CO
 The carbon monoxide can be reacted with water in a 2nd stage to
make more hydrogen.
 CO + H2O ====> CO2 + H2
and the carbon dioxide is removed to give the desired
hydrogen gas.
These are called 'reforming' reactions.
Cont..

or (ii) from cracking an alkane hydrocarbon from crude oil

e.g.C8H18 ====> C8H16 + H2
The Haber process is based on the reversible reaction
between nitrogen and hydrogen to form ammonia and using
an iron catalyst.
The balanced equation for the Haber Synthesis reversible
reaction is ..
N2(g) + 3H2(g) ↔ 2NH3(g) ΔH = -92.6 kJ/mol
 Cont.…
Applying Le-chatelier’s principle to produce optimal products of NH3
 A low temperature of 500°C or 773 K
 A high pressure of 200 atm
 Finely divided iron oxide as a catalyst
 Al2O3 and K2O as a promoter
 Removal of NH3 from the mixture as soon
as it is formed
 Process description

• Ammonia synthesis gas (3 mole pure H2: 1 mole pure N2)

compressed (100-1000 atm, depends on the conversion)
• Passed through filter to remove impurities
• Passed over porous iron catalyst at 500-550 °C
• 8-30 % conversion achieved which is removed by condensation
• Unconverted mixture again recycled to achieve 85-90% conversion
Cont..
 Nitric Acid HNO3

 Nitric acid (HNO3). A color less liquid that is used in the

manufacture of inorganic and organic nitrates and nitro
compounds for fertilizers, explosives, and many different organic
chemicals. Continued exposure to vapor may cause chronic
bronchitis; chemical pneumonitis may occur.

 NITRIC ACID, RED FUMING is a pale yellow to reddish brown

liquid generating red-brown fumes and having a suffocating odor.
Very toxic by inhalation. Corrosive to metals or tissue.
Physical Properties
Mol. Wt. : 63.03
MP: -42 °C
BP: 86 °C with decomposition
Completely miscible with water
Forms a constant boiling mixture at 110 °C and 760 mm
of Hg, which contains 68 wt. % HNO3
Grades: Concentrated (95%), Fuming (>86%),
Red fuming (>95% with 10-15% excess oxides of
nitrogen), nitrating (50-80% HNO 3 -15-48% H2SO4)
CHEMICAL PROPERTIES
 Stability :Pure nitric acid is not very stable. Even at ordinary
temp. in presence of sunlight it undergoes slight decomposition.
4 HNO3→ 2 H2O + 4 NO2+ O2.
 Oxidizing properties: Nitric acid is a strong oxidizing agent as
shown by its large positive E° values.

NO3-(aq) + 2H+ (aq) e-→ NO2 (g) + H2O (l) E° = 0.79 V

CHEMICAL PROPERTIES
 Reactions with metals: Nitric acid dissolves most metals
including iron, copper, and silver, with generally the liberation of
lower oxides of nitrogen rather than hydrogen. It can also
dissolve the noble metals with the addition of hydrochloric acid.
Cu + 4HNO3 → Cu(NO3) 2 + 2NO2 + 2H2O
 Reactions with non-metals: Reaction with non-metallic
elements, with the exception of silicon and halogen, usually
oxidizes them to their highest oxidation states as acids with the
formation of nitrogen dioxide for concentrated acid and nitrogen
oxide for dilute acid.
C + 4HNO3 → CO2 + 4NO2 + 2H2O
Methods of Production
 Industrially nitric acid is prepared by following 3 methods:
•CHILE SALTPETRE METHOD BY NANO3
•BRIKLAND EYDE’S METHOD BY USING AIR
•OSTWALD’S METHOD BY AMMONIA SOLVEY PROCESS
CHILE SALTPETRE METHOD (By NaNO3)
 It is the first commercial process of manufacture of nitric acid
from sodium nitrate extracted from Chile saltpeter. The process is
now become obsolete since second decade of nineteenth century
 Raw materials
 Sodium Nitrate
 Sulfuric acid
The reactants
at heated at
2000 °C

Figure: manufacturing of nitric acid from Chile saltpeter

Cont..
Cont..
Cont..
Cont.…
 BRIKLAND EYDE’S METHOD (Arc Process)
 Raw materials
Air
Water
 Process:
CO2 and dust free air is heated in an arc furnace at 3000 °C. Nitric
oxide is formed. Gases coming out from the furnace are cooled at
1000oC by passing through cooler then gases are passed in a boiler
and cooled at 150oC. Cold water is circulated around the boiler to
cool the gases. Gaseous mixture is now passed through aluminum
tubes. The temperature of gaseous mixture becomes 50oC.
Gaseous mixture is passed in oxidizing tower where NO is oxidized
into NO2.
2NO + O2——–> 2NO2
NO2 is absorbed in water in absorption tower then dilute HNO 3 is
obtained.
3NO2+ H2O ——-> 2 HNO3+ NO
Now HNO3 is not manufactured by this method because consumption
of electricity is very high to maintain the temperature 3000 °C.
Figure: manufacturing of Nitric acid by arc process
OSTWALD’S METHOD
Principle :
NH3 is oxidized into NO by air at 800 °C in
presence of Pt (Platinum) catalyst.
 Raw Materials

 Ammonia
 Air
 Platinum

 Water
 Steam credit @ 200psig
 Power
 PROCESS:
 Mixture of NH3 and O2 is passed through catalyst chamber
containing Pt-gauge. Temperature of the catalyst is kept at 800
°C. About 95 % NH3 is converted into NO.
 4NH3+ 5 O2——–> 4NO + 6 H2O + 21.6 K.Calorie (exothermic)
 Heat liberated maintains the temperature of the catalyst. The
gases coming out are cooled to about 50 °C and mixed with more
O2. This gaseous mixture is passed in oxidizing tower where NO
is oxidized to NO2.
 2NO + O2——> 2NO2
 NO2 is passed in absorption tower. The dilute solution of HNO3 is
obtained.
 3NO2+ H2O ——> 2HNO3+ NO
Concentration

 In order to increase the concentration of HNO3, vapours of

HNO3 are passed over concentrated H2SO4. Being a dehydrating
agent, H2SO4 absorbs water from HNO3and concentrated HNO3
is obtained.
Nitric Acid Safety and Handling:
 Nitric Acid is an extremely corrosive acid capable of causing
severe chemical burns very rapidly.
 When handling Nitric Acid in the workplace, it is highly
recommended to wear:
 Chemical Safety Glasses.
 Face shield.
 Gloves

 As an added safety precaution, eyewash station and washing

stations should be easily accessible in case of exposure to nitric
acid.
First Aid:
 In the event of exposure to Nitric Acid, follow these first aid guides:
 Inhalation-Seek fresh air and immediate medical attention.
 Eye Contact-Immediately wash eyes with plenty of water for at least 15
minutes to prevent any further damage and seek immediate medical
attention.
 Skin Contact-Immediately wash affected area with water for at least 15
minutes and remove any contaminated clothing. Seek medical attention
as soon as possible.
 Ingestion-Do NOT induce vomiting. Rinse mouth with water and drink
a glass of water or milk. Seek medical attention immediately.
USES:

 As a starting material in the manufacture of nitrogen fertilizers

such as ammonium nitrate & ammonium etc. Large amounts are
reacted with ammonia to yield ammonium nitrate.
 As a nitrating agent in the preparation of explosives such as TNT,
nitro-glycerine, cellulose poly-nitrate, ammonium picrate.
 It is used as a medicine to remove chancres and warts.
 Used in fibers, plastics and dyestuffs industries
 Used in metallurgy and in rocket fuel production.
 It is used in calorimetric test to distinguish between heroin and
morphine.
Ammonia Fertilisers
 ammonium nitrate fertilizer …
NH3(aq) + HNO3(aq)  NH4NO3(aq)
 ammonium phosphate fertilizer
3NH3(aq) + H3PO4(aq)  (NH4)3PO4(aq)
 ammonium sulfate fertilizer …
2NH3(aq) + H2SO4(aq)  (NH4)2SO4(aq)
 urea fertilizer …
2NH3(aq) + CO2(g)  (NH2)2CO(aq) + H2O(l)
AMMONIUM PHOSPHATE

 Ammonium phosphate ((NH4)3PO4) also known as ammonium

orthophosphate is the salt of ammonia and phosphoric acid. It
consists of ammonium cations and phosphate anion. It is water
soluble and the aqueous solution on boiling losses ammonia.
 There are two major types of ammonium phosphate which are
mono ammonium phosphate (MAP, NH4H2PO4) and diammonium
phosphate (DAP, (NH4)2HPO4)
1. Monoammonium 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 55% and nitrogen
content 11-12%.
2. Diammonium phosphate (DAP)
With more ammonia, technical grade diammonium phosphate
(DAP) containing 16 to 18% nitrogen and 20 to 21 % phosphorus
(46% P2O5) is formed.
Raw Materials
Ammonia
Phosphoric acid
AMMONIUM SULFATE
 Ammonium sulfate containing 21% nitrogen is another important
nitrogenous fertilizer.
 MANUFACTURING METHOD
a) Flue Gas
Flue gases are source of the ammonium sulfate. The metallurgical
smelters and coal burning power plants liberate large quantities of
SO2 that pollute the atmosphere. SO2 is collected and converted into
sulfuric acid, (NH4)2SO4 is then produced by passing ammonia gas
through 60% sulfuric acid placed in lead lines vats at about 60°C the
crystals of ammonium sulfate separate out on cooling.
2NH4OH + H2SO4 (NH4)2SO4 + 2H2O
b) As by-product from caprolactam
(NH4)2SO4 solution is formed during the manufacture of
caprolactam. The waste liquor containing 35% solution of
ammonium sulfate is concentrated, and ammonium sulfate, is
recovered by crystallization, centrifuging and drying. The crystals
are dried after separation by filtration or by centrifuge. The mother
liquor overflowing from the crystallizer is acidified and recycled to
the absorber.
c) Direct neutralization or Synthetic manufacturing
Manufacturing process of Urea
Introduction:
 an important nitrogenous fertilizer
 It is used in solid fertilizer, liquid fertilizer, formaldehyde resins
and adhesives.
 Rouelle first discovered urea in urine in 1773.
 He was followed by the synthesis of urea from ammonia and
cyanic acid by Woehler in 1828. This is considered to be the first
synthesis of an organic compound from an inorganic compound.
 In 1870, Bassarow produced urea by heating ammonium
carbamate in a sealed tube in what was the first synthesis of urea
by dehydration.
 PROPERTIES OF UREA :
PHYSICAL PROPERTIES OF UREA
 Urea is a white, odorless, hygroscopic
solid. It is non-corrosive.
CHEMICAL PROPERTIES OF UREA
 Molecular weight 60.05
 Relative humidity 60 %
 Maximum Nitrogen content 46.6 %
 Specific gravity 1.335
 Heat of fusion 60 Cal/gm
(endothermic)
 Bulk density 0.74 gm/cc
USES OF UREA
 About 56 % of Urea manufactured is used in solid fertilizer.
 About 31 % of Urea manufactured is used in liquid fertilizer.
 Urea-formaldehyde resins have large use as a plywood (laminate)
adhesive.
Manufacturing process of Urea
 Urea is produced from NH3 & CO2 in two equilibrium reactions:
 1) CO2 + 2NH3 NH2COONH4 H= -37.4 Kcal/gm mol
 2) NH2COONH4 NH2CONH2+ H2O H= +6.3 Kcal/gm mol
(ammonium carbamate)

The urea manufacturing process are designed to maximize these reactions

while inhibiting biuret formation:

This reaction is undesirable, not only because it lowers the yield of urea,
but because biuret burns the leaves of plants. This means that urea which
contains high levels of biuret is unsuitable for use as a fertilizer.
Manufacturing process of Urea

 A mixture of compressed CO2 and NH3 at 180 atm is reacted to form

ammonium carbamate. This is an exothermic reaction, and heat is
recovered by a boiler which produces steam.
 A mixture of urea, ammonium carbamate, H2O and unreacted
(NH3+CO2) is produced.
 This liquid effluent is let down to 27 atms and fed to a special flash-
evaporator containing a gas-liquid separator and condenser
 Unreacted NH3, CO2 & H2O are thus removed & recycled. An
aqueous solution of carbamate-urea is passed to the atmospheric
flash drum where further decomposition of carbamate takes place.
 The off gases from this step can either be recycled or sent to NH 3
processes for making chemical fertilizer.
Manufacturing process of Urea
 The 80 % aqueous urea solution can be used as it is, or sent to a
vacuum evaporator to obtain molten urea containing less than 1
% water.
 The molten mass is then sprayed into a prilling tower. To avoid
formation of biuret and keep it less than 1 %,
 the temperature must be kept just above the melting point for
processing times of 1-2 seconds in this phase of the operation.
Manufacturing process of Urea

Granulation
 Oversized granules are crushed and combined with undersized
ones for use as seed.
 All dust and air from the granulator is removed by a fan into a
dust scrubber and discharges the air to the atmosphere.
 The final product is cooled in air, weighed and conveyed to bulk
storage ready for sale
Figure: Schematic representation of Urea synthesis
Process flow diagram
 Uses
 As a component of fertilizer and animal feed, providing a
relatively cheap source of fixed nitrogen to promote growth.
 As a raw material for the manufacture of plastics specifically,
urea-formaldehyde resin.
 As a raw material for the manufacture of various glues (urea-
formaldehyde or urea-melamineformaldehyde).The latter is
waterproof and is used for marine plywood.
 Uses
 As an alternative to rock salt in the de-icing of roadways and
runways. It does not promote metal corrosion to the extent that
salt does.
 As an additive ingredient in cigarettes, designed to enhance
flavor.
 Sometimes used as a browning agent in factory.
 As an ingredient in some hair conditioners, facial cleansers, bath
oils and lotions.
 Uses

 As a clean burning fuel for motor vehicles and stationary engines.

 to make urea nitrate, a high explosive
 Used, along with salts, as a cloud seeding agent to expedite the
condensation of water in clouds, producing precipitation.
 The ability of urea to form clathrates (also called “loose
compounds” ) was used in the past to separate paraffins.
Thank you

Questions?
 Assignment 1
Presentation

 Group 1. Nitrogen Fertilizers

 Group 2. Phosphate Fertilizers
 Group 3. Potash Fertilizers
 Group 4. Mixed Fertilizers
 Group 5. Pesticides
Requirements
 Introduction
 Raw material required to manufacture the final product
 Manufacturing process details(it should be more descriptive)
 Application
 Environmental impact
 Addition relevant points can also be included