Chapter 1 Introduction

1.1 About IFFCO

Indian Farmers Fertilizer Co-operative Limited (IFFCO) established on 3 rd November 1967, a multi-unit
co-operative organisation with broad objectives of augmenting fertilizers, Indian Farmers Fertilizer
Co-Operative Limited (IFFCO) was production, ensuring fertilizer distribution system and educating
training and guiding the former for improving agricultural productivity.

1.2 Objectives of IFFCO

1. Augmenting fertilizers production and ensuring fertilizer availability at farmers door step.

2. Strengthening co-operative fertilizer distribution.

3. Educating, training and guiding the farmers for improving agricultural productivity and
rural economy.

4. Promoting Nation’s growth modern farming techniques.

1.3 Aonla Unit

Towards increasing the fertilizer production under over all national planning for utilisation of natural
gas available in Bombay High a major program for setting of six new gas based fertilizer unit was
envisaged by the Government of India along the HBJ gas pipe line. IFFCO was entrusted for setting up one
fertilizer unit at Aonla , Bareilly unit annual capacity of 14.52 lakhs MT Urea. The Aonla-1 plant was
built in a record time of 36 months and started its commercial urea product on 16th July 1988. The plant
achieved a new record by attaining nearly 98% capacity utilization in the very first year of its
commercial production. Aonla-2 started commercial production on 25th December 1996.For
Ammonia, plant capacity is 2*1350 MT/day and for Urea, plant capacity is 2*1100 MT/day. Major
input is Natural Gas i.e. 3.3 Million Cubic Meter/day.

1
1.4 Achievements of IFFCO

There are many achieving standards of IFFCO Aonla unit that makes IFFCO pride of all other cooperative
fertilizer limit units. The achievements of IFFCO Aonla unit:

Aonla project “Mechanical Completion Achieved” within 36 months from zero date in spite of delay in
supply of natural gas by m/s GAIL and CO2 compressors by BHEL.

Implementation of Aonla project has been taken as model for future projects by Government of
India IFFCO has begged two prestigious awards. One for best implementation (second prize): other for
“Technical Film New Horizons - Aonla project” by FAI.

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Chapter 2 Ammonia-1 Plant

2.1 General

The fertilizers produced in India can be classified broadly into two group’s viz. nitrogenous
fertilizers, and phosphatic fertilizers. Plants may be producing only nitrogenous fertilizers like urea,
Ammonium Chloride, or only phosphate fertilizers like super phosphates.

Here in this study we are dealing with Ammonia. Ammonia is a compound of nitrogen and hydrogen. It is
a colourless gas with a characteristic pungent smell. It is a common nitrogenous waste, particularly
among aquatic organisms, and it contributes significantly to the nutritional needs of terrestrial
organisms by serving as a precursor to food and fertilizers. Ammonia either directly or indirectly, is also
a building block for the synthesis of many pharmaceutical products or is used in many commercial
cleaning products. It is mainly collected by downward displacement of both air & water.

2.2 Objectives

The specific objectives of the study are as follows:

1. To study about the ambient air quality, safety and occupational hazards and recent
development in IFFCO (Aonla).

2. To study about the production of Ammonia in the ammonia-I and ammonia-II plant at
IFFCO (Aonla).

2.3 Uses of Ammonia

India is an agrarian country. Here approximately 40% population depends upon farming for which
urea
is an important component. It has the following main uses:

1. Ammonia is used as a precursor to nitrogenous compounds.

2. Used as a reactant for the production of urea fertilizers.

3. Used as antimicrobial agent for food products.

 4. Used in the manufacturing of dyes.

5. As a raw material for many chemical products.

2.4 Ammonia synthesis

At IFFCO Aonla plant ammonia is produced by the action of nitrogen and hydrogen. The special
part of this plant is that the efficient use of natural gas is involved here so as to recover the
residual units.

2.5 Reaction involved in Ammonia synthesis

The main reactions involved in ammonia synthesis are as follows:

N2 + 3H2 2NH3

According to the stoichiometric ratio the percentage of nitrogen to hydrogen should be maintained
in the ratio of 1:3. The optimum condition for the production of ammonia is that low temperature
must be maintained so as to achieve high pressure for the production of ammonia show in the fig.
(2.1)
Fig 2.1: Flowsheet of Ammonia Plant

Source: IFFCO Ammonia Plant Manual

 Table 2.1 Physical properties of Ammonia

Molecular weight 17.031g/mol

Boiling point -33.34oC

Melting point -77.73oC

Density 0.86kg/m3

Standard molar entropy 193 J/mol/K

Enthalpy of formation -46KJ/mol

Dipole moment 1.42D

Refractive index 1.3327

Viscosity at -40⁰C 0.276 cp

Basicity 4.75

Acidity 32.5

Vapour pressure 857.3 KPa

Solubility in water 18-47 wt%

Source: IFFCO Ammonia Plant Manual

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Chapter 3 Ammonia Production

3.1 Introduction

Ammonia (NH3) is of great importance to the agriculture industry as a major constituent of the
nitrogen-rich fertiliser like Urea and as a nutrient.

3.1.1 Ammonia synthesis

Ammonia is synthesized from hydrogen (from natural gas) and nitrogen (from the air). Natural gas
contains some sulphurous compounds which damage the catalysts used in this process. These are
removed by reacting them with zinc- oxide, e.g.

ZnO + H2S ZnS + H2O

The methane from the natural gas is then converted to hydrogen:

CH4 + H2O 3H2 + CO

CH4 + 2H2O 4H2 + CO2

CO + H2O H2 + CO2

Air is mixed in with the gas stream to give hydrogen: nitrogen ratio of 3:1. Water, carbon monoxide and
carbon dioxide (all of which poison the iron catalyst used in the ammonia synthesis) are removed. The
carbon monoxide is converted to carbon dioxide for use in urea production, and the carbon dioxide
removed:

CO + H2O CO2 + H2

The remaining traces of CO and CO2 are converted to CH4 and then the gases cooled until the water
becomes liquid and can be easily removed.
3.1.2 Urea synthesis

Urea is made from ammonia and carbon dioxide. The ammonia and carbon dioxide are fed into the
reactor at high pressure and temperature, and the urea is formed in a two- step reaction:

2NH3 + CO2 NH2COONH4

(ammonium carbamate)

NH2COONH4 H2O + NH2CONH2

(urea)

The urea contains unreacted NH3 and CO2 and ammonium carbamate. As the pressure is reduced and
heat applied the NH2COONH4 decomposes to NH3 and CO2. The ammonia and carbon dioxide are recycled.
The urea solution is then concentrated to give 99.6% w/w molten urea, and granulated for use as
fertiliser and chemical feedstock.

3.2 The Ammonia Manufacture Process

3.2.1 Hydrogen desulphurisation

Hydrogen is produced by the reaction of methane with water. However, before this can be
carried out, all sulphurous compounds must be removed from the natural gas to prevent catalyst
poisoning. These are removed by heating the gas to 400ᵒC 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 770oC 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. Following reactions takes place:
 CH4 + H2O 3H2 + CO

CH4 + 2H2O 4H2 + CO2

CO + H2O H2 + CO2

This gaseous mixture is known as synthesis gas.

3.2.2 Nitrogen addition

The synthesis gas is cooled slightly to 735ᵒC. 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

In addition, 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. This is carried out in the next three steps.

3.2.3 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 360ᵒC and then
over a Cu/ZnO/Cr catalyst at 210ᵒC. The same reaction occurs in both steps, but using the two steps
maximizes conversion.
3.2.4 Water removal

The gas mixture is further cooled to 40ᵒC, at which temperature the water condenses out and is
removed.

3.2.5 Removal of carbon oxides

The gases are then pumped up through a counter-current of G.V. solution (an MDEA solution).
Carbon dioxide is highly soluble in G.V. SOLUTION, 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 325ᵒC:

2CO + 3H2 CH4 + H2O

CO2 + 4H2 CH4 + 2H2O

The water which is produced in these reactions is removed by condensation at 40ᵒC as above. The
carbon dioxide is stripped from the G.V. SOLUTION and used in urea manufacture. The G.V.
SOLUTION is cooled and reused for carbon dioxide removal.

3.2.6 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 5ᵒC. The ammonia present is removed and the unreacted gases heated to 400ᵒC at
a pressure of 330 bar 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
220ᵒC 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 occurring in
the ammonia converter is:

N2 + 3H2 2NH3
The ammonia is rapidly decompressed to 24 bar. 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.

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Chapter 4 Process Technology And Safety Measures

4.1 Process technology

Urea is produced by synthesis from liquid ammonia and gaseous carbon dioxide. Ammonia and
carbon dioxide reacts to form ammonia carbamate, a portion of which dehydrates to form urea and
water. The fraction of ammonia that dehydrates is determined by the ratio of various reactants, the
operating pressures, temperature and the residence time in the reactor.
The reaction of ammonia and carbon dioxide to produce urea takes place in two stages at elevated
pressure and temperature.

2NH3 + CO2 NH2COONH4 H=-38.1 kcal/kg

Liquid corbon ammonium
Ammonia dioxide carbomate
5 NH2COONH4 NH2CONH2 + H2O H=+7.1 kcal/kg
Ammonium urea
carbomate
The first reaction is strongly exothermic and therefore heat is liberated as this reaction occurs. With
excess Ammonia and carbon dioxide conversion to carbamate is almost 100%, provided solution pressure
is greater than decomposition pressure. Urea Reactor is shown in fig. 3.1. The decomposition pressure is
the pressure at which carbamate will decompose back into CO2 and NH3.i.e.
6 NH2COONH4 NH3 + CO2

The second reaction is endothermic. The heat for this reaction comes from the formation of carbamate.
The solution effluent from the reactor being a mixture of urea solution, ammonium carbamate,
unreacted ammonia water and carbon dioxide is extremely corrosive in nature.
Fig 4.1. Process flow diagram of Urea Plant

Source: IFFCO Urea Plant Manual

4.1.1 Stripping Process

In this process description of ammonium carbamate is done at the synthesis process by using either CO2
or NH3 vapours in the falling film type decomposer normally called stripper. The reactor effluent is
allowed to fall through the stripping agent from bottom, which travels upward. M.P steam condensing on
the shell side of stripper supplies heat for decomposition of ammonium carbamate. Currently SNAM
PROGETTI process does not require injection of ammonia vapours at the stripper bottom. Only high mole
ratio of CO2 and NH3 is maintained in the reactor.
At higher mole ratio of NH3 and CO2 ammonia liberated in the stripper is adequate to carry out
stripping effectively. Since the reactor stripper system, condenser system operates at nearly same
pressure; it is possible to feed recycle carbamate either by gravity flow which however necessitates
the installation of carbamate condenser at a much higher elevation so as to give the required head or to
use a recycle ejector using a part of feed reactants as motive fluid. SNAM PROGETTI was the first to
decide use of such ejector and locate condenser at the ground level. Since a major portion of unconverted
carbamate is decomposed and recycled to reaction at synthetic pressure, load on downstream
decomposition and recovery section is comparatively much less resulting in lower utility consumption.
Further since the synthesis pressure in the stripping is lower, it is possible to employ steam driven
centrifugal CO2 compressor, which have low maintenance and operating cost.

4.1.2 Theory of stripping process

The theory of stripping is based on the Henry’s law. The concentration of component in solution while in
equilibrium with vapour phase is directly proportional to partial pressure of component concentration
in solution can be changed.
This can be illustrated as follows:-
In stripper we introduce excess NH3 along with the reactor effluent. The NH3 vapours increase the
partial pressure of ammonia over the solution. As total pressure remains the
same, partial pressure of CO2 in vapour phase to approach the equilibrium concentration. Stripping by an
external source by condensation of medium pressure steam.

4.1.3 Effect of process variable

Carbamate formation takes place with liberation of heat and urea formation with adsorption of
heat.

The former reaction is rapid and the later is slow. The equilibrium conversion of urea will be favoured
under the following conditions:
1. Higher NH3 concentration.
2. Less H2O concentration.
3. Higher temperature.
4. Increased residence time.

4.2. Effect of NH3 and CO2 ratio

Theoretical ratio of NH3 and CO2 is 2, but in this condition urea yield is only around 43.44% at 170 atm &
1550C. This low yield can be improved by changing NH3 and CO2 ratio. When the excess ratio of ammonia
is increased to 80%, urea yield will change from 43.50% to 85.2%. In general almost all the urea plants are
operated and NH3 and CO2 ratio is around 2.5 to 5.0.

4.3 Effect of H2O and CO2 ratio

Water is a product of urea solution formation. One mole of water is produced every time, when one
mole of urea is formed. The presence of excess water shifts the equilibrium reaction in the reverse
direction and yield of urea is poor. However H2O has to add for recycling unconverted NH3 and CO2
batch back to the reactor. Lower the amount of H2O in reactor, higher is the yield of urea. Too low
concentration of water in low-pressure recovery reaction results in higher carbonate concentration and
this causes pumping problem in piping system. Study shows that presence of one mole of excess water
per mole of carbonate reduces equilibrium yield of urea to half.
4.4 Residence time

Urea conversion reaction is slow and takes 20 minutes to attain equilibrium. Considering the slowness of
reaction, urea reactor is so designed that the residence time should not be more than 20 minutes.

Higher residence time favours equilibrium conversion and normally reactors are designed for the
residence time of 30 minutes to 1 hrs, 68% urea conversion takes place with residence time of 30
minutes at a mole ratio of 4:1 and the temperature of 188ᵒC whereas to achieve 60% conversion
with the mole fraction of 2:8:1 at 181ᵒC almost a residence time of 55 minutes is required.

4.5 Biuret in Urea

A problem facing every manufacturer is the biuret formation during the production process. It is an
undesirable product as it is toxic to plants. It should not be exceeded to 1.5% in urea as per fertilizer
control order. Biuret formation takes place when urea suction is heated in absence of free
ammonia.

2NH2CONH2 NH2CONHCONH2 + NH3

Urea biuret ammonia

4.6 Factors of safety and health

4.6.1 Risk of accidents and harmful exposures: Areas of concern

1. Dangerous Materials
2. Hazards of Pressure Vessels
3. Flammable Gases, Vapours And Dust Hazards
4. Entry in to Confined Spaces
5. Working with Pipelines
6. Sampling and Gauging
7. Hazards due to Instrument Failures
4.6.2 Dangerous Materials

1. Explosives
2. Gases
3. Inflammable Liquids
4. Inflammable Solids
5. Oxidising substances
6. Toxic and Infectious substances
7. Radio Active Substances
8. Corrosive Substances

4.6.3 Health Hazards

1. Identification of potential health hazards.

2. Assessment of levels of physical and chemical hazards
3. Control of hazards by various techniques
4. Adequate awareness among the workers.
5. Periodic medical examination of the workers.
6. Personal protection for occasional exposures.
7. Proper hygiene and decontamination facilities.

4.6.4 Setup of fire and safety at IFFCO Aonla

All staff of Fire & Safety, Health and Environment sections are well qualified Engineers, Fire& safety
officers and Doctors.

4.6.5 Equipments for fire fighting

IFFCO-AONLA is well equipped with all Fire & Safety appliances like Fire Tenders-3 with a pick up van, all
types of extinguishers like DCP,CO2,WATER CO2 Foam types in adequate numbers, PPES like Breathing
Apparatus of different types &capacities, Online Air masks at various Hazardous areas, Gas tight Suits,
Aluminised Suits, Explosive meters, Portable Gas Detectors , Chlorine Emergency Leakage Kit, Air
compressor for air cylinders filling,
PVC apron & suits, gum boots, safety shoes, safety belts , Various types of hand gloves
,ladders, nylon lifesaving net, Canisters, safety torches, dust pads etc.
Fire Detection/ Alarm System for Plant Control Rooms, Administrative building, Cable Galleries,
Transformers are also provided. These are of Ionization, Optical & Heat sensing type.

4.6.6 Safety equipments

1. Gas masks for use in leakage of Gases like Ammonia, Chlorine, etc. are available in all the Plant.
Apart from this, breathing apparatus supplied by MSA, (USA) are available in all the control
rooms and at Ammonia storage tank area.

2. Air line systems are provided in Urea and Ammonia control rooms for which air is supplied
from instrument air header. These can be used by the operators working in control room in
case of Ammonia leak.

3. Explosive meters supplied by M/s. MSA, (USA) and RESPO PRODUCTS are available in all the
plants for checking any leak of gases and testing the vessel and operating areas, before
issue of hot work permit or permit for vessel entry etc.

4. Personnel Protective appliances like safety helmet, safety goggles hand gloves etc., are issued to
all the employees. Apart from this Eye wash showers, face shields, PVC suits etc. are installed in
all sections of the plant.

5. Gas tight suits, chemical splash suits, Fire proximity suits and other suits are available to handle
emergencies like toxic release, fire.

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Chapter 5 Summary and Conclusion

5.1 Summary

Based on the knowledge gained by the training:

1. Ammonia is natural occuring compound, which can be synthesized in laboratory as well as many
process industries.

2. Ingenuity is used to overcome the difficulty such as corrosion problems, recovery of off gases
and economic process routes that results in the present day development.

3. Urea is very useful fertilizer that is commercially used by the farmers.

4. It is prepared by treating ammonia and carbon dioxide.

5.2 Conclusion

This training report presents all the information about process methodology of the plant according to the
equipment individually, their process conditions, temperature, pressure and operating conditions. All the
necessary guidance for the preparation of the report is taken from the training manual of IFFCO Aonla.

There is a limitation in this training report regarding technical details like optimization simulation and designing.

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 BIBLIOGRAPHY

1. IFFCO Urea plant manual.

2. IFFCO AMMONIA plant manual

3. www.iffco.in/About/