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RISK MANAGEMENT IN AMMONIA/ UREA PLANTS

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DOI: 10.13140/RG.2.2.35168.20489

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RISK MANAGEMENT IN AMMONIA/ UREA

PLANTS
By
Prem Baboo
Former Sr. Manager, National Fertilizers Ltd, India

Abstract-
Risk Management is the Identification, Analysis
and Economic Control of those Risks which can Keyword
Threaten the Assets (Property, Human) or the
Ammonia plant, fertilizer production industry,
Earning Capacity of an Enterprise” Risk
risk management, Risk, Fire, Explosion,
management is the process of identifying,
assessing and controlling threats to an Introduction
organization's capital and earnings. These risks
stem from a variety of sources including Ammonia is one among the largest volume
financial uncertainties, legal liabilities, inorganic chemicals in the Fertilizers and others
technology issues, strategic management errors, chemicals process industries. About 80% or
accidents and natural disasters. The article more of the ammonia produced is used for
intended The Fertilizer Plant pose fire, explosion fertilizing agricultural crops. From 1980 to 2021,
and toxic hazards due to unwanted and the capacity of single stream ammonia plant has
accidental release of natural gas as well as increased drastically in the range from 1500-
process gas containing CO, H2, Methane and 3500 TPD. Presently, the largest ammonia plant
toxic gases like Ammonia and Chlorine. The has the capacity of 3300 TPD But very soon
effect zones of the fire and explosion hazard are will become as the largest single-stream
generally restricted within the plant boundary ammonia plant in the world, which is due on-
limits and near the source of generation itself. stream in the middle of 2022, has the capacity of
However, effect of accidental release of 4000 TPD. The large volume of Ammonia
Ammonia and other toxic gases may go outside storages are also very risky. It is expected that
the factory premises. This section deals with the capacity of single stream may even reach 5000
failure modes, listing of failure cases leading to TPD, considering current pace of development.
different hazard scenarios, consequence But these large plants also pose increased hazard
modeling and the risk evaluation. Consequence and risk associated with it. A successful risk
analysis is basically a quantitative study of the management program helps an organization
hazard due to various failure scenarios to consider the full range of risks it faces. Risk
determine the possible magnitude of damage management also examines the relationship
effects and to determine the distances up to between risks and the cascading impact they
which the damage may be affected using could have on an organization's strategic goals.
internationally accepted mathematical models. Risk management has perhaps never been more
important than it is now. The risks modern
organizations faces have grown more complex,
fueled by the rapid pace of globalization. New

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risks are constantly emerging, often related to digital technology. Climate change has been
and generated by the now-pervasive use of dubbed a "threat multiplier" by risk experts.
This article descriptive study which carried out explosion toxicity and Mond Indices
in observation using a cross sectional design. Computation of Ammonia plants. The
Variables in this study included hazard Toxicity Index is arrived at from fire and
identification, basic risk analysis, risk control explosion index. The Toxicity Index (TI) is
that has been done, existing risk analysis, and
computed using the health factor (Nh) ,
risk reduction assessment. The tools used for the
maximum allowable concentration (MAC)
data collection were observation sheets,
interview guide sheets, and Job Safety Analysis
value ranging between <5,5-50,>50
sheets. Data that has been obtained through respectively. Similarly for Nh rage from 0-4
observation and interviews was processed using ,a corresponding factor , The is assigned.
Fine semi quantitative technique. Results: The The TI can be calculated using the following
results of hazard identification known to have as formula
many as 6 potential hazards. The assessment
results in the basic risk analysis showed that the (𝐓𝐡 + 𝐓𝐬)𝐗 𝟏 + 𝐆𝐏𝐇 + 𝐒𝐏𝐇)
𝑻𝑰 =
initial risk level consisted of 3 risks with very 𝟏𝟎𝟎
high level, 2 risks with a substantial level and 1
The Degree of hazard is identified based on
risk with priority 3 level. After the risk control
effort was applied, the results of the assessment
FEI and TI range according to the following
in the existing risk analysis showed that the level criteria.
of risk has decreased significantly. The main
Sr. No. FEI range Degree of Hazard
reason for increase in the capacity of a single
1 0-60 Light
stream to reduce specific production cost
2 61-96 Moderate
through so-called economy of scale, i.e., if
3 97-127 Intermediate
design output is doubled, the capital cost
4 128-158 Heavy
increases by only 50- 60%. There are also some
5 159 & abobe Severe
savings on operating costs, particularly in terms
Table-1
of the thermal economy and labour. Though
ammonia plant has well proven technology; Sr. No. TI range Degree of Hazard
however, there are problems and failures of 1 0-5 Light
process equipments, machineries, instruments 2 5-10 Moderate
and control systems etc., many of these are not 3 >10 Severe
reported in the literature. Safety of a plant can be Table -2
improved, but cannot be guaranteed.
Hazard Identification In Fertilizers Complex the ammonia plant
Hazard indices computation helps in ranking constitutes one of the most hazardous area.It
the most vulnerable unit by assigning the is therefore of vital importance to collect and
penalties based on the properties of the analyze methodically the data based on
chemicals used and type of accidents.
installation.Table-1 shows the fire and

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Units M.F FEI Index Mond Toxicity of Degree

Index MI Hazard
FEI TI
Primary 21 130.4 2531 ---- Heavy ---
Reformer
Secondary 21 128 2579 ------ Heavy -----
Reformer
Converter 21 128.2 2568 ---- Heavy ------
HT
Converter 21 135.4 2562 ---- Heavy -------
LT
Metanator 21 252 2109 --- severe ----
Amm 21 166 2553 24.12 Severe High
Converter
Seperator 4 22.4 2075 21.2 High High
Amm 4 23.8 412 13.3 light High
Storage
Amm 4 23.8 412 14.2 Light high
Tanker
Table-3
Brief Description of Ammonia Production argon and methane to a limited extent. The
The raw material of Ammonia production are source of H2 is demineralized water and the
Natural gas, Steam, Air and Power. In old plant hydrocarbons in the natural gas. The source of
Heavy oil/Naphtha were used which requires N2 is the atmospheric air. The source of CO2 is
partial oxidation with oxygen. In the plant, the hydrocarbons in the natural gas feed. Product
ammonia is produced from synthesis gas ammonia and CO2 is sent to urea plant. The
containing hydrogen and nitrogen in the ratio of main function of the plant is illustrated in the
approximately 3:1. Besides these components, following sketch (figure-1)
the synthesis gas contains inert gases such as

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Fig-1

Brief Description of Process 4. The CO and CO2 residues in the gas

The process steps necessary for production of outlet of the CO2 removal unit are
ammonia from the above-mentioned raw converted into methane by reaction with
materials are as follows: - H2 (Methanation) before the synthesis
1. The hydrocarbon feed is de sulphurized gas is sent to the ammonia synthesis
to the ppb level in the desulphurization loop.
section. 5. The purified synthesis gas is compressed
2. The de sulphurized hydrocarbon feed is and then routed to the ammonia
reformed with steam and air into raw synthesis loop, where it is converted into
synthesis gas (process gas). The gas ammonia. In order to limit the
contains mainly hydrogen, nitrogen, accumulation of argon and methane in
carbon monoxide, carbon dioxide and the loop, a purge stream is taken. The
steam. – liquid ammonia product is depressurised
3. In the gas purification section, the CO is during which the dissolved gases,
first converted into CO2. Then the CO2 letdown gas and inert gas, are flashed
is removed from the process gas in the off.
CO2 removal section. –

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Fig-2
The natural gas feedstock coming from source is mixed with Hydrogen rich recycle stream
limit contains minor quantities of sulphur which is coming from syn gas compressor 2nd
compounds which have to be removed in order stage discharge. Then the Feed gas is heated in
to avoid poisoning of the reforming catalyst in Heater in the reformer flue gas section. Since the
the primary reformer, and the low temperature gas contains organicc sulphur compounds, the
shift catalyst in the CO converter, Particularly desulphurization takes place in two stages. The
the low temperature shift. Converter
Converter, is sensitive organic sulphur compounds are converted to H2S
to deactivation by sulphur and sulphur
sulphur-bearing by the hydrogenation catalyst, and the H2S
compounds. Prior to hydrogenation, the feed gas absorption takes place in the
sulphur absorption catalyst. After than 0.1 vol. ppm. A sketch of the
desulphurization, the content
nt of sulphur is less desulphurization section is given in Figure –3

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Fig-3
Hydrogenation The preheated natural gas is fed with hydrocarbons without the presence of
to the hydrogenator. The vessel contains hydrogen. The result would be poor conversion
Hydrogenation Catalyst, which is a cobaltcobalt- of the organic sulphur compounds causing an
molybdenum based catalyst. catalyzes the increased sulphur slip to the reforming section.
following reactions- The temperature also playslays an important role
RSH + H2 → RH + H2S with regard to catalyst activity; at low
R1SSR2 + 3H2 → R1H + R2H + 2H2S temperatures the hydrogenation reactions
R1SR2 + 2H2 → R1H + R2H + H2S progress very slowly and conversion is not
(CH)4S + 4H2 → C4H10 + H2S optimal while at high temperatures undesirable
COS + H2 → CO + H2S cracking reactions may occur with deactivation
Where R is hydrocarbon radical. The of catalyst duee to carbon lay-down
lay on the
hydrogenation catalyst must not get into contact catalyst itself. The optimum temperature range is

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between 350 and 400°C. In case natural gas After desulfurization and scrubbing, the natural
containing CO and CO2 is fed to the Hydro gas is sent to the primary reformer for steam
generator, the following reactions will take reforming, where superheated steam is fed into
place. the reformer with the methane. The gas mixture
CO2 + H2 ⇔ CO + H2O passed through reformer tubes which contains
CO2 + H2S ⇔ COS + H2O Nickel catalyst and externally heated by the
Therefore, the presence of CO, CO2 and H2O combustion of fuel, normally natural gas and
influences the sulphur slippage from purge gas, to approximately 770 0 C in the
downstream the Sulphur absorbers, The catalyst presence of a nickel catalyst where methane is
is oxidized at delivery and resumes its activity converted into CO/CO2 and H2. At this
when sulphided. The Catalyst can be sulphided temperature, the following endothermic
during initial start-up with natural gas feedstock reactions are driven to the right, converting the
at not high temperature and not high H2 flow to methane to hydrogen, carbon dioxide and small
minimize the possibility of the MoO3 being quantities of carbon monoxide.
reduced to MoO2 that means catalyst CnH2n+2 + 2H2O ⇔ Cn-1H2n + CO2 + 3H2 –
irreversible deactivation. In the sulphided state heat
the catalyst is pyrophoric and it must be not CH4 + 2H2O ⇔ CO2 + 4H2 - heat (39.4
exposed to air at temperatures above 70°C. kcal/mol)
The equilibrium composition for the reaction CO2 + H2 ⇔ CO + H2O - heat (9.84 kcal/mol)
between the zinc oxide and hydrogen sulphide is This gaseous mixture is known as synthesis gas.
expressed by the following equation: Conversion in primary steam reformer is about
K(p) T =PH2S/PH2O=2.5 X 10-6 at 3800C. 70% of the hydrocarbon feed into synthesis gas.
The catalyst is not reacting with oxygen or The reactions are endothermic, thus the supply
hydrogen at any practical temperature. Zinc of heat to the reformer is required to maintain
sulphide is not pyrophoric and no special care the desired reaction temperature. The hot flue
during unloading is required. Steam operations gases contain lot of energy and recovered upto
should not be carried out in 11-R-202 A/B: the maximum possible extent before releasing to
zinc oxide would hydrate and it would then be atmosphere through chimney.
impossible to regenerate the ZnO material in the
reactor.

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Fig-4
Studies on the prediction of remaining life and This may cause overheating of the tubes, which
ageing
ng of material for pressurized tubes of ultimately led to one tube rupture. Flame
industrial furnace operated at elevated impingement from a nearby leaky tube might
temperature. The results of mechanical result in overheating and the ultimate rupture of
properties tested at high temperature (800 and the other nearby tubes. Sometimes
times situation may
8500 C) had shown that the aged metal’s lead to explosion in reformer furnace furnac as
mechanical properties improved after the discussed an incident of fire in an ammonia plant
solution heat treatment. In other words, the which began with leakage in tube of a natural
outlet pigtail tubes after being employed to gas pre heater ignited a small fire. The small fire
about 80000 h can be further used continuously, ultimately developed into tube to burst resulting
resulti
operated at high temperature, for another design in large fire and plant shutdown. Reformer tube
life (100000 h) by using solution heat treatment can also fail by stress corrosion cracking. During
processing based on their proposed
posed methodology welding, the steel in the heat affected zone
for predicting the remaining life and ageing of (HAZ) can get sensitized and this may
material of furnace tubes. There are numerous subsequently lead to stress corrosion cracking.
incidents of reformer tube failure and fire in The premature failure off a primary reformer tube
ammonia plant. The probable causes of fire are in an ammonia plant in which ch number of catalyst
direct impingement of flame on the tube due to tubes found to have failed just below the inlet
the partial blockage of burner tips is possible. flange weld within about 2 years in service.

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Stress corrosion cracking (SCC) may get Therefore it is recommended to cool the steel
aggravated further due improper welding below 1000 C after every weld pass, use filler
procedure. Preventing such failure by following metal electrodes with low carbon content (such
the proper welding procedure is very important. as the 321
grades) and stabilising the steel grades with black outer surface indicative of high
addition of Nb (up to 1%) will help preventing temperature and the oxide scale was adherent.
sensitisation during welding.Reformer tubes There was no indication of any localised damage
from a fertilizer plant made of modified HK 40 in the form of pits.
steel which failed after 4 years service during Categories of Risk associated with the
startup of plant. At that time only 60 burners Fertilizers Complex
(out of 576 burners) were firing in the reformer. The manufacture of anhydrous liquid ammonia
The gas in the catalyst tubes was mainly involves processing of hydrocarbons under high
hydrogen and steam at low pressure of 3 kg/cm2 temperature, high pressure conditions in the
only. Seven tubes had ruptured in the bottom presence of various catalysts, chemicals etc.
portion in one corner of the radiant chamber. Typical risks are as follows:
Their visual observation - the tubes had a rather
Ammonia Plants
1 Fire / Explosion Risks  Glands/seal leaks in valves, pumps, compressors handling
hydrogen, natural gas, naphtha, synthesis gas etc.
 Hose/pipe failure, leakage from flanged joints carrying
combustible gases, vapours, liquids
2 High / Low  Burns due to contact with hot surfaces of pipelines,
Temperature Exposure equipments, etc. or leaking steam lines, process fluids at high
Risks temperature.
 Frost bite due to contact with anhydrous liquid ammonia at -33
deg. C
 Burns due to contact with pyrophoric catalyst
3 Toxic Chemicals  Asphyxia due to inhalation of simple asphyxiants like CO2 ,
Exposure Risks N2, H2, CH4, naphtha etc. and chemical asphyxiants like CO,
NH3, Nickel carbonyl, V2O5, Hydrazine, NOx, SOx, H2S etc.
 Acute toxicity due to inhalation of catalyst dusts containing
heavy metals like Ni, Cr, CO, Mo, Fe, Zn, Alumina etc. and
silica gel molecular sieves, insulation fibers/dusts.
4 Corrosive /  Severe burns, damage to eyes, skin and body tissues due to
Radioactive Chemicals contact with anhydrous ammonia
Exposure Risk
Table-4
The risks of process hazards resulting in major / policies of the particular organization. There
events (fires, explosions and toxic releases) are, are a number of models which illustrate the idea
in principle, minimized by good design and the of “Layers of Protection”. The basic unmitigated
application of process safety principles. Older risk posed by a process hazard is reduced by a
plant was not subjected to the same level of number of “barriers” which either prevent the
scrutiny that new plant is today. The adoption of hazard from being materialized or / and mitigate
process safety principles is influenced by the the effect of the hazard once the event has
country legislation, the linkages of the happened. A simple popular descriptive model,
organization to global companies and the vision

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is shown below Figure No= 5 to illustrate the concept.

Fig-5

Fig-6

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The barriers are also known as safeguards, fire. The higher the amount of chemicals
controls, safety measures or “Layers of released, the wider the area that has the potential
potentia
Protection”. Each barrier has a finite probability to be flammable as well as the greater the
of failure so multiple barriers are required to probability of chemical vapors released close to
reduce the risk of the event taking place to an the source of fire resulting in an explosion. This
acceptable level. The barriers need to be fully type of chemical is also very important to
independent of each other or else they may be consider. Some types of chemicals are not
subject to a form of common mode failure. The flammable yet some are very ver volatile and
barriers
arriers need to be maintained so that their flammable.
reliability does not decline. The barriers may be Based on Table 4,, it is known that DFEI value
of three major types. They may be hardware for secondary reformer was 289.74. This value
(e.g. pressure relief valve), systems (e.g. indicates that the impact caused by the
operating procedure), and people (e.g. training). fire/explosion secondary reformer is classified as
The ranking of vulnerable are shown in the severe. Table 4 This value did not include
figure- 6,7 trauma
ma treatment for employees, the ability to
The value of strength of explosion is a function rise the company and other non-technical
non
of the amount of chemical released, the factors.,
characteristics of chemicals and the source of

Fig-7

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Fig-8
Urea Plants Risk analysis & equipments. The Inters are vents in MP
All the Ammonia plants product uses in section in Ammonia stripping plants so the
Urea plant e.g. Ammonia, Carbon Dioxides , MP section is very risky similarly tin CO2
Hydrogen mixed in carbon Dioxides makes stripping the HP scrubber is very risky for
explosive mixture with Oxygen which is explosion. Numbers of explosion are
gives for passivation of stainless steel vessel recoded worldwide.
Fire / Ammonia leaks from glands/ pump seals or flanged joints piping resulting in
Explosion formation explosive mixtures in air.
Risks  Accumulation of H2 may take place in HP Section in case CO2 purity from
Ammonia Plant is not within allowable limits. Ignition of this accumulated H2
can occur due to dissipation of static charge.
High / Low  Burns due to contact with hot surfaces of pipelines, equipments, etc. or leaking
Temperature steam lines, process fluids at high temperature.
Exposure Risk  Frost bite due to contact with anhydrous liquid ammonia at -33 deg. C
Burns due to contact.
Toxic  Asphyxia due to inhalation of simple Exposure risk asphyxiants like CO2, N2,
Chemicals chemical asphyxiant and ammonia. Solution of Urea, Ammonium carbamate
Exposure and ammonium carbonate containing high NH3 content.
Risks  Irritation due to inhalation of urea dust.
Corrosive / Severe burns, damage to eyes, skin and body tissues due to contact with anhydrous
Radioactive ammonia, conc. Urea and Ammonium carbamate solutions
Chemicals
Exposure
Risks
Table-5

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Fig-9 sprung into the action diffuse the gas with water
Major incident occurred in NFL Panipat spray. The ammonia had released into the
detail analysis atmosphere from the open port of the safety
An incident of ammonia release occurred on valve in the form of the spray. Some person was
26th August 1992 in National Fertilizers Ltd. completely drenched with the liquefied
Panipat (Haryana) India. On the morning of ammonia. The atmosphere was suddenly filled
August 26 some pressure drop was observed in with dense cloud of ammonia involving the
the discharge end of the ammonia pump persons within it. The rescue and relief operation
provided before the urea reactor. When search were soon started but by the time the victims
was made it was observed that the safety valve taken to the factory hospital 11 persons had died
provided at the discharge end of the pump was and 10 others sustained serious injuries. On the
passing. On the instruction of the shift in charge day of accident also the valve had been
the stand-by pump was started and the pump C hammered to ensure total stoppage of the flow.
was isolated. The pump was depressurized and The maintenance team had brought another
flushed. While the safety valve was being safety valve. The task involved removing of the
replaced by the maintenance operator with his existing valve and fitting another valve at its
helper under the foreman maintenance, the place in order to bring the defective valve to the
operator of the urea plant and the shift in charge workshop for repairing and testing. The
of the urea plant, the isolation valve had failed condition found after the incident that the
and the liquefied ammonia start releasing at the existing had been removed isolation valve had
pressure of 26 kg/cm2. The routine job of failed and started releasing the ammonia gas
replacing the defective safety valve of the through the open port of the safety valve.
ammonia feed pump at 15 years old urea plant Immediately after that the area got covered with
and began to replacing the valve when the foggy fumes. The information of the event
unthinkable happened. Vaporizing within the reached to all quickly and rescuers with
seconds to form suffocating clouds of the deadly selfcontained breathing apparatus entered the
gas. This hit and choked to death eleven people cloud for searching the trapped persons.
and injured the ten even as their colleagues Emergency siren was raised, though no one

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acted as per the responsibility distribution in the due to repeated hammering of the lever. Lessons
onsite emergency plan. As soon as the learnt from the event the causes of the frequent
information of the ammonia leakage spread in failure of safety valves should be identified and
the plant, the about 25 breathing sets were necessary actions should be taken. The safety
brought from safety department to the site of valve and the isolation valve before the safety
incident. About 21 breathing sets were used by valves should be marked with the identified
the persons involved in the rescue operation. The numbers. The isolation valve before the safety
fire services of the plant were involved in valves should be locked open. The safety work
spraying of water in the leakage zone. Keeping permit should be signed by the safety officer
the wind direction in view the areas towards duly countersigned by the issuing authority. The
wind ward direction were being evaluated in the permit signing authority should ensure that the
plant. The urea plant was shut down by use of precaution indicated in the permit. The isolation
emergency push button which closes the of the machine having toxic or flammable
activities with shortest possible period. The substances should be dissolved in water by
nearest fire call point was broken to inform the suitable process and should be lagoon to release
fire department about the event. The first fire slowly in the atmosphere the designer
tender reached within 3-4 minutes after starting instructions regarding type of valve to be used
the event. After that the order fire tender also should be strictly followed. In case the
joined. There was need to stop the alternate deviations from the original designed are
ammonia pump. The switch was in the area required the manufacturer of the machines
where the cloud was dense. Nobody could should be consulted. Every proposal for change
approach the valve. Then electric department the process should be critically analyzed by
was asked to switch off the power from the main HAZOP study. Globe valve should be tested for
supply to the plant. The person who were any crack in the collar by dye penetration test or
rescued reach the factory hospital within 8-10 other equivalent technique. Condition of the
minutes. After the event has controlled the cause thread should also be checked to not allow any
of the valve failure was checked, it was found slip. The emergency plan should be made a
that the valve collar of the globe valve had practical instrument for mitigate the effect of the
broken allowing the spindle of the valve in events. The escape route from pump platform
upward direction. The person engaged in the should be increased to promote the escape of the
rescue and control operations were also affected person in case of such events. Provision of waste
by the ammonia exposure. They were first taken spray in ammonia compressor area should be
to the company hospital. But next day such considered. All the SCBAs should be equipped
people were admitted in the hospital. Cause of with low pressure alarms and working in
valve Failure The subsequent accident continuous positive pressure mode. The SCBA
investigations indicated that the cause of the working only on demand mode should be
incident was lifting of valve spindle due to marked and levels that these will not use when
rupture of the collar of the valve. The careful there is risk of live or health Quick modification
investigation of the broken pieces of the valve done in other units of NFL After the Panipat
indicated that about half of the collar had incident, the motorized valve provided in other
developed damage some time back as it has units of NFL so that in case of incident this
turned black, whereas the remaining part of the ammonia can be protected to vented out as fig
broken surface was shining white. This indicated No. 9
that the crack had taken place some time back

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Fig --10
Incident on dated 18/09/2018 failure of one situation; this lesson one has learnt from the
plunger packing of ammonia reciprocating pump Panipat incident. This motorized valve was
In NFL Vijaipur unit, one reciprocating plunger provided after Panipat incident. The manual
packing failed on date 18/09/2018. A huge valve cannot be operated in field because huge
amount dense ammonia cloud observed. The dense ammonia was there. In high pressure
ammonia pump has five plungers and discharge pump house area a water curtains also provided
pressure is about 250 bar. The plant was running with control valve which can be operated from
on full load at about 11.30 hrs. Ammonia control room. An ammonia sensor also provided
leakage was started due failure of 5th number in each pump house and at 50 ppm of ammonia
plunger. Immediately one stopped the plant and the alarm appears on central control room.
closed the booster pump motorized suction valve Immediately water curtains control valve open to
from control room to immediately control the control ammonia.

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Fig- 11

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Fig-12
Hazard Identification failure of a pipeline of even catastrophic failure
There are various modes in which flammable of the storage tank. Some typical modes of
and toxic chemicals can leak into atmosphere failures and their possible
ible causes are discussed
causing adverse affects. It may be small leaks below , Table No-6
from gaskets of the flanged joints, or guillotine

Sr. Failure Mode Probable Cause Remarks

No.
1 Flange / Gasket failure Incorrect gasket
Incorrect Attention to be paid during
installation selection and installation of
gaskets.
2 Weld failure It is normally due to poor quality Welding to be done by certified
of welds welders with right quality of
welding rods. Inspection and
radiography must also be done.
3 Pipe corrosion erosion Sometimes fabrication or Pipes material of construction
or failure due to stress installation leaves stress in the should be selected correctly.
pipes. Erosion or corrosion also is Design should take care of
sometimes the cause. erosion effects. And installation
of pipes should not leave any
stress

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4 Over pressurization of Over pressurization can occur due Necessary procedures should be
pipeline to failure of SRV or incorrect there to prevent.
operation.
5 Deficient installation of Pipes design and installation is It must be ensured that
pipes sometimes not as per appropriate installation is as per correct
standard. standards completely.
6 Leaks from valve Leaks from glands, bonnets or Right selection of valves and their
failures valves spindle is maintenance should be ensured.
sometimes the cause.
7 Instruments failure Multifarious instruments are used Reliability of instruments
for control of process parameters. working must be ensured through
Any such instrument failure can proper selection and maintenance.
cause mishap.
8 Failures of protective Protective system like SRV, Reliability of protective system
system bursting discs, vent header, drain must be ensured highest through
lines etc. are provided to take care inspection and proper
of abnormal conditions. maintenance.
9 Operational effort Plant operational parameters Operating procedures must be
should not be exceeded beyond complete and strictly followed.
the permissible limits.
10 Other failures There are external other reasons Design and operating philosophy
causing the failures. must consider all possible
reasons.
Table-6
Selected failure cases and likely consequences) facilities of onshore oil/gas production facilities
outlines the failure cases those selected for at Fertilizer Complex
Sr. Equipment Failure case Associated hazards
No.
Ammonia Plant
1 NG at B/L Instrument tapping failure Flammable
2 NG Compressor Discharge Instrument tapping failure. Flammable
3 HTS Effluent Large hole in bottom Flammable/ Toxic
4 Converter effluent Catastrophic Failure Flammable/ Toxi
5 HP ammonia scrubber vapour Instrument tapping failure, Flammable/ Toxic
6 Instrument tapping failure Toxic
7 Process condensate Large hole in bottom, Toxic
8 HP Ammonia scrubber liquid Large hole in bottom. Flammable/ Toxic
9 HP Ammonia scrubber liquid Large hole in bottom, Flammable/ Toxic
Urea Plants
1 Ammonia at B/L Instrument tapping failure Flammable/ Toxic
2 HP Ammonia pum 10 mm failure Flammable/ Toxic
3 Instrument tapping failure, Flammable/ Toxic
4 Reactor Large hole in bottom, Flammable/ Toxic
5 HP Carbamate pump Pump seal failure Flammable/ Toxic
6
Table-7

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Role of Oxygen and stainless steel higher temperature and pressure and where
The optimum passivation is required if more aggressive condition of urea Carbamate
than optimum the chances of explosive mixture exists, stainless steel of higher
mixture and also ammonia losses, i.e. danger chromium and nickel contents are found to
for environment also. Flammable gas be more effective against corrosion. At this
mixtures and the consequences there of on condition, the influence of Nickel is also
urea plant safety have been important issues apparent. However, the corrosion rate of
in the entire history of the urea process 2RE-69 stainless steel is about 5 times as
industry. High chromium stainless steel owe low as that of SS-316L which indicates that
their high resistance to corrosion under the favorable influence of Chromium is
oxidizing condition due to the formation of a much larger than the unfavorable influence
surface-oxide film which is very adherent of Nickel.
and highly impervious; thus the metal is Since the liquid phase in urea synthesis
protected from attack or we say it is passive. behaves as an electrolyte, the corrosion is of
However, if the oxidizing conditions are an electrochemical nature. Stainless steel in
lost, the metal is rapidly attacked. The a corrosive medium owes its corrosion
protective film once formed is not damaged resistance to the presence of a protective
in normal course. The presence of sulphur oxide layer on the metal. As long as this
compounds damages this protective film. It layer is intact, the metal corrodes at a very
is essential that the protective film is not low rate. Passive corrosion rates of
damaged during operation and as such austenitic urea grade stainless steels are
continuous feeding of air has been generally between <0.01and (max.) 0.10
incorporated in our process. It was found mm/a. Upon removal of the oxide layer,
from experiments that SS 316L stainless activation and consequently, corrosion set in
steel requires 5 ppm of 02 for passivation unless the medium contains sufficient
and 2RE-69 stainless steel requires 3 ppm. oxygen or oxidation agent to build a new
Although this value is low and in actual layer. Active corrosion rates can reach
practice as high as 6000 ppm of 02 is being values of 50 mm/a. Stainless steel exposed
maintained. Material of higher chromium to Carbamate containing solutions involved
content requires less oxygen to remain in urea synthesis can be kept in a passivation
passive than low chromium steels. This fact (non corroding) state by a given quantity of
also points to the suitability of using oxygen. If the oxygen content drops below
stainless steel with a chromium content of this limit, corrosion starts after some time
24.5% in HP stripper. Chromium slows depending upon process conditions and the
down and nickel accelerates the corrosion of quality of the passive layer. Hence, If the
materials in the active state .This is best CO2 after the elimination of the air used for
illustrated by corrosion rates of a number of preventing corrosion is as following
materials in relation to their Ni contents. At

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Sr. No. Components Percentage The Composition of the vent gases assuming
(Volume) that all ammonia added and CO2 has been
1 Carbon Dioxide 94.7 eliminated , analysis is as following.
2 Hydrogen 1.2 Sr. No. Components Percentage
3 Air 3.8 (Volume)
4 Inerts Gases 0.3 2 Hydrogen 22.6
3 Air 71,7
Table-8 4 Others 5.7
Table-9
If we neglect others combustible , the Gas mixture inside the triangle is formed by
Hydrogen/Total combustible ratio must the base line and the lines labeled.
equal as unity The mixture indicated by the star is laying
inside the above mentioned explosive area
𝟏=
𝐇𝐲𝐝𝐫𝐨𝐠𝐞𝐧 and thus explosive as shown in the figure-
𝐓𝐨𝐭𝐚𝐥 𝐂𝐨𝐦𝐛𝐮𝐬𝐭𝐢𝐛𝐥𝐞 𝐄𝐱𝐩𝐥𝐨𝐬𝐢𝐨𝐧 𝐌𝐢𝐱𝐭𝐮𝐫𝐞 13

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Fig-13
In CO2 Stripping Gas analysis tabulated in Table No-10, and this is found in Explosive range.

Analysis of HP Scrubber Gases

Categories Components [%(v/v)] Total % INDIVIDUAL
NH3 37.50 76.84
H2 11.30 23.16
Inflamables CH4 0.00 48.80 0.00
C2H6 0.00 0.00
C3H8 0.00 0.00
N2 6.06 100.00
Inertes Ar 0.00 18.56
CO2 12.50
Oxygen O2 32.64 32.64
O2+Ar 0.00
Total 100.00 100.00

Table -10

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Brief Description of High P

Pressure Scrubber
The HP scrubber consisting following three from LP section and where the NH3
parts. As shown in the 1 6 & 17. and CO2 are almost tottaly
1. Blanketing sphere, which receive the condensed.
gases coming from reactor.
2. A Heat exchanger part, which is The synthesis loop is provided with a central
equipped with central down comer drain line connecting all the HP vessel to the
through which degasified flow down. outlet of the HP heat Exchanger then to the
A gas distributer with vortex is central drain line. The central drain line and
installed in bottom. other parts of the HP synthesis section are
3. A scrubbing part, in which the connected to the HP flush water source, so
remaining gases are scrubbed with as to enable them to be flushed.
carbonate
nate solution which is coming

Fig-14

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In case that there are some NH3 and CO2 according to the following compositions
Sr. Components Percentage 𝐇𝐲𝐝𝐫𝐨𝐠𝐞𝐧
𝟎. 𝟐𝟑 =
No. (Volume) 𝐇𝐲𝐝𝐫𝐨𝐠𝐞𝐧 + 𝐀𝐦𝐦𝐨𝐧𝐢𝐚
1 Hydrogen 11.3
2 Air 35.9 The above mixture gas mixture will be if it
3 Other 2.8 is situated inside the triangle formed by the
4 Ammonia 37.5 0.23 explosion limits and the base line.
5 Carbon 12.5 In the operating point marked total
Dioxide combustibles 48.8%, air 35.9%, this point is
Table-11 outside the explosion area as shown in the
figure-15
Then The Hydrogen/Total combustibles are

Analysis of HP Scrubber Gases

Components [%(v/v)] Total % INDIVIDUAL

NH3 18 49 36.73
H2 31 63.27
Inflammables CH4 0 0
C2H6 0 0

C3H8 0 0
Inertes N2 28 42 100
Ar 0
CO2 14
Oxygen O2 9 9
O2+Ar 0
Total 100 100
Table-12

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Fig-15

Calculation for Explosively CO2 =95%

Hydrogen=1.1%
The hydrogen present in Carbon Dioxide, Air=3.6%
hence the composition of vent gases Noncombustible material=0.3%
calculated by carbon Dioxide given to Vented Gas D/S HP Scrubber=3000
Stripper. Nm3/Hr
Carbon Dioxide to HP stripper=37500 Vented Hydrogen=412 Nm3/hr
Nm3/hr Vented Air=1350 Nm3/hr
Composition of Carbon Dioxide
Non Combustible Gases=112 Nm3/hr Ammonia & Carbon Dioxide in Vent
Total (Hydrogen +Air + Gas=3000-1875=1125 Nm3/hr
Noncombustible)=1875Nm3/Hr Then the Vent gas from HP Scrubber

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1. Hydrogen=(412*100/3000=13.75%
2. Air=(1350*100/3000)=45% 5. Ammonia=1125-
3. Non 187.5=937.5Nm3/Hr=937.5*100/300
Combustible=112.5*100/3000=3.75 0=28.13%
% 6. Combustible Gases
ases are Hydrogen
4. Carbon Dioxide
Dioxide- and Ammonia, so the=
37500*0.05=187.5Nm3/hr=281*100/ 7. 13.75/41.875 = Hydrogen/
Hydrogen
3000=9.37% (Hydrogen + Ammonia)
Ammonia
32.8%
So according to the above figure the point 32.85 is an Explosive mixture

Fig-16

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Fig-17

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Calculation for Ammonia Stripping can often be reliably predicted by

Process using the following formulas
Where mixtures of two or more suggested by Le Chatelier:
flammable gases are encountered, the
limits of flammability of the mixture

Where: P1 . . . Pn = volume fractions of

components 1, 2, 3, . . . , n of the mixture
LFL1… LFLn = lower flammable limits of
components 1, 2, 3, .. n of the mixture
UFL1…. UFLn = upper flammable limits of
components 1, 2, 3, .. n of the mixture
EXPLOSIVE LIMITS

Explosion Limits Explosion

Minimum
Gases in Air Limits in O2 Minimum O2 Content
Flammable
Lower Upper Lower Upper
CH4 5 15 5.5 60 12.25 6
H2 4 74 4.5 94 5 4.3
CO 12.5 74 15.5 94 6 13.75
NH3 15.5 27 13.5 79 - -
Table-13

The oxygen concentration in the Carbon If we need 0.1 % of oxygen in this gas
dioxide "range from 0.1 to 0.8% of oxygen. mixture and we feed this as air the final
Let ns examine the two above mentioned composition of the non condensable
concentrations as examples. Normal components becomes;
compositions of carbon dioxide feed gas at Hydrogen 0.6 moles 40% moles
the battery limits of the urea plant are: Nitrogen 0.4 moles 53% moles
Air 0.1 moles O2 7.0 % moles
C02- 99.0 % (mole)
+0.4moles N2
H2- 0.6 % (mole) Total 1.5 moles 100% moles
N2- 0.4 % (mole) including Argon etc. Table-14
Example 1_
This mixture is within the explosion limits % mole will be within the explosive limits-.
limits
as can be seen from figure-18 We may thus conclude that each high
efficiency urea process
All of the carbon dioxide gas mixtures with
oxygen concentrations between 0.1 and 0.8

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Fig-18

will end up with a hazardous gas mixture, not occur so far. The potential danger is
unless provisions are being made to remove there however as practice has shown. In a
the hydrogen from carbon dioxide de and if the few plants Stamicarbon has experienced
experi
ammonia contains hydrogen, to remove this explosions in the 18 ata purification step of
hydrogen as well.There are many plants, conventional urea plants as well as in the
running during normal operation or upset 140 ata purification step in CO2 stripping
conditions, emitting gas mixtures within the urea plants in HP scrubber section.
explosion limits» k great many plants
however have never experienced exploexplosion. Gas sample analysis
In those plants all of the conditions required Gas Flow -524.5 NM3/Hr,
for an explosion (an explosive gas mixture
and an ignition source simultaneously) did CH4-6.78%,
6.78%, Hydrogen 7.45, Ammonia
18.45, Inerts (N2+O2)-67.32,
67.32,

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Fig-19

Conclusion process of energy release. Once the vapor

The fundamental method for prevention of vapor explosion takes place, the catastrophic accident
explosion is how to reduce the possibility of becomes inevitable due to the high speed of
leakage. Vapor explosion is an instantaneous phase transformation. A leakage detection
process of energy release. Once the vapor system should be developed due to impurities in
explosion takes place, the catastrophic accident steam-damaged steels. The barrier of having an
becomes inevitable due to the high speed of effective start-up procedure was totally
phase transformation. A leakage detection ineffective as this not apply to the specific
system should be developed due to impurities in conditions applicable on the day. Failure of
steam-damaged steels. people undermined the entire risk management
The fundamental method for prevention of vapor process. Whilst people represent a source of
explosion is how to reduce the possibility of failure they also are the last barrier to detect
leakage. Vapor explosion is an instantaneous problems and save the day. Safety Model of a

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hazard protected by a series of protective In addition, administrative control also need to

barriers is not understood by the Fertilizers and be conducted, such as: posting information about
support personnel. the national Fire protection association (NFPA)
Engineering control that should be conducted rating of Chemicals which will eventually help
include: periodic maintenance of the gas detector minimize the risk.
and provide cleaning tools to clean the oil spills.
References
1. Book “Fertilizers Technology pure
knowledge” by Prem Baboo
published in Notion Press-2021.
2. Section of material in fertilizers
Industries by Prem Baboo,
published in Global scitific journal,
Vol-9 issue -1, January-2021.
3. Operational Experience of De-
hydrogen Reactor at GFGL by
Ashok Agrawal, published in Indian
Journal of Fertilizers,Vol-2, Dec-
2006.
4. Probabilistic risk assessment of
Fertilizers Plants by R.S
olaniya,H.N. Mathurkar,A.W.
deshpandey published in Indian
Journal of chemical Technology,
Vol-3, March 1996.
5. Guidelines for integrated risk
assessment and management in large
industrial areas Jan-98.

Legends
PHA (Process Hazard Analysis), HP-High
Pressure, LS-Low pressure steam, MP- medium
pressure, LP-Low pressure.

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