CHAPTER 1

INTRODUCTION

When we refer to hazards in relation to occupational safety and health the

most commonly used definition is A Hazard is a potential source of harm or
adverse health effect on a person or persons. A hazard is any source of potential
damage, harm or adverse health effects on something or someone under certain
conditions at work. Due to presence of various hazards in the work place workers
are likely to be injured or any other accidents like property damage can be
occurred. These accidents and property damage can be prevented by several
techniques. One of these techniques is Hazard Analysis.
Hazard analysis is the process of determining the release probabilities and
quantities, emission or release rates, the routes/pathways by which the released
substances could reach the receptors, the fate of the substances in environmental
media through which they are transported or moved and characteristics of the
receptors at risk. Risk evaluation is the process of identifying, whether the
estimated level of risk is tolerable. Tolerable risk is not equated with
acceptability; it refers to a willingness to live with a risk so as to secure certain
risk benefits, and in the confidence that the risk is being properly controlled.
Hazard analysis involves the identification and quantification of the various
hazards (unsafe conditions) that exist in the plant. On the other hand, risk analysis
deals with the identification and quantification of risks, the plant equipment and
personnel are exposed to, due to accidents resulting from the hazards present in
the plant. Hazard and risk analysis involves very extensive studies, and requires
a very detailed design and engineering information.
Many Hazard Identification techniques are available for identifying the
hazards. There are reactive (post hazard scenario) or proactive (predictive) tool or

hazard identification. Some of the proven tools are mentioned below. These are
not exhaustive
Reactive approach
Accident Investigation
Plant Inspection
Critical Incidence Technique (CIT)
Incident Recall Technique
Proactive approach
Job Safety Analysis (JSA)
Failure Mode and Effect Analysis (FMEA)
Hazard and Operability Study (HAZOP)
Fault Tree and Event Tree Analysis (FTA & ETA)
Management Oversight Risk Tree (MORT) Analysis
Fire Explosion and Toxicity Index (FETI)
Material / Chemical Reactive Analysis
Consequence analysis etc.

The common terms used in Risk Assessment or Hazard Analysis are elaborated
below:
Risk is defined as a likelihood of an undesired event (accident, injury or
death) occurring within a specified period or under specified circumstances. This
may be either a probability depending on the circumstances.
Hazard is defined as a physical situation, which may cause human injury,
damage to property or the environment or some combination of these criteria.
Hazardous substance means any substance or preparation, which by
reason of its chemical or physic chemical properties or handling is liable to cause
2

harm to human beings, other living creatures, plants, microorganisms, property

or the environment.
Hazardous process is defined as any process or activity in relation to an
industry which may cause impairment to the health of the persons engaged or
connected therewith or which may result in pollution of their general
environment.

In this Project, Hazard Analysis was done in The Fertilizers and Chemicals
Travancore Limited (or FACT Ltd), a fertilizer and chemical manufacturing
company in Kochi, Kerala. It consists of several plants but hazard analysis was
carried out in Ammonia Production Plant and its Storage Area.

CHAPTER 2
FACT ABOUT THE COMPANY

The Fertilizers and Chemicals Travancore Limited (or FACT Ltd), a fertilizer and
chemical manufacturing company in Kochi, Kerala, India, was incorporated in
1943, by Maharajah Sree Chithira Thirunal Balarama Varma. In 1947 FACT
started production of ammonium sulphate with an installed capacity of 50,000
MT per annum at Udyogamandal near Cochin. It is the first fertilizer
manufacturing company in independent India and also the largest Central public
Sector Undertaking (CPSU) in the State of Kerala.
The company has 2 production units Udyogamandal Complex (UC) at Eloor,
Udyogamandal, and Cochin Division (CD) at Ambalamedu. The Caprolactam
plant in Udyogamandal was commissioned in 1990. Main products of the
company include Ammonium PhosphateSulphate (FACTAMFOS), Ammonium
Sulphate, Zincated Ammonium Phosphate, Caprolactum, Sulphuric Acid,
Ammonia and other complex fertilizers. Gypsum, nitric acid soda ash and
coloured Ammonium Sulphate are major by-products.
The factory commenced production of ammonium sulphate in 1947 at the dawn
of Indian independence using wood as the raw material for production of
ammonia. With the effect of time, wood gasification became uneconomic and was
replaced with naphtha reforming process. Through a series of expansion
programmes, FACT soon became the producer of the widest range of fertilizers
suited for all crops and all soil types in India. It became a Kerala State public
sector enterprise in 1960 and in 1962, it came under the Government of India.

Diversification to full-fledged engineering services (FEW) in the fertilizer field

and allied areas followed. The next major step forward was the diversification of
petrochemicals, an important milestone in the growth of the company. FACT has
formed a Joint Venture Company with Rashtriya Chemicals & Fertilizers Limited
4

for manufacturing load bearing panels and other building products using
phosphogypsum.
The factory is situated in an area of 20.2 hectares at the bank of river Periyar. The
area around the factory contains a market, a hospital and schools, two shopping
complexes and more than 1100 quarters. The neighboring factories are the
Travancore Cochin Chemicals Ltd (TCC), Hindustan Insecticides Ltd (HIL),
Indian Rare Earths Ltd(IRE). The factory is located in the Eloor Panchayat which
has a density of population more than 3000 per square kilometer. The present
operating plants in Udyogamandal division are the following.
Sulphuric Acid
Ammonium Sulphate
Phosphoric Acid
Ammonium Phosphate
Ammonia Plant

2.1 UDYOGAMANDAL DIVISION

FACT started with a low profile of nearly 4950 MT per annum of ammonium
sulphate production and 49500 MT of super phosphate. Later on, the production
capacity was raised in four stages of expansion. Some of the old process/plants
were scrapped adding new and sophisticated ones. The present production
capacity is as follows. Ammonium sulphate is a co-product of caprolactam.
FACT manufactures Caprolactam, the raw material for Nylon-6 which is
extensively used for the production of tyre cord, textile filament yarn and
engineering plastics. FACT, one of the only two manufactures of this product in
India, has the capacity to produce 50,000 tonnes of Caprolactam in a year.
Ammonium Sulphate liquor obtained as a by-product from the Caprolactam Plant
is converted as a useful fertiliser product in a New Ammonium Sulphate Plant,
2,25,000 TPA capacity put up in October 1990, at a cost of Rs.35 crore. As a
replacement to the existing high energy consuming old Ammonia plants at
5

Udyogamandal, a new 900 TPD capacity Ammonia Plant at a cost of Rs.642 crore
was put up in March 1998. FACT Udyogamandal plants received ISO 14001
certification in March 2000 for conforming to the Environmental Management
System standard.
FACT's Caprolactam exported to various countries including in USA, not only
earns precious foreign exchange, but also appreciation on account of its excellent
quality. The Caprolactam Plant also produces 2,25,000 tonnes of Ammonium
Sulphate per year as coproduct and small quantities of Soda Ash and Nitric Acid
as by products. The plant has been certified ISO 9001:2002 since April 1996 by
RWTUV, Germany and ISO14001 since December 1999 by DNV, Netherlands.
Installed capacity/annum
Ammonia

330,000 MT

Sulphuric Acid

379,500 MT

Phosphoric Acid

33,000 MT

Ammonium Sulphate

225,000 MT

Ammonium Phosphate

148,000 MT

(FACTAMPHOS 20:20)

2.2 ENVIRONMENTAL POLICY

FACTUD is committed to
1. Continual improvement in its environmental performance and prevention of
pollution
2. Compliance with environmental rules, regulations and other requirements
applicable
3. Conservation of resources and waste minimization
4. Improvement of communication with interested parties
5. Training for improved environmental management

2.3 PRODUCTS
STRAIGHT FERTILISERS
AMMONIUM SULPHATE: Ammonium Sulphate is a nitrogenous fertiliser
containing 20.6% nitrogen, entirely in ammonical form. It has excellent physical
properties nonhygroscopic, crystalline and free flowing. It is ideal as a straight
nitrogenous fetiliser and also as an ingredient in fertiliser mixtures. It is the most
widely preferred nitrogenous fertiliser for top dressing on all crops. Another
unique advantage is that it contains 24% sulphur, an important secondary nutrient.

COMPLEX FERTILISERS
FACTAMFOS (AMMONIUM PHOSPHATE SULPHATE): FACTAMFOS
20:20:0:13 is a chemical blend of 40 parts of ammonium phosphate and 60 parts
of ammonium sulphate. It contains 20% N and 20% P2O5. The entire N is in
ammonical form and P is completely water soluble. In addition, FACTAMFOS
contains 13% sulphur, a secondary plant nutrient which is now attaining great
importance in the agricultural scene. FACTAMFOS 20:20:0:13, with the granular
form and nonhydroscopic and free flowing nature, have excellent physical
properties. It is ideal for application on all soils and all crops. FACTAMFOS
20:20:0:13 can also be used for foliar application.

FACTMIX
FACT prepares on a very large scale all the standard NPK mixtures under the
brand name 'FACTMIX' for different crops for Kerala as stipulated by the
Department of Agriculture. In addition, FACT prepares special tailor made
fertiliser mixtures of any required grade for plantation crops like coffee, tea,
rubber, etc. FACT mixtures are superior in quality with the presence of
ammoniacal nitrogen, water soluble phosphorus, and other major nutrients like
sulphur, calcium, etc.

GYPSUM
A by-product of phosphoric acid, is a rich and cost effective source of 16%
sulphur and 22% calcium. FACT is marketing bagged gypsum in brand name
FACT Gypsum all 4 southern states as a soil conditioner with fertilising
properties.

IMPORTED FERTILISERS
FACT markets imported Urea and Potash from Gulf Countries and Russia for
consumption in all 4 southern states as per requirement. Urea with 46% Nitrogen
in the granular/prilled form and Potash with 60% K20 serves the nutritional
requirement in the 4 southern states.

ZINCATED FACTAMFOS
This special product containing 0.3% Zinc in FACTAMFOS has been launched
to address the widespread deficiency of Zinc in most soils of South India.

ZINCATED GYPSUM
This soil amendment and ameliorant contains 2% Zinc in addition to 16% Sulphur
and 22% Calcium for rectifying alkaline soils and improving soil fertility and
physical properties.

FACT ORGANIC
FACT is also marketing organic manure produced from city compost, in brand
name FACT ORGANIC

CHAPTER 3
METHODOLOGY

Visiting the Thermal Power Plant

Identifying Hazardous Area

Inspecting Plant

Identifying Harzards

Selection of Tools for Evaluation

Evaluation of hazards and recommendations

Report Preparation

Fig.3.1.Hazard Analysis Methodology

9

CHAPTER 4
AMMONIA COMPLEX

Ammonia is produced from a gaseous mixture of hydrogen (H2) and nitrogen (N2)
in the stoichiometric ratio 3 to 1.The gas mixture will contain limited amounts of
inert (argon & methane) coming from the raw materials. The preparation of this
synthesis gas takes place in the various steps mentioned below
For this ammonia plant the sources of hydrogen and nitrogen are naphtha and
atmospheric air respectively.
The processes for producing ammonia from these raw materials are as follows:
a. Predesulphurisation of the raw naphtha. The bulk part of sulphur is removed in
this section.
b. Final desulphurization of the hydrocarbon feed in one step: Removal of
remaining sulphur compounds.
c. Reforming of the desulphurized hydrocarbons in two steps by steam and air.
The process gas from these steps contains hydrogen and nitrogen as well as carbon
monoxide (CO), carbon dioxide (CO2), methane and argon. The reforming takes
place at a pressure of about 35 kg/cm2g.
d. In the gas purification section, CO is first converted to CO 2 and H2 yield. CO2
is then removed in the CO2-removal section, and afterwards the remaining CO
and CO2 in the converted gas are removed in the methanator.
e. The purified synthesis gas is compressed to a pressure of about 135 kg/cm2g
and converted into ammonia by a catalytic reaction.
f. The plant is designed to a nominal production of 900 MTPD ammonia and
10,800 N3 /h of synthesis gas. The ammonia product produced in the plant is
sent to the atmospheric storage in Caprolactam plant. Synthesis gas is consumed
in the Caprolactam plant as well, and in combination with part of the CO2
produced.

10

4.1 PREDESULPHURISATION OF THE RAW NAPHTHA

Usually raw naphtha contain 1000ppm sulphur. As the presence of sulphur is
poisonous to the reforming catalyst, desulphurization of naphtha is carried out. In
the Predesulphurisation process, the organic sulphur compounds are removed
from the naphtha by catalytic conversion to hydrogen sulphide which is separated
from the naphtha by distillation.
The raw naphtha contain a small amount of dissolved oxygen. If this oxygen is
not removed it will cause the formation of gum in the feed heating system and
hydrogenation catalyst. So the dissolved oxygen is removed by stripping with off
gas in the deaerator.
The deaerator naphtha is mixed with hydrogen rich gas and heated to about
3800C and sent to hydrogenation reactor, R 101.which is filled with cobalt
molybdenum catalyst. Sulphur in naphtha is converted to H2S. The product from
the reactor is cooled and sent to a separator where most of the H 2S is separated
from the liquid naphtha. Naphtha is again stripped in the stripper at a temperature
1880C by using reboiler and at a pressure of about 10 kg/cm2 to remove H2S to a
level of less than 5 ppm sulphur.

4.2 FINAL DESULPHURIZATION

The stripped naphtha is again mixed with recycle gas and heated in a super heater
to a temperature of 380 0C and sent to hydrogenator R 201,filled with cobalt
molybdenum hydrogenator catalyst. Most of the residual sulphur is converted to
H2S. H2S is absorbed in the sulphur absorber R 202 filled with ZnO catalyst. The
ZnO reacts with H2S according to the following equation.
H2S + ZnO

ZnS + H2O

The gas leaving the absorber contain less than 0.05 ppm sulphur

11

4.3 REFORMING - PRIMARY REFORMER

The desulphurized naphtha is then mixed with steam and heated to 490 0C and
sent to the reformer tubes in the primary reformer furnace. There are 184 tubes,
each tube contains three types of reforming catalyst
1. RKNR 13/6x7(top)
2. RKNR 19/19x19(middle)
3. R-67-7H (bottom)
and are externally heated by 144 burners fixed on the sides of the reformer
furnace. The flue gas out let temperature is about 1010 0C . The gas leaving the
reformer tubes will be at a temperature of about 7900C and the hydrocarbon
content, which is methane only, will be about 10.2 mole%
The hot flue gas from the reformer is utilized for superheating steam, raising
steam in the waste heat boiler and also for heating of the combustion air to
burners.

4.4 REFORMING -SECONDARY REFORMER

The gas from the primary reformer is sent to the secondary reformer where hot
process air is injected. In the first step the heat is supplied by combustion of the
part of the gas achieved by mixing air into the gas. The burning gas provides heat
for the rest of the reforming. The reforming taking place in the primary reformer
is so adjusted that the air supplying the reaction heat in the secondary reformer
will give the required hydrogen/nitrogen ratio of 3 to 1.
In the second step, air is mixed into the partly reformed gas and reacts in the upper
empty space of the secondary reformer. The reaction here is mainly a combustion
resulting in a temperature rise. The outlet temperature will be about 9700C and the
methane concentration approximately 0.3 mole%. The reaction mixture will
contact the catalyst at about 1100 to 1200 0C.

12

4.5 CO CONVERSION
The process gas is cooled to 3600C before being introduced into the HT shift
converter. The shift reaction takes place in the converter is
CO + H2O

CO2 + H2 + heat.

This will produce only in contact with a catalyst.

Thus the CO conversion is performed in two steps. A copper/chromium promoted
iron based catalyst is used in the high temperature (HT) shift converter, and a
copper based catalyst is used in the low temperature (LT) shift converter. At the
selected steam/dry gas ratio, this arrangement ensures a low CO content and a low
formation of byproducts.
4.6 CO2- REMOVAL
The gas leaving the CO conversion section has a CO2 content of 21-21.5 mole %.
The CO2 is removed from the gas by absorption in a MDEA solution. In the
absorber the CO2 is removed from the gas by countercurrent absorption in two
stages. In the lower part of the absorber, flash-regenerated solution is used for
bulk CO2 removal. In the upper part strip-regenerated solution is used for
scrubbing. At the outlet of the absorber, the CO2 content in the gas is reduced to
less than 500 ppm.
The CO2 released in the LP flash drum is saturated with water at a temperature of
750C.This mixture is cooled to 40 0C. Part of CO2 produced (2755 kg CO2/h) is
sent through the CO2 blower to Caprolactam plant and sold to the outside parties.
The balance CO2 is vented to the atmosphere.
4.7 METHANATION
In the methanator the CO and CO2 present in the synthesis gas is converted to
CH4 by Nickel based methanator catalyst .In the methanator the reverse of the
reforming reaction takes place. The chemical reactions are as follows:
CO + 3H2

CH4 + H2O + heat

CO2 + 4H2

CH4 + 2H2O + heat

13

The exit gas from the methanator contains H2 & N2 in the ratio 3:1 and inert with
less than 10 ppm CO + CO2.
4.8 AMMONIA SYNTHESIS
The gas from the methanator contains H2 & N2 in the ratio 3:1. The synthesis unit
is constructed for a maximum pressure of 158 kg/cm2, and the normal operating
pressure is in the range of 140 145 kg/cm2. The reaction temperature in the
catalyst bed is 370 490 0C which is close to optimum level. The catalyst is a
promoted iron catalyst containing small amount of non -reducible oxides.
A considerable amount of heat is liberated by the reaction (about 750 kcal/kg
produced ammonia), and the heat is utilized for production of HP steam and for
preheating of HP boiler feed water.
Only about 25 % of the hydrogen and nitrogen flow contained in the synthesis
gas at converter inlet is converted in to ammonia per pass, and it is there for
necessary to recycle the unconverted synthesis gas to the converter. In addition to
the converter .the synthesis loop includes a recirculating compressor as well as
equipment for steam production, boiler feed water preheat, for cooling of the
synthesis gas and condensation as well as separation of ammonia.
The converter is a radial type with the gas flowing through the two catalyst beds
in radial direction.
4.9 PROCESS CONDENSATE TREATMENT
During operation of the ammonia plant small amounts of ammonia are formed in
the secondary reformer, furthermore small amounts of methanol are formed in the
CO converters. Together with CO2 present in the raw synthesis gas, these are
stripped off in the process condensate stripper .The impurities, CO2, NH3 and
methanol are stripped off the condensate by means of MP steam.
The MP steam with the impurities leaving the process condensate stripper will be
used as process steam in the primary reformer.

14

4.10 PROCESS DESCRIPTION USING RLNG AS FEED

The plant was originally designed based on steam reforming of naphtha and using
naphtha as fuel. The present revamp enables the plant to operate with LNG feed,
naphtha feed and mixed feed. LNG or naphtha are used as fuel for the feed
preheaters and primary reformer. The revamp has resulted in addition of new
pieces of equipment and modification of some of the process parameters in the
desulphurization and reforming sections. The major changes are the following
- Addition of an LNG Preheater (H 206) upstream the existing H 205
- Addition of a Sulphur Absorber (R 202A) upstream the existing absorber (R
202)
- Addition of LNG fuel preheater (E 207)
4.10.1 AMMONIA PLANT
In the plant, ammonia is produced from synthesis gas containing hydrogen and
nitrogen in the ratio of approximately 3:1.
Besides these components, the synthesis gas contains inert gases such as argon
and methane to a limited extent.
The source of H2 is steam and the hydrocarbons in the natural gas. The source of
N2 is the atmospheric air. The source of CO2 is the hydrocarbons in the natural
gas feed. The main function of the plant is illustrated in the following sketch:

Fig.4.10.1.1.Plant Layout

15

4.10.2 DESULPHURIZATION SECTION

Since the gas contains both H2S and organic sulphur compounds, the
desulphurization takes place in two stages. The organic sulphur compounds are
converted to H2S in the Hydrogenator (R 201), and the H2S absorption takes place
in the sulphur absorbers (R 202 and R 202 A). After desulphurization, the content
of sulphur is less than 0.1 ppm.

Fig.4.10.2.1.Desulhpurization Section

16

4.10.3 FEED PREHEATING

The LNG feed is preheated to 380oC in the newly added LNG heater (H 206),
which is an LNG fired heater. The existing Process Feedstock Preheater (E 216)
and Process Feedstock Superheated (H 205) remain as originally and are only in
operation when naphtha feed is used.
4.10.4 HYDROGENATION
The preheated natural gas is fed to the Hydrogenator (R 201). The vessel contains
Topsoes hydrogenation catalyst TK-550, which is a cobalt-molybdenum based
catalyst.TK-550 catalysis the following reactions:
RSH + H2
R1SSR2 + 3H2
R1SR2 + 2H2
(CH)4S + 4H2
COS + H2

2S
1H
1H

+ R2H + 2H2S

+ R2H + H2S

4H10

+ H2S

2S

Where R is hydrocarbon radical.

The hydrogenation catalyst must not get in contact with hydrocarbons without the
presence of hydrogen. The result would be poor conversion of the organic sulphur
compounds causing an increased sulphur slip to the reforming section. In case
natural gas containing CO and CO2 is fed to the Hydrogenator, the following
reactions will take place:
CO2 + H2
CO2 + H2

2O

(shift reaction)
2O

Therefore, the presence of CO, CO2 and H2O influences the sulphur slippage from
the downstream sulphur absorber. The TK-250 catalyst is in oxidised state at
delivery and resumes its activity when sulphided. In the sulphide state the catalyst
is pyrophoric and it must not be exposed to air at temperatures above 70oC.When
operating with LNG feed, water needs to be added to the preheated natural gas
upstream the Hydrogenator (R 201) to avoid risk of hydrocracking in the

17

hydrogenation catalyst, TK-550.The target is to achieve a water concentration of

0.1 mole% H2O in the natural gas.
4.10.5 H2S ABSORPTION
The hydrogentated natural gas is fed to the sulphur absorbers: the existing R 202,
and the newly added R 202 A. Since the LNG feed contains a greater amount of
sulphur than naphtha, it has been necessary to add R 202 A to ensure a
desulphurization lifetime of 2 years. R 202 A is placed upstream and R 202
downstream. R 202 acts as a guard in case of sulphur breakthrough from R 202 A
or in case R 202 A is taken out of service for catalyst replacement. Each vessel
has one catalyst bed, which contains HTZ-3 catalyst. This zinc oxide catalyst is
in the form of 4 mm extradites. The normal operating temperature is
approximately 380oC. The zinc oxide reacts with the hydrogen sulphide and
carbonyl sulphide in the following equilibrium reactions:
ZnO + H2

2O
2

The catalyst is not reacting with oxygen or hydrogen at any normal temperature.
Zinc sulphide is not pyrophoric and no special care during unloading is required.
Steam operations should not be carried out in R 202 and R 202 A since the zinc
oxide would hydrate and it would then be impossible to regenerate the ZnO
material in the reactor. The sulphur content in the natural gas leaving the final
desulphurisation is reduced to less than ppm by weight.
4.10.6 REFORMING SECTION
In the reforming section, the desulphurized gas is converted into synthesis gas by
catalytic reforming of the hydrocarbon mixture with steam and addition of air.
The steam reforming process can be described by the following reactions:
(1) CnH2n+2 + 2H2
(2) CH4 + 2H2
(3) CO2 + H2

n-1H2n
2

+ CO2 + 3H2 - heat

+ 4H2 - heat
2O

- heat

18

Reaction (1) describes the mechanism of reforming the higher hydrocarbons,

which are reformed in stages to lower and lower hydrocarbons, finally resulting
in methane, which is reformed as shown in reaction (2). The heat input required
for the reverse shift reaction (3) is very small compared to the heat input required
for reactions (1) and (2). The reactions take place in two steps, primary reforming
and secondary reforming as illustrated in figure 3:

Fig.4.10.6.1.Reforming Section
After reforming section, ammonia gas is synthesized as same as naphtha used as
fuel. Then after synthesis of ammonia gas it pumped to the atmospheric storage
tank where it is stored in refrigerated condition because its boiling point is very
low.

19

CHAPTER 5
HAZARDS IDENTIFIED
The manufacture of ammonia involves processing of hydrocarbons under high
temperature, high pressure conditions in the presence of various catalysts,
chemicals etc.
Hazards Identified are as follows:
Fire / Explosion Hazard
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.
Fire box explosions in furnace
Leakage of petroleum products during tanker unloading operations.
Overflow from storage tanks.
Overheating / pressurization of storage tanks.
Improper earthing / lightning protection of storage tanks and pipelines.
Improper sealing of floating roof tanks.
In adequate / improper breather valves leading to tank failures.
Fire Box Explosion in cracker Furnace
High / Low Temperature Exposure Hazards
Burns due to contact with hot surfaces of pipelines, equipments, etc. or
leaking steam lines, process fluids at high temperature.
Frost bite due to contact with anhydrous liquid ammonia at -33 deg. C
Burns due to contact with pyrophoric catalyst.
Toxic Chemical Exposure Hazards
Asphyxia due to inhalation of simple asphyxiants like CO2 , N2, H2, CH4,
naphtha etc. and chemical asphyxiants like CO, NH3, Nickel carbonyl,
V2O5, Hydrazine, NOx, SOx, H2S etc.
20

 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
Other Hazards
Poor House Keeping
Bund wall damaged in storage areas
High Noise
High Vibrations
Steam Leakage from Condensate Pipe
Pipes are corroded may easily subjected to rupture
Fall from Height
Hydrocarbon Exhausts if burner not functioning
Spillage of Chemical during unloading of Naphtha
LNG leakage during pumping
Unsafe acts by worker during regular routine maintenance work were noted
Improper guarding of suction area of blowers
Damages in Flame Arrestors
5.1 DANGEROUS OCCURRENCE IN AMMONIA PLANT
When we are in the Plant there were two dangerous occurrences happened.
Those two dangerous Occurrences were as follows:
Occurrence 1:
Ammonia gas leakage from the Pipeline which is inlet of the compressor.
Due to leakage of gas, pressure has been reduced to the inlet of compressor results
in tripping of compressor. The main cause for the leakage was due to the flange
failure connecting the pipe bends. Flange failure happen because of improper
maintenance and also there is no arrangements for finding the smaller leak in

21

flanges. Ammonia gas released which is less than TLV hence no harm or injury
occurred to workers. Leakage stopped by shut-off valve closure.
Occurrence 2:
Gasket failure in the reactor door in the Secondary Reformer because of this
there was a huge leakage of synthesis gas into the atmosphere at ground level.
The synthesis gas which comprises of hydrogen and other gases which is highly
explosive. No ignition source available there hence no fire / explosion occurred.
The leakage had stopped by opening the reactor door and all gases escaped to
atmosphere.
5.2 MAJOR ACCIDENT HAZARDS
Storage of large amount of produced ammonia about 10,000 tons in
atmospheric storage tank in refrigerated condition. This is extremely hazardous
because if any leakage is there huge explosion / IDLH condition can be lead to a
catastrophic disaster. Also dealing with several raw materials such as naphtha,
RLNG, etc., which are highly hazardous if any leakage of them occurs may leads
to a major accident.
5.3 NAPHTHA MSDS
Naphtha is the raw material used for the production of Ammonia. It is a
liquid hydrocarbon, highly volatile, flammable, explosive and slightly toxic.
Physical properties
Specific gravity

- 0.670

Carbon/hydrogen ratio

-5:3

Flash point

- 21 -55 deg C

Auto ignition temp

- 220 deg C

Health Hazard

Inhalation of concentrated vapour can cause intoxication and headache. Ingestion

may cause burning sensation and vomiting. Frequent contact of Naphtha with skin
can cause Dermatitis
TLV : 500 PPM
22

Fire & Explosion Hazard

It is highly flammable and forms explosive mixture with air.
LEL

- 0.9 %

UEL

-6.0 %

5.4 AMMONIA MSDS

Physical properties
Molecular weight

- 17.03

Boiling point at 1 atm deg C

- (-) 33.4

Vapour Density (Air= 1)

- 0.60

Melting point deg C

- (77.7)

Specific Gravity at 15.5 deg C

- 0.62

Ignition temp deg C

- 651

Health Hazard
Skin: Prolonged contact with the gas can cause skin damage. Contact
with liquid can lead to frost-bite.
Eyes: Extremely irritating can cause permanent damage.
Inhalation: Extremely irritating can cause permanent damage,
prolonged contact at high concentration can be fatal.
TLV

- 25 PPM

STEL

- 35 PPM

IDLH

- 5000 PPM

Fire and Explosion Hazard

It forms explosive mixture with air.
LEL - 16 %
UEL - 25 %

23

CHAPTER 6
HAZARD IDENTIFICATION TOOLS AND EVALUATION

The Hazard Identification Tool used for evaluation of ammonia plant and
ammonia storage are FMEA, FTA and HAZOP.
6.1 FAULT TREE ANALYSIS
A logic tree for system behaviour may be oriented to success or failure. A
fault tree is of the latter type, being a tree in which an undesired or fault event is
considered and its causes are developed. A distinction is made between a failure
of and a fault in a component. A fault is an incorrect state that may be due to a
failure of that component or may be induced by some outside influence. Thus
fault is a wider concept than failure. All failures are faults, but not all faults are
failures.
A component of a fault tree has one of two binary states: essentially it is
either in the correct state or in a fault state. In other words, the continuous
spectrum of states from total integrity to total failure is reduced to just two states.
The component state that constitutes a fault is essentially that state which induces
the fault that is being developed.
As a logic tree, a fault tree is a representation of the sets of states of the
system that are consistent with the top event at a particular point in time. In
practice, a fault tree is generally used to represent a system state that has
developed over a finite period of time, however short. This point is relevant to the
application of Boolean algebra. Strictly, the implication of the use of Boolean
algebra is that the states of the system are contemporaneous.
Faults may be classed as primary faults, secondary faults or command
faults. A primary fault is one that occurs when the component is experiencing
conditions for which it is designed, or qualified. A secondary fault is one that
occurs when the component is experiencing conditions for which it is unqualified.

24

A command fault involves the proper operation of the component at the wrong
time or in the wrong place.

Fig.6.1.1 FTA Symbols

Fig.6.1.2. FTA Symbols

25

6.2 FAULT TREE ANALYSIS ON AMMONIA STORAGE

Fault Tree Analysis drawn using PTC windchill Quality Solution Software
Based on the top event in fault tree bottom events are brain-stormed. All possible
events that can lead to top event are included in the tree. Minimal cut sets are used
for calculation of results.

Fig.6.2.1.FTA Leakage of ammonia from storage tank

Fig.6.2.2.FTA Material Failure

26

Fig.6.2.3.FTA Overpressure in Tank

Fig.6.2.4.FTA Over filling

27

Fig.6.2.5 FTA High Temperature

Fig.6.2.6 FTA ERP Failure

28

6.3 RESULTS OF FTA

From the above drawn fault trees the minimal cut sets can be more than
400.So for cut sets that resulting in top event can be considered and a
probabilities are calculated. The result is as follows
Minimal Cut Set

Probability

(271)(402)(253)(272)(191)

4.3E-7

(271)(802)(253)(272)(191)

2.3E-7

(271)(402)(233)(272)(191)

2.3E-7

(271)(402)(232)(272)(191)

2.3E-7

(271)(402)(231)(272)(191)

2.0E-7

(271)(402)(251)(272)(191)

2.0E-7

(271)(802)(252)(272)(191)

1.2E-7

(271)(802)(233)(272)(191)

1.2E-7

(271)(802)(232)(272)(191)

1.2E-7

(271)(802)(231)(272)(191)

1.1E-7
Table.6.3.1 FTA Result

From the result we inferred that the probability values are very low for minimal
cut sets from fault tree analysis, this shows that likelihood of the leakage from
ammonia storage tank is very less. But if it occurs there will be a severe
consequences. Hence suggesting that all necessary precautions had to be taken.

29

6.4 HAZOP
Hazard and Operability study - the process of assessing hazards and developing
control measures to prevent accidents involving toxic, flammable or explosive
materials to facilitate safe operation of major hazard installations. It takes a
representation of a system and analyses how its operation may lead to an unsafe
deviation from the intent of the system.
The next step of the assessment phase is to consider the deviations from normal
operations in systems, or operational malfunctions identified in the preliminary
hazard analysis (PHA) that could lead to a hazardous situation. This entails a
detailed examination of the system and mode of operation.
The hazard and operability study enables a critical in-depth evaluation of the
system and process classified as relevant in the preliminary hazard analysis. The
HAZOP technique questions systematically every part of the process in order to
establish how deviations from the intended design can occur and determines how
these deviations can give rise to hazardous situations.
The study is progressed from one part of the design to the next until the whole
plant has been examined. Possible deviations and all associated hazards identified
during the examination are then addressed if the solutions are obvious and not
likely to affect other parts of the design. However, additional information is often
required before modifications to designs can be made. The outcomes from
examinations will normally consist of a combination of decisions and additional
questions that have to be addressed by re-evaluations. This process will continue
until the desired outcome is achieved.

Guide words
Guide words are simply words used as keys to suggest the various ways in which
deviations from an intention can occur. A list and their meaning is provided.

30

GUIDE WORDS

MEANING

NONE

No forward flow when there should be, i.e. no flow or

reverse flow

MORE OF

More of any relevant physical property than there should

be, e.g. higher flow (rate or total quantity), higher
temperature, higher pressure, higher viscosity, etc.

LESS OF

Less of any relevant physical property than there should

be, e.g. lower flow (rate or total quantity), lower
temperature, lower pressure, etc.

PART OF

Composition of system different from what it should be,

e.g. change in ratio of components, component missing,
etc.

AS

WELL

AS More components present in the system than there

MORE THAN

should be, e.g. extra phase present (vapour, solid),

impurities (air, water, acids, corrosion products), etc.

REVERSE

A parameter occurs in the opposite direction to that for

which it was intended e.g. reverse flow.

OTHER THAN

Complete substitution e.g. sulphuric acid was added

instead of water.

EQUIPMENT

What else can happen apart from normal operation, e.g.

WORDS OTHER

start-up,

shutdown,

uprating,

low

rate

running,

alternative operation mode, failure of plant services,

maintenance, catalyst change, etc.
Table.6.4.1 Guide Words
The GUIDEWORDS are applied to a range of process PARAMETERS. Usually
only a limited number of combinations of guidewords and process parameters are
used. The most common process parameters are shown in the Table and the four
in the first column are the ones most frequently used - FLOW, PRESSURE,
TEMPERATURE and LEVEL, others will be tested and used on a case by case
31

basis if required. Each guide word is combined with relevant process parameters
and applied at each point (study node, process section, or operating step) in the
process that is being examined. The following is an example of creating deviations
using guide words and process parameters:
GUIDE WORDS

PARAMETER

DEVIATION

NO

+ FLOW

NO FLOW

MORE

+ PRESSURE

HIGH PRESSURE

AS WELL AS

+ ONE PHASE

TWO PHASE

Guide words are applied to both the more general parameters (e.g. react, mix) and
the more specific parameters (e.g. pressure, temperature). With the general
parameters, it is not unusual to have more than one deviation from the application
of one guide word. For example, more reaction could mean either that a reaction
takes place at a faster rate, or that a greater quantity of product results. On the
other hand, some combinations of guide words and parameter will yield no
sensible deviation (e.g. as well as with pressure). With the specific
parameters, some modification of the guide words may be necessary. In addition,
we often find that some potential deviations are irrelevant because of a physical
limitation. For example, if temperature parameters are being considered, the guide
words more or less may be the only possibilities. The following are other
useful alternative interpretations of the original guide words:

or pressure
When dealing with a design intention involving a complex set of interrelated plant
parameters (e.g. temperature, reaction rate, composition, and pressure), it may be
better to apply the whole sequence of guide words to each parameter individually
than to apply each guide word across all of the parameters as a group.
32

6.5 HAZOP ON RLNG PIPELINE

Hazard and Operability Study was done in RLNG pumping pipeline.
RLNG is also being used as a fuel in the production of ammonia in FACT
ammonia plant. It is being pumped from Cochin Refinery Storage of LNG
through pipeline. It may involve several operability hazards to find out hazop was
used. Hazop sheet as follows:

Fig.6.5.1.Hazop sheet

33

Fig.6.5.2. Hazop Sheet

Fig.6.5.3. Hazop Sheet

34

6.6 FMEA
The purpose of an FMEA is to identify the failures which have undesired effects
on system operation. Its objectives include:
(1) identification of each failure mode, of the sequence of events associated with
it and of its causes and effects;
(2) a classification of each failure mode by relevant characteristics, including
detectability, diagnosability, testability, item replaceability, compensating and
operating provisions
The identification of the failure modes, causes and effects is assisted by the
preparation of a list of the expected failure modes in the light of (1) the use of the
system, (2) the element involved, (3) the mode of operation, (4) the operation
specification, (5) the time constraints and (6) the environment. The failure modes
may be described at two levels: generic failure modes and specific failure modes.
The example of set of generic failure modes: (1) failure during operation, (2)
failure to operate at a prescribed time, (3) failure to cease operation at a prescribed
time and (4) premature operation. As examples of specific failure modes, gives:
(1) cracked/fractured, (2) distorted, (3) Undersized, and so on.
The failure causes associated with each mode should be identified. The
failure effects involve changes in the operation, function or status of the system
and these should be identified by the analysis. Failure effects can be classified as
local or as end effects. Local effects refer to the consequences at the level of the
element under consideration and end effects to those at the highest level of the
system.
Where FMEA is to be applied within a hierarchical structure, it is
preferable to restrict it to two levels only and to perform separate analyses at the
different levels. The failure effects identified at one level may be used as the
failure modes of the next level up, and so on.
FMEA is an efficient method of analysing elements which can cause failure
of the whole, or of a large part, of a system. It works best where the failure logic
35

is essentially a series one. It is much less suitable where complex logic is required
to describe system failure. FMEA is an inductive method. A complementary
deductive method is provided by fault tree analysis, which is the more suitable
where analysis of complex failure logic is required.
To use the Risk Priority Number (RPN) method to assess risk, the
analysis team must, calculate the RPN by obtaining the product of the three
ratings:
RPN = Severity x Occurrence x Detection
The consequences of a failure as a result of a particular failure mode. Severity
considers the worst potential consequence of a failure, determined by the degree
of injury, property damage, or system damage that could ultimately occur.
The possible outcomes of FMEA hazard tools as follows:
Identification of any design weaknesses.
Identification of failure modes that are most likely to cause failure of the
product during operation.
Identification of failure modes that could lead to hazardous conditions.
Identification of the product times that are most likely to fail.
6.7 FMEA ON AMMONIA PLANT
FMEA was conducted in several items / components in ammonia plant and
their failure modes, effects, potential causes of failures, severity, occurrence,
detection and RPN (risk priority number) had been calculated for each of the
components. Based on RPN the suggestion has to be given which components
has likely to involve or withheld hazard and its risk is high. The FMEA table is
given below. In FMEA table which item having highest RPN has to be provided
first attention for hazard control.

36

Item

Failure

Effects

Causes

RPN

Modes
Reactor

Torn

Gasket

Gasket

Flange

Rupture,

Recommend
ed Action

Leakage of H2

Leakage of NH3

8 Wear,

64

Testing,

Improper

Proper

Installation

Installation

5 Corrosion,

20

Proper

Abraded

Over

Maintenance,

flange.

pressure

Maintain
Pressure

Pipelin

Cracks,

Leakage of

9 High Stress,

189

Proper

Bends,

flammable gases

Over

Maintenance,

Corrosion

leads to fire

Pressure

Pressure
gauges

Valves

Breakage,

Leakage, Build

7 Improper

63

Proper

Jamming

up pressure if

Maintenanc

Maintenance,

jammed

e, sudden

Interlock

closure

system
provision

Welded

Weld

Leakage of

Joints

breaks-off

Chemical

in Pipes
Reactor

Cracks,

Explosion, Fire

Corrosion

8 Improper

48

Design with

design of

factor of

weld area

safety

9 High

18

Provide

Pressure,

Control

Control

Interlocks,

failure

Pressure
gauges

Compr

Tripping

essor

Leads to system
shutdown

3 Low

Pressure,

Maintain
pressure

leakages etc
Acousti

Loss of its

High Noise

c Insul

properties

cannot be

tal

attenuated

conditions

ation

3 Environmen 2

Table.6.7.1. FMEA Sheet

37

18

Replace
periodically

CHAPTER 7
CONCLUSION

Thus by visiting the plant several hazards were identified and those hazards
were evaluated by hazard assessment tools such as Fault tree analysis, Failure
Mode and Effect Analysis, and Hazard Operability study. From the evaluation,
some of the suggestions were given for ammonia plant and it includes design
changes for flange to compressor inlet, reactor gasket sealing should be replaced
and has to be checked frequently, the gas monitoring and detection system has to
be installed around the plant.
The Hazard analysis were conducted in both ammonia plant and storage
area. In which storage area is considered to be more hazardous but likelihood of
occurrence of accident in storage area is less. Even though likelihood of
occurrence is less the severity of the accident will be very disastrous in storage
area. Hence recommendations such as monitoring system has to be maintained
correctly, hydrants line and firefighting equipment has to periodically maintained.
Thus all the hazards of the plant and storage area was evaluated using
hazard assessment tools and required suggestions were given to the plant.

38

REFERENCE
Lees loss prevention in Process Industries by Sam Mannan
Hazard Evaluation Guidelines by Recht
Crowl DA, Louvar JF. (2001) Chemical Process SafetyFundamentals with Applications. 2nd ed., Prentice Hall PTR
Lees FP. (1996) Loss prevention in the process industries 2nd ed.,
Butterworth-Heinemann, London, A14/1-26

39