Risk analysis of a chemical industry using ORA procedure

Journal of Loss Prevention in the Process Industries 14 (2001) 4359
www.elsevier.com/locate/jlp
Risk analysis of a typical chemical industry using ORA procedure

Faisal I. Khan 1, S.A. Abbasi
Computer Aided Environmental Management Unit Centre for Pollution Control and Energy Technology, Pondicherry University, Pondicherry
605 014, India
Abstract
This paper presents a risk assessment study of a typical chemical process (sulfolane manufacturing) industry using optimum risk
analysis (ORA) methodology recently proposed by these authors (Khan, F. I., & Abbasi, S. A. (1995). Risk analysis; a systematic
method for harzard identification and assessment. Journal of Industrial Pollution Control, 9(2), 66; Khan, F. I., & Abbasi, S. A.
(1998a). Techniques for risk analysis of chemical process industries. Journal of Loss Prevention in Process Industries, 11(2), 91.)
The paper also describes briefly the different steps of ORA methodology and the available techniques and tools to conduct each
step of the ORA. The study suggests that the reactor and the storage units of the industry are highly vulnerable to accidents and
need elaborate safety arrangements. The damage potential of these units is such that its impact would permeate far beyond the
plant boundaries and would cause damage to nearby areas. A few recommendations have been made to reduce the existing risk
potential. However, the industry still needs to have high level safety arrangements and emergency procedures in position to counter
any unwanted situation in the industry. 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Risk analysis; Hazard assessment; Safety analysis; Consequence analysis; Sulfolane industry
1. Introduction
The science of risk assessment (RA), which has
emerged in recent years with ever-increasing importance
is defined as a process, which includes both qualitative
and quantitative determination of risks and their social
evaluation. As more and more industries are commissioned and more and more accidents come to light,
there is ever increasing importance being attached to
RA. The following key aspects of accidents in chemical
process industries are addressed during RA:
1. development of techniques and tools to forecast accidents. This is aimed at creating opportunities to rectify problems (of man and materials) before any harm
can result;
2. development of techniques and tools to analyse
consequences of likely accidents. Such consequence
analysis fulfils two objectives:
it helps in siting of industries and management of
* Corresponding author. Fax: +91-41-385-2263.

E-mail address: profFabassi@vsnl.com (S.A. Abbasi).
1
Visiting Research Professor, Thew Memorial University of Newfoundland, St John, NF, Canada.
sites so as to minimise the damage if accident

does occur;
it provides feedback for other exercises in accident
forecasting and disaster management;
3. development of managerial strategies for emergency
preparedness and damage minimisation.
Considering the serious and ever increasing risk posed

by the chemical process industries as elucidated above,
it is necessary to conduct risk assessment and develop
strategies to prevent the accidents or, if preventive measures fail, to cushion their adverse impacts.
Such exercises in risk assessment would involve the
following essential steps:
1. identifying vulnerable spots or high risk points in

an industry;
2. simulation of accidents and assessment of the damage
they may cause;
3. use of the results of the previous step in identifying
the priority areas where preventive measures would
be needed;
4. development of disaster management plans based on
1 and 2 above.
0950-4230/01/$ - see front matter 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 9 5 0 - 4 2 3 0 ( 0 0 ) 0 0 0 0 6 - 1
44
F.I. Khan, S.A. Abbasi / Journal of Loss Prevention in the Process Industries 14 (2001) 4359
2. Brief review of the available risk assessment

techniques
In the last two decades, a few techniques have been
proposed for risk and safety study (Khan & Abbasi,
1998a). These techniques may be broadly characterised
into three main groups.
1. qualitative techniques such as hazard and operability
studies HAZOP (Lawley, 1974; Knowlton, 1981;
CCPS, 1989) failure mode effect analysis FMEA
(Henevely & Kumanoto, 1981; Lees, 1996) and
Checklists (Balemans, 1974; Hessian & Rubin, 1991);
2. quantitative techniques such as maximum credible
accident analysis MCAA (ILO, 1988; Mallikarjunan, Raghavan & Pietersen, 1988); quantitative risk
assessment, (CCPS, 1989; Van Sciver, 1990; Arendt,
1990), Hazard analysis HAZAN (Kletz 1985,
1990); and consequence analysis (WHO, 1984;
Kayes, 1986; Abbasi & Khan, 1996; Kletz, 1990; Pietersen, 1990); and
3. probabilistic techniques such as probabilistic safety
analysis PSA (Papazoglou, Nivoliantiou & Christou, 1992; Kafka, 1994; Bekjord, Cunningham &
Murphy, 1993) and probabilistic risk analysis PRA
(Guymer, Kaiser & Mckelvey, 1987; Lai, Shenoi &
Fan, 1986). These techniques have been proposed for
one or other specific applications but do not deal with
the rest of the steps needed in a complete risk analysis. For example; MCAA is a technique that identifies
and assesses the hazards based on the worst accident
scenario. However, it is not capable of drawing out
the causes and probability of occurrence of these hazards. Similarly consequence analysis provides a
detailed assessment of the consequences of an accident but does not give any information regarding the
mode of occurrence, causes and probability of occurrence of such accidents.
3. Optimal risk analysis (ORA)

We have proposed a new methodology named ORA
(Optimal Risk Analysis Khan & Abbasi, 1998a). ORA
involves four steps : i) hazard identification and screening, ii) hazard assessment (both qualitative and
probabilistic), iii) quantification of hazards or consequence analysis, and iv) risk estimation. These steps of
ORA and corresponding methodology to be used in each
step are presented in terms of ORA algorithm (Fig. 1).
The methodology is named as optimal risk analysis as
it is swift, less expensive to implement, less time-consuming, and is as (or possibly more) accurate and precise, as existing methodologies.
ORA aims to identify and assess hazards and to esti-
mate the risk factors due to any mishap/accident in the

chemical process industry. The ORA framework enables
modelling of probable accidents based on the chemical
and process characteristics, evaluation of mode of occurrence of these accidents, estimation of detailed consequences and finally prediction of risk factors.
3.1. Hazard Identification
HIRA (Hazard Identification and Ranking Analysis)
is a technique proposed by these authors to conduct the
very first step of risk analysis (hazard identification and
ranking). The objective of this step is to identify the
chemicals and unit operations that constitute potential
hazard. HIRA is based on a multi-attribute hazard identification and ranking method detailed elsewhere (Khan &
Abbasi, 1998b). lt considers hazard potential in a unit
as a function of material, capacity, type of unit operation,
operating conditions, and surroundings (degree of conjunction, location of other hazardous units etc.). The output of HIRA gives two indices, fire and explosion damage index (FEDI) for fire and explosion hazard, and toxic
damage index (TDl) for toxic release and dispersion hazard (Fig. 2). The procedure to estimate FEDI is presented
in Fig. 3.
The indices for fire and explosion (FEDI) and toxicity
(TDI) proposed here have some advantages over the conventional indexing techniques formulated by the Dow
and the Mond chemical companies, and IFAL
(instantaneous fractional loss). HIRA is more systematic
and predicts results with more reliability as it takes into
account a larger number of parameters and leads to
quantification. HIRA methodology is simple in
implementation, modular in structure, and can be easily
automated to reduce expert time. The important features
of HIRA are:
1. it takes into consideration impact of various process
operations, and the associated parameters for hazard
identification;
2. it provides quantitative results of good reliability;
3. most of penalties used in computing FEDI and TDI
(on which HIRA is based) are derived from the welltried and tested models of thermodynamics, transport
phenomena, heat transfer and fluid dynamics. A few
penalties are quantified with the help of empirical
models and hazard ranking procedures such as NFPA
(NFPA, 1991) and EHC (EHC, 1987);
4. it does not need case-by-case calibration as its magnitude directly signifies the level of hazard;
5. it may be used for very rapid reconnaissance of risk.
3.2. Hazard assessment
3.2.1. Qualitative hazard assessment
Qualitative hazard assessment is part of the detailed
risk analysis of chemical process industries and a hazard
Fig. 1.
45
Simplified block diagram shwoing various steps with techniques and/or tool to conduct optimal risk analysis (ORA).
and operability (HAZOP) study is the best technique to

carry out this step. It is a systematic study conducted by
a team of experts of different disciplines to identify and
assess hazards using brainstorming discussions of deviation in operational parameters from normal/standard
conditions. This study needs high levels of expertise and
substantial time commitments. The various steps
involved in any typical HAZOP need a sustained high

level of mental performance and alertness for a long span
of time, but the repetitive nature of these steps inevitably
generates a feeling of drudgery and mental fatigue, even
exhaustion. This may not only reduce the effectiveness
of HAZOP, but even render it incomplete or erroneous.
These authors have made an effort to overcome some of
46
Fig. 2.
Algorithm of hazard identification and ranking (HIRA) system.
47
such that the recommendations made by the study can

be followed easily and economically (Khan & Abbasi,
1997a). To fulfil the above objective a systematic procedure along with various recommendations has been
developed. This procedure has been named optHAZOP
(Khan & Abbasi, 1997a). This procedure uses an already
developed expert knowledge-base; the procedure as
shown in Fig. 4. This knowledge-base is a large collection of facts, rules and information regarding various
components of process plant. Along with the use of
knowledge it also suggests a few recommendations to
reduce the time of discussion and produces effective and
reliable results.
Fig. 3. Systematic procedure for fire and explosion damage index

(FEDI) calculation.
these limitations and proposed an optHAZOP methodology. It is detailed in Khan and Abbasi (1997a), however a brief description is presented below.
The optimal and effective HAZOP (optHAZOP) signifies the application of hazard study in such a way that
the duration of the study should be optimum, and most
of the hazards should be identified and assessed. The
level of efficiency, and reliability of results, should be
3.2.2. Probabilistic hazard assessment

Fault tree analysis involves identification of causes of
an accident, frequency of occurrence of an accident, and
contribution of each cause to the accident. It is a useful
methodology but is besieged with the same types of limitations which we find with other methodologies such as:
need of large volumes of precise data and requirement
of much expert time. We have made attempts to overcome these limitations by incorporating a combination
of analytical methods and the MonteCarlo simulation
technique (Rauzy, 1993) with fuzzy set theory (Khan &
Abbasi, 2000a). A software PROFAT (Probabilistic
Fault Tree Analysis) has been developed on the basis of
this recipe (Khan & Abbasi, 1999a).
A methodology has been developed to conduct probabilistic fault tree analysis during risk assessment in the
chemical process industries. The methodology is based
on a system involving a) development of a fault tree, b)
determination of minimum cutsets or shortest pathways
leading from initiating events (malfunctioning) to the top
event (the major accident), c) probability analysis, and
d) working out improvement index values. To this end
techniques of Boolean algebra, structure modelling, analytical method of finding cutsets (top-to-bottom
algorithm), MonteCarlo simulation, optimisation technique and fuzzy probability set have been used. The
methodology has been termed by us analyticalsimulation methodology (ASM) and a software package PROFAT (PRObabilistic FAult Tree analysis) has also been
developed by us to facilitate the use of the methodology
in a rapid and effective, yet user-friendly manner. PROFAT enables the user to find out, in an industry, i) initiating events which may eventually lead to a major accident, ii) minimum cutsets (a series of initiating events
aiding each other in causing the accident), iii) the probabilities of occurrence of such initiating events, iv) relative contributions of each of the initiating events and,
finally, v) identifying initiating events with the greatest
potential to cause the top event (major accident) so that
accident prevention strategies and emergency preparedness plans can be focused on them. The noteworthy attributes of the system are: resilience towards lack of pre-
48
Fig. 4.
Algorithm for optHAZOP procedure.
cision in the basic data, swift processing with moderate

requirements of computation capacity (sophistication of
computers needed), ease of use, and directly utilizable
output.
3.3. Consequence analysis
Consequence analysis involves assessment of likely
consequences if an accident scenario does materialise.
The consequences are quantified in terms of damage
radii (the radius of the area in which the damage would
readily occur), damage to property (shattering of window
panes, caving of buildings) and toxic effects
(chronic/acute toxicity, mortality). The assessment of
consequence involves a wide variety of mathematical
models. For example source models are used to predict
the rate of release of hazardous material, the degree of
flashing, and the rate of evaporation. Models for
explosions and fires are used to predict the characteristics of explosions and fires. The impact intensity models are used to predict the damage zones due to fires,
explosion and toxic load. Lastly toxic gas models are
used to predict human response to different levels of
exposures to toxic chemicals.
3.3.1. MOSEC (Modelling and simulation of fires and
explosions in chemical process industries)
A software MOSEC (MOdelling and Simulation of
Fire and Explosion in Chemical process industries) has
been developed specifically to estimate the impacts of
accidents involving explosion and/or fire (Khan &
Abbasi, 2000b). MOSEC comprises of state-of-the-art
models to deal with : i) pool fire, ii) flash fire, iii) fire
ball, iv) jet fire, v) boiling liquid expanding vapour
explosion (BLEVE), vi) confined vapour cloud
explosion (CVCE), vii) unconfined vapour cloud
explosion (VCE), and viii) vented explosion. The
software has been developed in an object-oriented programming environment using C++ as a coding tool. It
has been made user-friendly by incorporating such features as graphics, on-line help, ready-to-use output format, etc.
3.3.2. HAZDIG (Hazardous dispersion of gases)
HAZDIG is computer software specifically developed
to estimate the consequences (damage potentials and
risks) due to release of toxic chemicals, accidentally or
voluntarily (Khan & Abbasi, 1999b). The modular structure of HAZDIG (developed in an object oriented
environment) enables swift processing of data and computation of result. It is also easy to maintain and upgrade.
HAZDIG incorporates latest models for estimating
atmospheric stability (Van Ulden & Holtslag, 1985) and
dispersion (Pasquill & Smith, 1983; Erbrink, 1995;
Khan & Abbasi, 1997b; Khan & Abbasi, 2000c). The
data needed to run the models is easy to obtain and feed,
49
e.g. properties of chemicals, operating conditions, ambient temperature, and a few commonly available meteorological parameters. A database containing various proportionality constants and complex empirical data has
been built into the system. It is capable of handling various types of release and dispersion scenarios: two phase
release followed by dispersion, momentum release followed by dispersion, dispersion of heavier-than-air
gases, etc. The Graphics option enables the user to draw
any industrial site/layout using freehand drawing or
using any already defined drawing tool. The contour
drawing option has the facility for drawing various
damage/risk contours over the accident site.
3.3.3. DOMIFFECT (DOMino EFFect analysis)
Most of the risk analysis methodologies deal with
accidents in a single industry, more so in one of the units
of an industry. But it is always possible that a major
accident in one unit say an explosion or a fire can
cause a secondary accident in a nearby unit which in
turn may trigger a tertiary accident (Khan & Abbasi,
1998c). The probability of such domino or cascading
effects occurrence is increasing day by day with more
new industries being built in already congested industrial
areas (Khan & Abbasi, 1998c).
We have developed a computer automated methodology DOMIFFECT (DOMino efFECT) which enables
one to know a) whether domino effects are likely to
occur in a given setting, b) if they do what would be the
likely accident scenarios, and c) what would be the likely
impacts of the different scenarios (Khan & Abbasi,
1998d). Finally, the tool guides us towards strategies
needed to prevent domino effects (Khan & Abbasi,
1998d). DOMIFFECT is menu driven and interactive,
capable of the following:
1. estimation of all possible hazards from toxic release
to explosion;
2. handling of interaction among different accidental
events (generation of domino or cascading accident
scenarios);
3. estimation of domino effect probability;
4. estimation of domino effect consequences.
3.4. Risk estimation

The results of risk assessment are represented in the
form of two different risk factors. These risk factors are
in turn represented in two forms either as FN curves
(frequency of occurrence vs. numbers of fatality) or risk
contours over the area. The FN curves, also known as
risk profiles, are the curves of various risk potential
values represented in an XY diagram, where the Y axis
represents the cumulative frequency of occurrence of an
event and the X axis represents the degree of damage in
50
terms of number of fatalities. The FN risk profiles are

mainly used to show the risk variation and acceptable
criteria of risk. This presentation is specially beneficial
for planning control strategies development.
The risk contours are the most common and significant way of representing the risk. Different levels of risk
circles are plotted in terms of contours over the site. A
site layout, with risk contour drawn over it provides a
clear visual picture of the areas under risk. This representation is particularly beneficial when carrying out
the study of an industrial complex surrounded by different types of locations and industries. This representation
also gives a direct idea of the domino or cascading
effect.
The above described ORA procedure has been used
to study a typical chemical plant engaged in the manufacture of sulfolane. The industry has been put up in an
industrial complex about 25 km from Thane, Maharastra,
India. The industry is surrounded by densely populated
villages Bandukhadi, Balramkhadi, and Ramnagar,
and various other industries (Fig. 5).
Fig. 5.
4. Typical application of ORA

A risk assessment study has been conducted of a sulfolane manufacturing plant (Khan, Akthar, Fatima &
Parveen, 1992). Sulfolane is a trade name of sulfur and
butadiene compound, chemically known as 2,3,4,5
tetrahydrothiophene11dioxide. It is used as a solvent
for the extraction of benzene, toluene, and xylene (BTX)
as well as a raw material for many chemical process
industries. The simplified process flow diagram of the
sulfolane manufacturing plant is shown in Fig. 6, while
a brief process description is presented below.
4.0.1. Process description

Butadiene and sulfur dioxide are stored in the liquid
state under high pressure. The process involves their
reaction under controlled conditions of temperature and
pressure in a three stage continuous stirred tank reactor
(CSTR) to produce sulfolene. The temperature of CSTR
Layout of the plant and its surroundings.
51
Fig. 6. Simplified process flow diagram of sulfolane plant (S1: butadiene storage; S2: sulfur dioxide storage; S3: hydrogen storage; S4: liquid
vapor separation tank; R1: reactor 1; R2: reactor 2; E1: evaporator; STR1: stripper; C1 and C2: compressors;
is maintained at about 85C by using cooling liquid

(water mixed with methanol). The ratio of butadiene to
sulfur dioxide in the reactor is kept as 1:1.2.
The reaction between butadiene and sulfur dioxide is
exothermic under normal operating conditions (pressure
10 atm and temperature 85C) and is highly susceptible to causing undesirable side reactions under high
temperature and low pressure conditions. Addition of
about 200 ppm of solvent (tertbutyl cethchol) inhibits
the side reactions, Later, the effluents of the reactor
(butadiene, sulfur, and butadiene sulfone) are sent to a
flash evaporator where sulfur dioxide is separated and
compressed to the liquid state and recycled back to the
reactor. The remaining traces of sulfur dioxide is separated out in a stripper and finally recycled back to the
reactor. The pure sulfolene (butadiene sulfone) is passed
to the hydrogenator, where it is hydrogenated to give
sulfolane (terta hydrothiophene-11 dioxide). The conversion efficiency of the hydrogenation reaction is
around 99%. The output of the reactor is the final product sulfolane , having 99% sulfolane and 1%
impurity.
Most of the operations such as storage, transportation
through pipe lines, reaction, and separation are carried
out under high pressure. Moreover, butadiene and hydrogen are highly flammable whereas sulfur dioxide is toxic.
A slight increase in temperature in the sulfonation reactor causes a runaway reaction which generates excessive
heat that leads to sudden rise of pressure and finally may
cause bursting of the tank (BLEVE/CVCE) and/or
release of chemical. The decrease in butadiene to sulfur
dioxide ratio below 1:1 may also cause a side reaction
(formation of polymer butadiene sulfone; an undesirable
hazardous chemical). Further, presence of excess sulfur
dioxide in the hydrogenation reactor decreases the product quality and increases the chances of hazardous
side reactions.
The separation of unreacted sulfur dioxide is carried
out in the flash evaporator and subsequently compressed
to a liquid state. There is sufficient probability of sulfur
dioxide leakage from evaporator as well as compressor
unit. Moreover as sulfolene and butadiene (flammable)
are also hazardous chemicals thus the leak of sulfolene
or butadiene from evaporator or compressor units would
also lead to undesirable situations (fire or vapour cloud
explosion). However, compared to sulfur dioxide the
quantity of butadiene and sulfolene involved in the evaporator and compressor is less.
52
A detailed risk assessment study has been conducted

of the above described process plant using optimal risk
analysis methodology, with the following objectives:
1. to identify the type of hazards present at each location
or units of the plant,
2. to identify the basic causes that lead to such hazards,
3. to quantify the hazards in terms of probable damage,
4. to quantify the probability of occurrence of such hazards,
5. to quantify risk factors.
The results of the study are presented in subsequent sections.
4.1. Hazard identification, and screening
The complete plant of sulfolane manufacturing has
been divided into six different units according to the
process/operation involved in them, they are : a) storage,
b) reactor 1 (sulfonator), c) mass transfer unit, d) pumping and compressing unit, e) reactor 2 (hydrogenator),
and f) transportation unit. The most commonly used hazardous chemicals in these units are; i) butadiene, ii) sulfur dioxide, iii) hydrogen, and iv) sulfolene.
The hazard identification and ranking (HIRA) technique (detailed earlier) has been applied to different units
of the plant. As per HIRA technique, two indices fire
and explosion damage index, and toxic damage index
have been calculated for each unit.
The results of HIRA indices for different units of the
plant are presented in Table 1. It is evident from the
table that storage units, reactor 1 (sulfonator), reactor 2
(hydrogenator), evaporator, and pipe line numbers 11
and 19 have high damage potential and need a
detailed study.
4.2. Hazard analysis

The units screened (found hazardous) have been subjected to a hazard assessment step. optHAZOP methodology has been used for qualitative hazard assessment
(cause finding), while a modified fault tree analysis
(MFTA) technique has been used for probabilistic hazard assessment to estimate the frequency of occurrence
of unwanted situations and the relative contribution of
each cause to lead to the unwanted situations. A brief
note on the results of each study is presented below.
4.2.1. Qualitative hazard assessment optimal
hazard and operability study (optHAZOP)
optHAZOP methodology has been applied to every
component of the screened (hazardous) units. The objectives of this study were to identify and assess the hazards
qualitatively, to find the main causes and consequences
of such hazards and if possible some recommendations
to control and/or mitigate these hazards. The optHAZOP
study result for reactor 1 (sulfonator) is presented in
Table 2. The study reveals that high temperature, change
in normal operating pressure and change in ratio of reactants are the most vulnerable deviations for the reactor.
Any one of these deviations may cause a runaway reaction which may lead to explosion in the reactor. Similarly, for the flash evaporator it has been observed that
high temperature or high flow rate causes high pressure
development in the unit, which may lead to instant
(explosively) release of chemical.
The optHAZOP study for reactor 2 (hydrogenator)
reveals that high pressure, and presence of impurity
(sulfur dioxide) are the most vulnerable deviations.
These deviations have a high likelihood of causing the
runaway reaction which later may cause the release of
highly flammable chemical hydrogen, which on meet-
Table 1
Damage and risk index values for different units of sulfolane plant
Units
Chemicals
Type of hazard
Fire and explosion

damage indexa
Toxic damage indexb
Storage 1
Storage 2
Storage 3
Line no. 11
Line no. 12
Line no. 14
Line no. 19
Reactor 1
Reactor 2
Evaporator
Pump no. 3
Pump no. 5
Pump no. 7
Butadiene
Sulfur dioxide
Hydrogen
Butadiene
Sulfur dioxide
Sulfolene
Hydrogen
Sulfur, Butadiene
Hydrogen, Sulfolen
Sulfur dioxide, Sulfolene
Sulfur dioxide
Butadiene
Hydrogen
Fire and explosion

Toxic release
Fire and explosion
Fire and explosion
Toxic release
Fire and toxic release
Fire, explosion and toxic
Toxic release
Fire and explosion
Fire and explosion
511.5
432.12
377.12
243.2
154.67
138.74
341.78
467.34
415.3
338.34
67.57
63.62
58.51
56.78
100.0
100.0
25.67
87.1
57.6
95.67
85.67
75.67
87.3
87.56
35.41
21.32
a
b
release
release
release
release
Fire and Explosion damage index represent damage radii in meters due to fire and explosion.
Toxic damage index represent percentage of people that get affected in a area of 500 m radius.
53
Table 2
HAZOP study results for sulfonation reactor (Reactor 1)
Guide words
Deviation
Possible causes
Consequences
More
High temperature
Cooling system fail reactant temperature

increase reactant ratio decrease
mechanical heating
Reactant flow increase Pressure controller
fail
Runaway reaction leading to excessive

pressure development
High pressure
High reactants ratio
Less
No
Part of
As well as
Reverse
Excess heat generation, chances of

runaway reaction which leads to high
pressure development
Slow reaction rate
Ratio controller fail flow controller fail

pump speed increase
Butadiene flow increased
Flow controller fail pump speed increase Chances of runaway reaction
ratio controller fails
.. same as above ..
Reaction rate decrease high pressure in
SO2 flow increased
the reactor
High stirring speed
Voltage rise speed controller fail
Mechanical heating and so chances of
runaway reaction
Low temperature
Excess cooling reactant temperature
Reaction rate decrease
decrease
Low pressure
Low pressure of reactant leak in reactor Chances of runaway reaction
pressure controller fail vent valve open
Low ratio of reactants
Increase in butadiene flow decrease in
Chances of temperature rise and runaway
reaction.
SO2 flow ratio controller fail
Low butadiene flow rate
Leak in pump or in line capacity in
Reaction rate decrease low quality
storage decrease valve not working
product
properly
..same as above..
Decrease in reactant ratio hence chances
Low SO2 flow rate
of runaway reaction
No flow of butadiene
Pump fail valve get stuck pipe fracture
No reaction
material not available
No flow of sulfur dioxide
...same as above...
Ratio will decrease hence chances of
runaway reaction
No stirring
Power fail shaft fracture stirrer motor fail Hot spot formation and ultimately leading
to unwanted side reaction.
No cooling
Cooling water not available cooling
Rise in reactor temperature and so
jacket fouled cooling water temperature chances of side reaction
high
Decrease in pressure leak in line/pump
Chances of side reaction
SO2 quality decrease
Decrease in solvent conc.
Impure solvent solvent not available
Chances of side reaction decrease in
efficiency
Decrease in butadiene quality
Decrease in pressure leak in line impure Conversion effeciency decreases with
butadiene
chances of side reaction
Presence of propane inferior quality and Inferior quality
Chances of side reaction sharp decrease
pentane with butadiene
in reaction efficiency product quality
decrease
Leak in line/pump inferior SO2
Hazardous side reaction conversion
Presence of air with liquid SO2
efficiency decrease
Chances of runaway reaction
Decrease in pressure
Slow reaction rate chances of toxic
Phase change of SO2
release side reaction
Phase change of butadiene
Decrease in pressure
Slow reaction rate chances of explosive
mixture formation
ing an ignition source would cause vapour cloud

explosion and/or fire.
The qualitative hazard assessment study for pipe lines
(pipe line numbers 11 and 19) reveal that low pressure and
high temperature are the most vulnerable deviations. These
deviations are likely to change the phase of chemical which
may cause development of excessive high pressure in the
line. This excessive high pressure may lead to the release
of chemical instantly and/or continuously depending upon
the material of construction of pipes, reliability of joints

and degree of overpressure in the line. Similarly storage
of butadiene is susceptible to high temperature and high
pressure while sulfur dioxide storage is susceptible to low
pressure and high temperature. Any of these deviations
would cause far reaching consequences as the capacity of
chemical stored and the conditions of the storage are severe
enough (liquefied storage under high pressure and ambient
temperature) to cause a catastrophic event.
54
4.3. Probabilistic hazard assessment modified fault

tree analysis (MFTA)
Table 4
List of important initiating events (basic events) leading an explosion
sulfonation reactor with improvement index
The fault tree analysis technique has been used to

quantify the hazard in terms of probability of occurrences and to identify the basic events and their contribution in causing pre-identified hazard (identified in previous steps). The fault tree is solved by an algorithm
named MFTA recently proposed by these authors. The
algorithm is detailed elsewhere, whereas, a brief description is presented in an earlier section. The procedure
MFTA starts with the development of a fault tree for
each unit and subsequently solving it to find out the
minimal cutsets leading to the top event (unwanted
situation/an accident). In subsequent steps, the probability of a top event is calculated using fuzzy probability space concept and reliability data of basic events.
The reliability data of various basic components has
been adopted from literature (Contini, Ziomas & Amendola, 1991; AlChE, 1989; Khan & Abbasi, 1997c,d).
Table 3 presents the probability of occurrence of various
undesirable events in pre-identified hazardous units of
the plant. It is evident from the table that line numbers
11 and 19, evaporator and pump numbers 2,5 and 7 have
a high probability of causing (103 to 104/yr) accidents.
The contribution of basic events to lead the top event
(unwanted situation in unit) has been analysed by estimating the Improvement Index (IN). The IN gives the
clear identification of the most vulnerable events
(variables) for system safety, and their contribution in
causing the top event (fire, explosion, toxic release
and/or a combination of these). The higher the IN for
an event means the higher contribution to system failure.
For sulfonation unit (Reactor 1) the list of IN for different basic events is shown in Table 4. The probabilistic
hazard assessment study of sulfonation unit predicts that
failure of ratio controller, failure of emergency system
and error in temperature measurement have maximum
contribution in causing the explosion in the reactor.
Initiating event
Table 3
Probability of occurrence of different accidental events in various units
of the sulfolane plant
Units
Type of Hazard
Frequency (/yr)
Storage 1
Storage 2
Storage 3
Line no. 11
Line no. 12
Line 14
Line 19
Reactor 1
Reactor 2
Pump 2
Pump 5
Pump 7
Fire and explosion

Toxic release
Fire, explosion and
Fire and explosion
Toxic release
Fire, explosion and
Fire, explosion and
Fire and explosion
Fire, explosion and
Toxic release
Fire and explosion
Fire, explosion and
8.1*E-06
5.5*E-05
3.4*E-05
1.2*E-03
3.2*E-03
5.4*E-04
7.05*E-04
3.2*E-05
1.5*E-05
2.5*E-03
3.6*E-03
3.8*E-03
toxic release
toxic release
toxic release
toxic release
toxic release
Improvement
index
1. Failure of ratio controller

15.21
2. Valve V-1 stuck
0.05
3. Value V-2 stuck
0.175
4. Flow controller FC1 fails
1.23
0.85
6. Temperature Controller TC-1 fails
1.75
7. Temperature Controller TC-2 fails
2.35
0.05
9. Temperature T1 is high
5.15
10. Cooling jacket fouled
3.25
11. Valve-V3 stuck
1.75
12. In sufficient quantity of cooling liquid
1.95
13. Pump PC1 fails
1.87
14. Leak in line-L11
0.50
15. Leak in line-L12
0.75
16. PC (Pressure Controller) in line-L11
0.075
17. PC (Pressure Controller) in line-L12
0.099
18. Pump-1 is not working
0.055
19. Pump-2 is not working
0.062
20. Stirrer motor fails
2.52
21. Stirrer speed control system fails
1.05
22. Stirrer shaft broken
0.05
23. Temperature sensor of reactor fails
7.53
24. Temperature TRC fails
10.55
25. Emergency system does not work
25.65
26. Impure Butadiene
1.15
2.15
27. Impure SO2
28. Solvent concentration below permissible limit 1.50
Similarly for storage vessels failure of cooling system, error in temperature measurement and transmission,
and failure of vent valve have maximum contribution in
leading vessel failure (explosive release of toxic
chemical). For Reactor 2 (hydrogenator) the maximum
IN has been observed for the leak in line and flow controller failure.
4.4. Consequence analysis
The screened units have been further processed to estimate the damage consequences and risk factors for various probable accident scenarios. The damage consequences are estimated using standard models of fire,
explosion, toxic release, and dispersion. In the present
study, each unit has been subjected to all probable hazards such as i) fire, ii) explosion, and iii) toxic gas/liquid
release and dispersion. To conduct this step, these
authors have used two software programmes MOSEC
and HAZDIG. This software was developed for detailed
damage potential estimation due to any accident involving fire, explosion, toxic release, and dispersion, and/or
a combination of these. Detailed description of this
software are presented elsewhere.
The estimated damage potentials (using software

MOSEC and HAZDIG) are subsequently converted into
percentage of lethality over the area using vulnerability
models (Greenbook, 1992; Lees, 1996).
The process of consequence analysis starts with an
accident scenario development subsequently estimating
the damage potential of these accident scenarios and
finally calculating the risk factors. The results of the
consequence analysis step are discussed in the forthcoming section.
4.4.1. Development of accident scenarios
Accident scenarios have been developed for each unit
considering the type of hazard present, process operation, chemicals involved in the unit, and operating conditions of the unit.
The accident scenario for Reactor 1 (sulfonator) is
visualised as, explosion due to excessive development of
pressure in the reactor (runaway reaction) which causes
release of toxic and flammable chemicals (sulfur dioxide,
butadiene, and butadiene sulfone). The released chemicals (unburned flammable chemical butadiene and
butadiene sulfone) on meeting ignition sources leads to
fire (flash fire).
The accident scenario for Reactor 2 is anticipated as
confined vapour cloud explosion (CVCE) followed by
fire ball. This scenario is explained as; an excessive high
pressure in reactor (due to excess feed, change in phase
of hydrogen or auto-ignition of hydrogen) leads to the
bursting of reactor as CVCE and the released unburned
chemical (hydrogen with butadiene sulfone) on meeting
ignition source forms a fire ball.
The accident scenarios visualised for accidents in different storage units (butadiene and sulfur dioxide) are
boiling liquid vapour cloud explosion (BLEVE) followed by fire (flash fire) for butadiene storage unit and
BLEVE followed by dispersion of sulfur dioxide.
BLEVE has been visualised for both the units because
these storage units are operating under high pressure
(liquefied state) hence an instantaneous release of chemicals would cause BLEVE. This scenario has been verified with the past study of similar storage units (Khan &
Abbasi, 1997b; Contini et al., 1991).
The accident scenario for pipe lines (numbers 11 and
19) has been conceived as continuous release of butadiene followed by flash fire in case of pipe line number
11, and instantaneous release followed by fire ball in
case of pipe line number 19. The difference in both scenarios are due to differences in properties of the chemicals
and transportation conditions. Hydrogen is a highly
flammable gas which on ignition leads to a fire ball,
whereas butadiene is comparatively less flammable and
having more chance of continuous release which leads
to either jet fire or flash fire, whereas flash fire has more
probability of occurrence.
The accident scenario for the evaporator is visualised
55
as: continuous release of chemicals (sulfur dioxide and

butadiene sulfone) followed by dispersion. It is because
the evaporator unit is a flash evaporator working under
ambient conditions, hence more possibility for the
chemical to escape continuously either through valves
(safety or relief) or through some leaks (joints, weld,
etc.) which are subsequently followed by dispersion.
4.4.2. Damage potential estimation
The results of consequence analysis for Reactor 1
(sulfonator) are presented in Tables 5 and 6. It is evident
from the tables that an area of 700 m radius would be
under lethal toxic, overpressure and heat load (more than
50% probability of lethality). The results for Reactor 2
has been presented in Tables 7 and 8. The results reveals
that lethal overpressure (50% probability of lethality)
would be observed over an area of 500 m radius, while
lethal heat load would be persistent over an area of 300
m radius. The probable accidents in storage vessels
(butadiene and sulfur dioxide) reveals severe damage
potential due to fire, explosion and toxic load. The damage potential of different accidental events for these units
are presented in Tables 9 and 10. It has been observed
from the tables that 50% lethality condition would persist over an area of more than 1000 m radius. The results
of consequence analysis for pipe line numbers 11 and
19 (Tables 11 and 12) reveals that lethal heat load would
be observed over an area of 300 m radius. The results
of other units shows comparatively lower hazards than
in case of Reactor 2.
4.5. Risk estimation
Using the results obtained by consequences analysis
step and probabilistic hazard assessment step
(probability of occurrence of the accident scenarios),
individual risk factors have been estimated. The individual risk factor is a direct representation of likelihood of
fatalities of an individual in an area (taking into consideration both damage potential and probability of
occurrence). The individual risk factors have been categorised in three main groups, severe risk (having a
value higher than 1103) high risk (1104), and moderate
risk (1105).
In order to enable swift visualisation of accident scenarios, these risks have been depicted (in-terms of
contours) over the study area (Figs. 710). It is clear
from Fig. 7 (accident scenario for Reactor 1) that an area
of 600 m radius is under severe risk while moderate
risk contours extend up to 850 m. The severe risk contour for an accident in Reactor 2 (Fig. 8) would
encompass an area of 400 m radius while the risk contour of moderate potentiality would extends up to 650
m radius. The severe risk contour for an accident scenario in the storage units (butadiene and/or sulfur dioxide)
would extend more than 800 m, which envelops the
56
Table 5
Result of consequences analysis for an accident in sulfonation reactor (Reactor 1)
Damaging events
Distance (m)
500
200
700
Accident scenario: CVCE followed by flash fire and toxic release and dispersion
CVCE
3.59
1.62
Heat intensity (kW/M2)
Peak over pressure (kPa)
334.10
165.75
Shock wave (m/s)
485.13
365.72
Missile Effect
Missile velocity (m/s)
433.14
251.65
314.18
Kinetic Energy of missile (kj/m2) 627.34
Fire: flash fire
532.45
334.38
Heat intensity (KJ/m2)
Toxic release & dispersion
Toxic load (ppm)
2277
1198
Table 6
Lethality effect of various potentiality over the area due to an accident
in sulfonation reactor (Reactor 1)
Lethality effect
200
Distance
(m)
500 700
1000
0.213
51.24
165.45
0.06
25.16
78.95
78.882
198.45
34.15
72.34
192.55
76.69
477
165
Table 8
in hydrogenation reactor (Reactor 2)
Lethality effect
1000
200
(%age) chances of particular effect

100% lethality by radiation
50% injury due to shock wave
100% lethality due to toxic gas
100% chances of damage due to
missile
100
100
100
100
91
72
100
85
76
55
73
31
42
32
45
19

100
87
87
100% chances of damage due to missile 82
Distance
(m)
500 700
1000
85
61
61
55
25
18
18
6
63
34
34
23
Table 7
Result of consequence analysis due to an accident in hydrogenation
reactor (Reactor 2)
Hazard effect
200
Distance
(m)
500
700
Table 9
Result of consequence analysis due to an accident in storage units
(butadiene and sulfur dioxide)
1000
Damaging event
Accident scenario: CVCE followed by fire ball

CVCE
2.18
0.98
0.14
Heat intensity (kW/m2)
Peak over pressure (kPa) 193.12
146.76
39.56
Shock wave (m/s)
428.41
326.23
131.45
Missile Effect
355.342 198.41
65.241
Kinetic Energy of missile 574.21
245.86
110.34
(kj/m2)
Fire: fire ball
471.2
301.3
115.34
Heat intensity (KJ/m2)
200
0.044
18.64
56.45
26.413
35.67
56.3
densely populated areas, while the moderate risk contours would envelop an area of 1120 radius (Fig. 9). For
pipe lines the severe risk contour (Fig. 10) would extend
only up to a distance of 200 m, while moderate risk contour would extend up to a distance of 400 m. The area
enveloped by risk contours of various potentiality for
probable accident in other units are lower.
Distance
(m)
500
700
1000
Butadiene
Accident scenario: BLEVE followed by flash fire and toxic release
and dispersion
CVCE
5.23
4.21
3.19
1.97
Heat intensity (kW/m2)
Peak over pressure (kPa)
535.63
405.23 324.21
157.45
Shock wave (m/s)
765.34
573.34 302.65
187.23
Missile Effect
611.73
487.45 333.23
189.23
Kinetic Engery of missile
874.45
613.34 435.67
284.75
(kj/m2)
Fire: fire ball
671.23
413.45 298.23
179.45
Heat intensity (kJ/m2)
Sulfur dioxide
Accident scenario: Instantaneous release followed by dispersion
Toxic release & dispersion
Toxic load (ppm)
3774
2011
987
245
57
Table 10
in storage units (butadiene and sulfur dioxide)
Lethality effect

100% chances of damage due to missile
200
Distance
(m)
500 700
1000
100
100
100
100
100
100
100
100
71
65
100
54
93
81
100
78
Table 11
Result of consequence analysis due to an accident in pipe lines numbers 11 and 19
Damaging event
200
Fig. 7. Risk contours indicating the impact area for an accident

occuring in Reactor 1 (sulfonator) due to severe risk (A), high risk
(B), and moderate risk (C).
Distance
(m)
500
700
1000
Pipe line number 11 containing butadiene

Accident scenario: continuous release followed by flash fire
Fire: flash fire
312.45
176.67
98.56 34.78
Pipe line number 19 containing hydrogen
Accident scenario: instantaneous release followed by fire ball
Fire: fire ball
413.56
225.47
108.45 35.56
Table 12
in pipe lines numbers 11 and 19
Damaging event
200
(% age) chances of particular effect
100% chances of damage due to missile
87
Distance
(m)
500 700
65
21
1000
It may be seen that the risk contours for accidents in

the storage vessel and Reactor 1 (Figs. 7 and 9) are
extending beyond the boundaries of the industry and
envelop other industries and nearby populated areas.
Whereas the risk contours for accidents in other units
are confined to the campus of the sulfolane plant but
the risk contours for accident in hydrogenation reactor
(Reactor 2) extends up to the storage units of the plant
(Fig. 8). This may cause secondary accidents, and the
impacts of which may go beyond the plant confines.

occuring in Reactor 2 (hydrogenator) due to severe risk (A), high risk
(B), and moderate risk (C).
5. Summary and conclusion

The paper introduces the methodology of optimal risk
analysis (ORA) developed by us. It constitutes a set of
techniques developed by us which enable risk analysis
to be conducted at lesser time, effort, and costs but as
(or more) accurately as the existing methodologies. The
paper has also detailed an illustrative application of ORA
on a sulfolane industry.
The hazard identification study for a sulfolane manufacturing plant showed that the storage vessels, Reactors
1 and 2, evaporator, and pipe line numbers 11 and 19,
are its most hazardous units. A detailed study was consequently recommended and carried out for these units.
This suggested that high temperature, low pressure, pres-
58
urgent and thorough minimisation/mitigation measures

should be taken. The following suggestions are made in
this context:

occuring in storage vessels due to severe risk (A), high risk (B), and
moderate risk (C).
1. Instead of one or two large-capacity vessels, several

vessels of smaller capacity should be used for storage.
2. Adequate space should be kept between the storage
vessels and buffers provided between them so that
adverse consequences of failure in one of them do not
cause second or higher order accidents.
3. Sensitive gas detecting devices for flammable and
toxic gases should be installed in the premises of storage area and other units.
4. There should be regular and thorough inspections of
electronic control equipment followed by meticulous maintenance.
5. Sufficient quantities of inert gases should be made
readily available to dilute the concentrations of
toxic/flammable gases if they escape to the atmosphere.
6. A thorough emergency preparedness strategy should
always be kept in position, fortified by periodic drills
or dry runs so that the damage is contained if an
accident does occur.
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Journal of Loss Prevention in the Process Industries 14 (2001) 4359

Risk analysis of a typical chemical industry using ORA procedure

* Corresponding author. Fax: +91-41-385-2263.

sites so as to minimise the damage if accident

Considering the serious and ever increasing risk posed

1. identifying vulnerable spots or high risk points in

2. Brief review of the available risk assessment

3. Optimal risk analysis (ORA)

mate the risk factors due to any mishap/accident in the

and operability (HAZOP) study is the best technique to

involved in any typical HAZOP need a sustained high

Algorithm of hazard identification and ranking (HIRA) system.

such that the recommendations made by the study can

Fig. 3. Systematic procedure for fire and explosion damage index

3.2.2. Probabilistic hazard assessment

Algorithm for optHAZOP procedure.

cision in the basic data, swift processing with moderate

3.4. Risk estimation

terms of number of fatalities. The FN risk profiles are

4. Typical application of ORA

4.0.1. Process description

Layout of the plant and its surroundings.

is maintained at about 85C by using cooling liquid

A detailed risk assessment study has been conducted

4.2. Hazard analysis

Fire and explosion

Toxic damage indexb

Fire and explosion

Cooling system fail reactant temperature

Runaway reaction leading to excessive

High reactants ratio

Excess heat generation, chances of

Ratio controller fail flow controller fail

ing an ignition source would cause vapour cloud

the material of construction of pipes, reliability of joints

4.3. Probabilistic hazard assessment modified fault

The fault tree analysis technique has been used to

Fire and explosion

1. Failure of ratio controller

The estimated damage potentials (using software

as: continuous release of chemicals (sulfur dioxide and

(%age) chances of particular effect

(%age) chances of particular effect

Accident scenario: CVCE followed by fire ball

(%age) chances of particular effect

Fig. 7. Risk contours indicating the impact area for an accident

Pipe line number 11 containing butadiene

It may be seen that the risk contours for accidents in

Fig. 8. Risk contours indicating the impact area for an accident

5. Summary and conclusion

urgent and thorough minimisation/mitigation measures

Fig. 9. Risk contours indicating the impact area for an accident

1. Instead of one or two large-capacity vessels, several

ence of impurity and leak in the line/unit are the most

Hessian, R. T., & Rubin, J. N. (1991). In Greenberg & Crammer,

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