INSTITUTE OF TECHNOLOGY, NIRMA UNIVERSITY, AHMEDABAD – 382 481, 08-10 DECEMBER, 2011 1

Comparative Study between PHA (Process

Hazard Analysis) Evaluation Techniques for
Chemical Process Industries
Tapan Shukla, Parin D. Shah

Abstract-- Process Hazard Analysis (PHA) and Risk
Assessment Techniques are two of the most important
elements of the PSM (Process Safety Management). The
PSM allows the use of different analysis methods and
preventions of hazards in process industries, but the selected
method must be based on the process being analyzed.
HAZard and Operability studies (HAZOP) and Quantitative
Risk Assessment (QRA) are part of the PHAs. HAZOP is
used to identify the hazards presents in the process and plant
designing whereas QRA is a tool which gives us
quantification of hazards identified during the HAZOP
process. QRA can also assess risk for the worst situation that
can be created by a process plant. In general there are lot of
misconceptions and misunderstandings about applicability
of HAZOP and QRA in industrial practise. This paper
compares results of HAZOP & QRA applied on hypothetical
case study. This comparison reveals difference between
HAZOP and QRA for the discussed hypothetical study and
it can be applied for all chemical process industries also.
Key Words: HAZOP, QRA, Hazard, Risk, Process Hazard
Evaluation Techniques, Process Safety Tools
I. INTRODUCTION
S afety is a concept covering hazard identification, risk
assessment and accident prevention. Safety should
always come first and remain so despite of costs. Good
design and forethought can often bring increased safety at
less cost [1].
PSM is a part of safety management, which focuses
on the concerns of major hazards impacting safety,
environmental damage and business losses. Oil & Gas
companies are significant users of PSM (Process Safety
Management) methods, particularly where there are
hazardous processes or large inventories of flammable or
toxic materials. Regulators expect operators of volatile
plants to implement measures to ensure that their plants
are operated and maintained in a safe manner. PSM
techniques are numerous - from process screening and
concept selection, through hazard identification,
consequence evaluation, risk assessment, ALARP study,
pre start-up action response auditing, to inspection and
auditing during operation. A hazard is a condition with the
potential of causing an injury or damage. A chemical
process normally has a number of potential hazards, for
example raw material and intermediate toxicity and
reactivity, energy release from chemical reactions, high
temperatures, high pressures, quantity of material used
etc. Each of these hazards impacts the overall process. A
pursuit of safety is largely a matter of identifying hazards,
eliminating them where possible or otherwise protecting
against their consequences. Often two hazards need to be
present simultaneously to cause a major accident. In Fig.
1 the techniques for identifying hazards and the
techniques for assessing those hazards have been shown
[2]. The best known measure for safety is risk, which is
defined as the possibility of loss. The problem of
awareness of risk can be seen as one of failure of
communication and of mismanagement. Risk by the
Chartered Insurance Institute (1974) is the mathematical
probability of a specified undesired event occurring, in
specified circumstances or within a specified period. In a
process plant the losses may be such as damage to
equipment, a loss of production or an environmental
damage as well as an injury or a death. Risk involves two
measurable parameters consequence and probability.
Some events are more probable to occur than others, but a
unique consequence of the sequence of events cannot be
predicted.
III. HAZOP
Hazop refers to HAZard and OPerability studies. HAZOP
is a structured and systematic technique for examining a
defined system, with the objective of identifying potential
hazards in the system. The hazards involved may include
both those essentially relevant only to the immediate area
of the system and those with a much wider sphere of
influence, e.g. some environmental hazards.
Fig. 1: Methods of identifying and Assessing Hazards
INSTITUTE OF TECHNOLOGY, NIRMA UNIVERSITY, AHMEDABAD – 382 481, 08-10 DECEMBER, 2011
Identifying potential operability problems with the system
and in particular identifying causes of operational
disturbances and production deviations likely to lead to
nonconforming products. An important benefit of the
Hazop study is resulting knowledge, obtained by
identifying potential hazards and operability problems in a
structured and systematic manner, is of great assistance in
determining appropriate remedial measures. A
characteristic feature of a HAZOP study is the
“examination session” during which a multidisciplinary
team under the guidance of a study leader systematically
examines all relevant parts of a design or system. It
identifies deviations from the system design intent
utilizing a core set of guide words. The technique aims to
stimulate the imagination of participants in a systematic
way to identify hazards and operability problems. HAZOP
should be seen as an enhancement to sound design using
experience-based approaches such as codes of practice
rather than a substitute for such approaches [3].
The overall aims to which any HAZOP Study
should be addressed are:
To identify all deviations from the way the design
intended to work, their causes and all the hazards and
operability problems associated with these deviations.
To decide whether action is required to control the hazard
or the operability problem, and if so, to identify the ways
in which the problems can be solved.
To identify cases where a decision cannot be taken
immediately and to decide on what information or action
is required.
To ensure actions decided are followed through (i. e.
HAZOP Close-out report) [4].
IV. ASSESSING THE RISK (QRA)
Risk is defined by the likelihood of an undesired
event within a specified period. It is a complex function of
probability, consequences and vulnerability.
Why Risk Assessment is required?
• All activities are associated with some risk.
• In order to make a commercial enterprise successful, it is
necessary to identify and manage the risks.
Figure 2: Risk funnelling
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• The two-dimensional nature of risk (likelihood and
consequence) has to be recognised for effective risk
management.
• Not only the experts' world-view of risk, but that of the
non-expert should be given due consideration in the risk
management process, if the latter have an input into
decision making.
• A decision made based on risk assessment, followed by
the implementation of a risk management process would
go a long way to ensuring project success.
This raises the question:
'How to know that a risk is low enough to be
acceptable? In other words, how low is low enough?'
To answer this question, some measures of risk
are required, so that relative risks can be compared [5].
Risk measures can range from the purely
qualitative to fully quantitative, accompanied by
uncertainty analysis. In most cases of risk management,
measures are applied along a continuum in order to ensure
minimum work for the maximum effect. It is important
that appropriate measures are used throughout the process
life cycle and within a particular project. It is also
important that the measures used in a project are
commensurate with the stage of analysis and the level of
understanding. Fig. 2 shows the risk measurement
continuum with some examples of techniques in each
class. Chemical process Quantitative Risk Analysis
(QRA) is a methodology designed to provide management
with a tool to help evaluate overall process safety in the
chemical process industry (CPI). Management systems
such as engineering codes, checklists and process safety
management (PSM) provide layers of protection against
accidents. However, the potential for serious incidents
cannot be totally eliminated. QRA provides a quantitative
method to evaluate risk and to identify areas for cost-
effective risk reduction. The QRA methodology has
evolved since the early 1980s from its roots in the nuclear,
aerospace and electronics industries. The term "Chemical
Process Quantitative Risk Analysis"
is used throughout this book to emphasize the features of
this methodology as practiced in the chemical,
petrochemical, and oil processing industries. QRA
enables the engineer to evaluate risk. Individual
contributions to the overall risk from a process can be
identified and prioritized. A range of risk reduction
measures can be applied to the major hazard contributors
and assessed using cost-benefit methods. Comparison of
risk reduction strategies is a relative application of
CPQRA. At each stage of increasing safety (decreasing
risk), the associated changes may be evaluated to see if
INSTITUTE OF TECHNOLOGY, NIRMA UNIVERSITY, AHMEDABAD – 382 481, 08-10 DECEMBER, 2011
they are worthwhile and cost-effective. Some
organizations also use CPQRA in an absolute sense to
confirm that specific risk targets are achieved. Further risk
reduction, beyond such targets, may still be appropriate
where it can be accomplished in a cost-effective manner
[6]. There are different phases of a plant when risk
management can be applied on it. But with different
phases its applicability, cost and effectiveness varies with
reference to the phase on which it is being applied.
Possible phases where Risk Management can be applied
are with different phases its applicability, cost and
effectiveness varies with reference to the phase on which
it is being applied. Possible phases where Risk
Management can be applied are shown in Fig. 3 below.
V. COMPARISON BETWEEN HAZOP AND QRA
REVEALING SOME MISCONCEPTIONS.
a. 'Hazop and QRA' are two sides of a coin and are more
or less synonymous. 'Hazop and QRA are often
confused. The above figure 1 makes the difference
clear[7].
b. Once the Hazop and QRA exercise is carried out,
management competence is irrelevant and can be
overlooked. The assumption while utilising the
sophisticated technique of 'Hazop and QRA is that the
plant will be operated and maintained in the manner
assumed by the design team and in accordance with
good management and engineering practices. There is
also another hidden assumption, that the protective
systems will be tested regularly and repaired promptly,
whenever necessary. If these assumptions are not true,
then 'Hazop and QRA are a waste of time. It is no use
identifying hazards or estimating their probability, if
no one wants to do anything about them. It is no use
installing trips and alarms, if no one is going to use or
maintain them. The time spent on a 'Hazop and QRA
would be better spent on bringing the safety
consciousness of employees and management up to
standard. This aspect is very important for developing
countries like India [8].
c. By using the Hazop and QRA technique, we will
foresee every hazard and accidents will be eliminated.
Despite all our efforts, we shall fail to foresee every
hazard and some will result in accidents. This
limitation must be clearly borne in mind while using
the 'Hazop and QRA technique.
d. Once hazards are identified by using Hazop technique,
accident history is irrelevant. As stated earlier, despite
all our efforts, we shall fail to foresee every hazard and
some will result in accidents. One must, however,
remember that people should learn from these
accidents. People should analyse not only the
accidents, which have resulted in serious injury or
damage, but also from those which have not, e.g. leaks
that do not ignite. If these 'near misses' are not
investigated and the lessons learned are not known to
3
those concerned, injury or damage will result next
time.
e. Hazop and QRA can essentially be carried out at any
stage of a project. This need not be always true. In
fact, in ICI, from where the technique originated,
'Hazop and QRA were used to form a part of a series
of six 'hazard studies': (i) Exploratory phase (ii) Flow
sheet phase (iii) Detailed design (iv) Construction (v)
Commissioning (vi) Post-commissioning The
rigorous use of the Hazard and operability studies was
carried out during the stage (iii), i.e. 'Detailed design'.
In other words, an organization can develop a strategy
or a definite policy as to when and how to use the
technique. Therefore, the thumb rule that the technique
must essentially be used at any stage of the project need
not always be true[9].
f. Hazop and QRA technique need not be rigorously
followed for computer-controlled plants. In computer-
controlled plants, the instructions to the computer (the
applications software) should be studied as well as the
line diagrams. For example, if the computer is
instructed to take a certain action when the
temperature rises, the Hazop team should consider the
possible consequences of this action as well as the
consequences of the computer failing to take action. In
a batch plant, the consequences may be different at
each stage of the batch. On a continuous plant, the
consequences may be different during the various
phases of the process, such as start-ups, shut-downs,
catalyst regeneration, etc. Dangerous incidents have
occurred because the 'Design and Operating Teams'
assumed that the computer would always take care of
alarm situations and they need not consider in detail
the consequences of each action at each stage.
g. The team leader can be effective, if he is an expert in
process engineering. It is possible for a team to get
carried away by enthusiasm and install expensive
equipment to guard against unlikely hazards. The team
leader must counter this by asking how often the
hazard will occur and what will be the consequences.
The most effective team leader must therefore not only
be trained in 'Hazop' but also in 'QRA [10].
h. Since plant people do not have time, a design
contractor can effectively carry out 'Hazop'. The user
of the plant must be involved in the Hazop exercise
because it will give the operating staff an
understanding of the reasons for the various design
features and help them write the operating instructions.
The only effective team is one that owns the problem.
The user is responsible for changes in the procedure.
Hence, he should be involved in the 'Hazop' exercise
along with the design contractor. However, the design
contractor cannot be a substitute for the plant user.
i. 9. Leave it until the Hazop. Whenever someone
suggests a change in design, the design engineers react
saying, 'Don't bother now. There will be a Hazop later
on. Let us talk about it then'. This is not a correct
INSTITUTE OF TECHNOLOGY, NIRMA UNIVERSITY, AHMEDABAD – 382 481, 08-10 DECEMBER, 2011
approach. A Hazop should be a final check on a
basically sound design to make sure that no unforeseen
effects have been overlooked. It should not replace the
normal consultations and discussions during the design
development; a Hazop meeting is not the right place
for redesigning the plant.
j. 10. Computers can carry out a Hazop. Hazop is a
creative exercise. Factors such as intuition and flair
play a very large part in thinking of the team members.
The knowledge used in a Hazop is broad and deep.
The expert systems are suitable for narrow and deep
knowledge. Hence, computers can certainly be used as
an aid in Hazop studies. However, they presently
cannot substitute a 'Hazop team'.
VI. COMPARISON BETWEEN HAZOP AND QRA ON A
HYPOTHETICAL CASE STUDY
Fig. 3: A sample system of mixing TBC in Butadiene (Note that this is
purely representational, and not intended to illustrate an actual system.)
Fig. 3 shows a simple system of mixing TBC (4-
t-p-butyl catechol) in to butadiene. TBC is mixed into
Butadiene to prevent self-polymerization of Butadiene
while its storage. Butadiene has tendency of self-
polymerization whenever it comes into contact of oxygen.
But in the mixture of TBC and Butadiene, TBC acts as an
Oxygen Scavenger which does not allows butadiene to
undergo self-polymerization. Now, when butadiene
undergoes self-polymerization under a closed storage
vessel, temperature in the vessel will increase due to
exothermic nature of the polymerization process. This will
also lead to pressurization of the vessel. After certain
extent of pressure rise if pressure reduction measures are
not taken then pressure in vessel may go beyond the
design pressure of the storage vessel and the final
consequences will be catastrophic rupture of the storage
vessel leading to explosion and fire in the storage facility.
Now to apply HAZOP technique on the system
which is shown in Figure 4 leads we have to select a
parameter first to start with. Step by step methodology
and learning from it are described as below:
1. Selecting a parameter from list of parameters
provided by UK ICI, which are flow, pressure,
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temperature, level, concentration, composition,
viscosity etc. Here others parameter also can be
selected but for the example study initiation flow
parameter is selected.
2. After selecting the parameter next step will be to
applying the guidewords (i.e. Less, More, No,
Reverse etc.) Here less flow of TBC from tank 1 to
vessel V 1 through the pump and strainer is being
considered.
3. Now next step is finding the cause. This is where the
brainstorming comes into the picture. After
discussion with the HAZOP team causes were found
for selected parameter deviation. In this case causes
of less flow are choking or pump strainer or pump
malfunctioning.
4. After determining the cause it is found that what will
be the consequence if the cause takes place. Here the
consequence will be less mixing of TBC in line
mixture with butadiene resulting in less composition
of TBC in Butadiene storage. So as explained in
system description above less TBC can lead to self-
polymerization BD storage and further lead to over
pressurization and explosion. So maintaining TBC
appropriate composition in TBC is very critical.
5. Next step is evaluating the safeguards already
provided in the system we assume that there is a PDI
is already provided across the strainer to know
choking of strainer. This is the only safeguard
currently. This completes the study for one deviation
of selected parameter which in our case is less Flow.
Further study can be continued by discussing others
deviation such as more flow, no flow, reverse flow
etc. A sample worksheet is shown in Fig. 4, which is
normally used for the recording of HAZOP
proceedings. Conclusion from this study is mentioned
at the end of the article by comparing it with the
conclusions of QRA of the same system [11].
This was about HAZOP, but now if QRA is to be
applied on the same above scenario then a different
approach has to be taken. Unlike HAZOP where
concentration was on finding the root cause of the
problem. But QRA starts with the worst possible
consequence and studying its impacts, affecting area
along with Risk Identification. When talking about Risk,
it by default considers likelihood of the accident as well as
severity. Both are taken care during QRA studies. Here to
carry out QRA, Phast Risk Micro software is used which
is developed by DNV AS Ltd., and which is licensed to
M/S ZEPPELIN SYSTEMS INDIA LTD. To do risk
identification of this scenario some assumption have been
made which were required for software inputs. Those
assumptions are listed below
A random site layout has been taken here in which
location of BD storage tank is assumed.
All storage parameters and condition are assumed.
INSTITUTE OF TECHNOLOGY, NIRMA UNIVERSITY, AHMEDABAD – 382 481, 08-10 DECEMBER, 2011
An average whether category and random wind
speed are assumed for the QRA results.
Population data inside as well as around the site.
Failure frequency of the BD tank V 1.
Fig. 6 and 7 shows results of QRA done by the Phast Risk
software. Though here results are shown only in pictorial
form, in practise a theoretical report which includes other
information like Conc v/s Distance data, radiation level
distances, explosion overpressure distances, individual
risk, societal risk, toxic exposure distances, dispersion
data, discharge data is also given with the QRA report.
This QRA report helps to mitigate the consequence and
reduce the risk associated with the process plant.
VII. DISSCUSION FROM RESULTS OF BOTH STUDIES.
HAZOP recommendation: HAZOP always focuses on
removing the cause of the consequences rather than
applying mitigation measures.
In this case root cause of BD vessel explosion was
because of strainer choking. The first thing can be
done is to change the location of the strainer and take
it to upstream of the TBC tank T 1. So we can remove
impurities at the inlet of tank only so it can’t come in
pump suction.
Figure 4: Sample worksheet for the recording of the HAZOP proceedings
5
Second suggestion will be addition of duplex strainer
so that if the PDI shows high PD (pressure difference)
operator can immediately go and isolate that choked
strainer and takes second strainer in line.
QRA recommendations: Fig 5 shows explosion contours.
How much pressure will be experienced at a particular
distance from the location of explosion if the BD storage
tank explodes. And fig 6 is the risk contour, which shows
individual risk. It means probability of one fatality with
respect to duration of one year in and around the plant
location. Whereas Fig 7 shows F-N curve representing
societal risks. The main recommendations from this study
are
Looking at the explosion contour it can be seen that
the control room is coming within the overpressure
zone of 0.2068 bar which is the level at which heavy
damage to structures and 100% fatality is expected.
Therefore it is recommended that the control room
should be shifted to a safer location.
Looking at the Fireball contour it can be seen that the
admin building and the control room are falling in the
radiation zone of 4 KW/m2. At this level of radiation
no significant burns are expected for the human body.
INSTITUTE OF TECHNOLOGY, NIRMA UNIVERSITY, AHMEDABAD – 382 481, 08-10 DECEMBER, 2011 6

Looking at the overall risk contour it can be seen

that the maximum risk level that the plant is exposed
to due to the failure of Butadiene Tank is in the
range of 10-7 per average year which is the
acceptable level of risk according to the UK HSE’s
Risk Acceptance Criteria.
F-N curve shows that the societal risk is partially in
the acceptable region and partially in the ALAP
region.

Fig. 5: Explosion Contours
VIII. CONCLUSIONS
A result of HAZOP identifies the hazards whereas a
result of QRA assesses the hazards.
HAZOP is a preferred technique and almost being
applied on every project, whereas QRA is being applied
on selective projects, especially where it is a legal
requirement.
HAZOP is a qualitative technique where QRA as its
name itself tells, it is a quantitative technique
HAZOP is a tool which requires a multi-disciplinary
team to carry out it, whereas QRA requires only one or
two engineers with good knowledge of QRA software.

IX. REFERENCES

[1] DOE HANDBOOK of CHEMICAL PROCESS HAZARDS

ANALYSIS; DOE-HDBK-1100-2004 August 2004, U.S.
Department of Energy, Washington, D.C. 20585, February 1996.
[2] Heikkilä; AnnaMari; “Inherent safety in process plant design An
indexbasedApproach;” TECHNICAL RESEARCH CENTRE
OF FINLANDESPOO 1999.
[3] Hazard and Operability Studies (HAZOP Studies) – Application
Guide. Hazop guideline BS IEC 61882. International Electro
technical Commission.
[4] Kletz, T.A., “HAZOP & HAZAN: Identifying and Assessing
Process Industry Hazards,” Fourth ed. Institution of Chemical
Engineers, Rugby, UK, 1999.
Fig. 6: Risk contours [5] Cameron, I. T.; “PROCESS SYSTEMS RISK
MANAGEMENT”; Department of Chemical Engineering;
Computer Aided Process Engineering Centre University of
Queensland; Brisbane, Australia
[6] GUIDELINES FOR Chemical Process Quantitative Risk
Analysis; SECOND EDITION, CENTER FOR CHEMICAL
PROCESS SAFETY of the AMERICAN INSTITUTE OF
CHEMICAL ENGINEERS;3 Park Avenue New York, New
York 10016-5991
[7] Raghu. Raman; “Safety Engineering and Risk Management”
Kellog Brown & Root Pty Ltd; ELSEVIER ACADEMIC
PRESS;Sydney, Australia 2005
[8] Gujar A. M.; “Myths of Hazop and Hazan Myths of Hazop and
Hazan”; J. Loss Prey. Process Ind. Vol. 9. No. 6. pp. 357-361.
1996
[9] 'Loss Prevention Bulletin', Issues 121, 122, 123. Institute of
Chemical Engineers, UK.
[10] P.A.M. Ujit de Haag, B.J.M. Ale, “Guidelines For Quantitative
Risk Assessment”, PGS 3 edition, Ministry Of Netherlands,
December 2005.
[11] Guidelines For Safety Studies, DOC no: APS-SSP-301;
Fig. 7: F-N Curve Diagram Zeppelin Systems India Pvt. Ltd.