DR Risza Paper

Accepted Manuscript
Resolving inherent safety conflict using quantitative and qualitative technique

Mardhati Zainal Abidin, Risza Rusli, Azizul Buang, Azmi Mohd Shariff, Faisal Irshad
Khan
PII:
S0950-4230(16)30225-X
DOI:
10.1016/j.jlp.2016.08.018
Reference:
JLPP 3306
To appear in:
Journal of Loss Prevention in the Process Industries
Received Date: 15 May 2015

Revised Date:
24 July 2016
Accepted Date: 28 August 2016
Please cite this article as: Zainal Abidin, M., Rusli, R., Buang, A., Shariff, A.M., Khan, F.I., Resolving
inherent safety conflict using quantitative and qualitative technique, Journal of Loss Prevention in the
Process Industries (2016), doi: 10.1016/j.jlp.2016.08.018.
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Title
Resolving Inherent Safety Conflict using Quantitative and Qualitative Technique
Author names and affiliations
Azizul Buang
Chemical Engineering Department
Universiti Teknologi PETRONAS
32610 Bandar Seri Iskandar
Perak Darul Ridzuan Malaysia
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Risza Rusli*
risza@petronas.com.my
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Mardhati Zainal Abidin

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Azmi Mohd Shariff

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Faisal Irshad Khan

Safety and Risk Engineering Group
Faculty of Engineering and Applied Science
Memorial University
St. Johns, NL A1B 3X5, Canada
*corresponding author
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Abstract
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Inherent safety strategy is an integral component of all engineering activities that strive towards
simpler, cheaper, and safer processes. This also implies that less energy and maintenance are
required and less waste and pollution are produced, which are the underlying principles of the
chemical process industry. However, potential hazards that arise from inherently safer design
(ISD) modification must be evaluated carefully to avoid misapplication of the inherent safer
design strategy. In the previous work, the author developed a qualitative review tool, the ThreeStage ISD Matrix Tool, with the objective to help assessors understand the impact of ISD
modification. In this paper, the Three-Stage ISD Matrix Tool will be combined with quantitative
technique, Hazard Identification and Ranking System methodology, with the aim to quantify the
impact of ISD modification. Two case studies will be presented in order to demonstrate the
applicability of this approach. In the first case study, we show how this technique is capable of
identifying the potential hazard that arise from a modification of Union Carbide India Limited
facilities prior to the Bhopal accident. In the second case study, we show the applicability of this
technique to select the safer options for ammonia storage system considering the fatalities
potential and environmental impact. The results show that the combination of qualitative with
quantitative technique can help assessors to effectively perceive the total impact of ISD
modification.
Keywords
conflicts; inherently safer design; trade-off issues;qualitative; quantitative; ISD conflict
1
Introduction
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Process risk management in a chemical process industry (CPI) involves four strategies:
inherent, passive, active, and procedural. The first layer is an inherent strategy known as
inherently safer design (ISD), an approach that eliminates the root causes of the hazards. The
other strategies involve the addition of safety devices or work processes to control or manage
hazards and are considered as layers of protections (Center for Chemical Process Safety, 2009).
Previous accidents in CPI (Table 1), however, proved that equipping a plant with a layer of
protection is ineffective in controlling hazards. The accidents still occurred due to the
combination of system failures, which were attributed to the hazard still remaining in the system.
Hence the ISD approach is considered a more effective solution than accepting the hazard and
attempting to mitigate the effect. ISD eliminates/reduces hazards based on four basic principles
(Table 2) The maximum benefits of ISD can be obtained by implementing the concept at the
earliest possible stage of process design. However, due to limited available data at this stage,
several studies highlighted the need for a suitable methodology or tool that can facilitate
assessors to quantify the impact of inherent safety implementation (Khan and Amyotte, 2003,
2002; Koller et al., 2001). This necessity then spurred the progress of the methodology
development particularly in assessing the safety level of ISD application. Table 3 summarises the
quantitative tools that have been developed and used to assess the impact of ISD implementation.
Nevertheless, the implementation of ISD is unable to ensure that all potential hazards
associated with a process disappear. In many instances, it is impracticable to remove the hazard
because the same characteristic that produces the material or technology hazardous makes it
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2
2.1
Methodology
Qualitative review (TIM tool)
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useful. To understand the preeminent ISD process, a substantial view is required and the tradeoff must be thoroughly deliberated. Any change in the process that can reduce one hazard might
introduce a new hazard or raise the magnitude of the existing hazard. Accordingly, previous
study highlighted the importance of a review process in order to understand the hazards
associated with ISD alternatives (Hendershot, 1995). The process that has not been evaluated
thoroughly at the early stage will cause repeated evaluations of process alternatives, which
require extra time and efforts (Study, 2006). In the authors previous work, a qualitative
procedure called Three-Stage ISD Matrix Tool (TIM tool) was developed with the aim to help
assessors review ISD alternatives systematically. Under this procedure the keywords that
indicate the deviation of ISD variables of alternatives from the base case will serve as a guidance
for the review process. The result will be in qualitative output that will be documented to ensure
the assessor highlight his or her understanding when reviewing the ISD alternatives. As the
information is preserved, the knowledge transfer process can be facilitated within organisations.
In the present study, the TIM tool was combined with a quantitative evaluation method namely
Multivariate Hazard Identification and Ranking System (HIRA) to quantify the impact of the
ISD modification. The results showed that the combination of qualitative review tools and
quantitative evaluation techniques has guided the assessor in understanding the trade-off
potential and subsequently choose the suitable model to quantify the impact of the ISD
implementation.
Quantitative evaluation (HIRA methodology)
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Fig. 1 shows the framework for a qualitative review of ISD alternatives using the TIM Tool.
A detailed procedure for this tool follows the one adopted in a previous work (Zainal Abidin et
al., 2016) in which the ISD variables for the process alternatives were compared with the base
case one by one. Deviation of ISD was assessed using three key words-higher, lower, and change
phase-to review the impact of the modification on several criteria according to the scope define
by the assessor. In this paper, the outcome from this stage will be the impact of the modification
towards the safety and environment, which will be used as a guidance to select the model for
quantitative evaluation (Section 2.2).
The impact of the modification was then evaluated using the HIRA methodologya
consequence-based method that quantifies potential damage on the basis of energy factors and
penalties (Khan and Abbasi, 1998). Developed according to the type of process units commonly
involved in CPI, the HIRA methodology is unique because it takes into account the potential
energy from chemical, physical, and reaction in the process unit. Thus, several energy factors
and penalties could be considered and may have different formulations to estimate the penalties
in the process unit because it may not necessarily contain similar conditions. The HIRA
methodology was selected for this study because it provides reliable results. The models and
penalty were derived from tried and tested mathematical model and a few penalties were
quantified using empirical models and hazard ranking procedures. Additionally, the index serves
as the basis for the development of several indexes, such as Accident Hazard Index (AHI) (Khan
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Results and Discussion
3.1
Modification of storage system (Bhopal accident)
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and Abbasi, 1997); I2SI (Khan and Amyotte, 2005, 2004); and Safety Weighted Hazard Index
(SWeHI) (Khan et al., 2001). Table 4 shows the formulation of the HIRA model and penalties
used to quantify fire and explosion model and toxic impact. The formulation presented for fire
and explosion model is for unit involving chemical reaction. A similar model was used to
evaluate units involving physical reaction minus several parameters, i.e. reaction energy (F4),
type of reaction (pn9), and side reaction (pn10).
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A qualitative review was conducted on the modification performed to the Bhopal facility
prior to the accident. The modification and the trade-off will be discussed from the ISD
perspective. On 3rd December 1984, about 41 metric tonnes of methyl isocyanate (MIC) were
released from the Union Carbide India Limited (UCIL) pesticide plant in Bhopal. MIC is known
as a hazardous material which possesses flammable, reactive, and toxic characteristics. The event
that caused the accident was traced to a runaway reaction created by the contamination of a MIC
storage tank (Tank 610) with a substantial amount of water (Wiley et al., 2006). Fig. 2 shows the
configuration of Tank 610 as included in the investigation report issued by Union Carbide in
March 1985. Table 5 summarises the hazardous properties of the materials and systems as
identified from the literature review.
Qualitative evaluation using TIM Tool
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According to Union Carbides report, a series of chronic MIC leaks had occurred at the
plant. The transfer pump at Tank 610 was never used when the factory was in operation. By
excluding the pump, the potential of MIC leaking from the pump can be reduced. A reverse flow
was created (Fig. 3) to send the MIC directly from the storage tank to the processing unit. This
measure involved isolating the tank from the PVH and raising the MIC storage tank pressure to
at least 14 psig with nitrogen (Bloch and Jung, 2012).
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Table 6 and 7 show the results of the review process. The review process was conducted
using TIM Tool for a modification performed in the UCIL facilities. From ISD point of view, the
action to exclude the pump can be categorised as a simplify strategy in which complexity is
reduced to decrease the likelihood of MIC leakage. However, to create a reverse flow, the tank
had to be isolated from the smaller equipment and the pressure in the tank needed to be raised.
Increasing the tank pressure is a clear violation of the moderate principle of ISD, which requires
the process to operate in a less hazardous condition. Isolating the tank from the smaller
equipment will also cause loss of protection provided by the nitrogen blanketing systema
practice widely adopted in CPI to protect equipment from structural corrosion damage by air and
moisture. The nitrogen blanketing system also functions to eliminate fire and explosion potential
and to prevent any contaminants from entering the vapor space that can cause product
degradation (Yanisko et al., 2011). In Bhopal case, when the system lost the protection provided
by the nitrogen blanketing system, smaller equipment made of carbon steel was prone to the
corrosion problem, which is a serious issue in CPI. A study reported that 6% out of 623 causes of
the accidents from 284 cases were related to corrosion problem (Kidam and Hurme, 2013).
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This paper analyses the impact of the loss of nitrogen protection due to the modification,
which was performed to reduce leakage potential. The MIC storage tank (Tank 610) was
designed to handle material with a maximum specification of 0.5% chloroform. However,
according to the investigation report, Tank 610 had higher chloroform content than that
allowable (12% to 16%) during the accident (Union Carbide Corporation (UCC), 1985). As
shown in Table 8, chloroform was converted to phosgene and hydrochloric acid when the inert
environment ceased to exist and in the presence of light and air. Under the acidic environment,
PVH, RVVH, and vent line made of carbon steel became corroded and produced rust (iron (iii)
chloride). With the presence of rust, MIC trimer was produced with heat release via a
polymerization process that led to the runaway reaction. A maintenance procedure was
performed to remove the MIC trimer inside the PVH and RVVH by flushing out the substance
using water (Bloch and Jung, 2012). This was the crucial point that needs to be analysed in order
to understand the leading factor of the Bhopal tragedy.
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It was believed that an exothermic reaction occurred due to water contamination and MIC
polymerization process had led to the runaway reaction in the tank. Residue analysis from Tank
610 after the accident contained MIC trimer with 40% to 55% composition. This analysis
attested that a polymerization reaction had occurred in the Bhopal accident. The company
claimed that sufficient quantity of iron catalyst was produced by the corrosion process in the tank
due to the presence of an abnormally high level of chloroform at high temperature, which led to
the polymerization reaction. This argument was supported with the experimental data by UCIL
to replicate the reaction to form the identified component from Tank 610 residues. Based on the
experimental work, a high corrosion rate for stainless steel (43.18 to 88.90 mm/y) was obtained
for MIC containing 18% chloroform and 2% to 7% of water at 200oC (accident temperature)
(Union Carbide Corporation (UCC), 1985). This conclusion, however, was contested by several
Indian experts who argued that the quantity of iron catalyst needed for the reaction could not
have solely come from the corrosion of the stainless steel tank. They believed that the iron mixed
with the water that seeped into the tank from the corroded vent line that had loss the moisture
protection due to the modification done as explained previously (Agarwal, 1986).
Quantitative hazard potential evaluation using HIRA
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Based on the review done in Section 3.1.1, the evaluation of hazard potential using the
HIRA methodology was performed for Tank 610. The objective of the analysis was to uncover
the impact of the changes in terms of damage radii, which had caused 50% fatalities after the
proposed modification in Section 3.1. Fig. 4 shows the severity calculation for Tank 610 before
modification (base case) and Fig. 5 shows the results after modification. The model used for
calculation in Fig. 4 is physical unit and Fig. 5 is a reaction unit with the aim to compare the
changes of damage radii due to the additional runaway reaction potential. In Fig. 4, severity of
the accident was estimated for original design (Fig. 2) where the tank operates at 20oC,
41.36kPa, and the tank is fully protected by a nitrogen blanketing system. In Fig. 5, hazard
potential was estimated for the modified tank design (Fig. 3) at 20oC, 138.20kPa, with the loss of
nitrogen protection that has made the tank prone to runaway reaction. The results show that the
modification in Bhopal facilities will increase the severity of the accidents by 23.68% from the
base case (Table 9). Other that additional energy released due to chemical reaction, significant
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severity increment was contributed by higher penalty given due to the potential of runaway
reaction and higher pressure. Apparently the modification aimed to reduce a likelihood of MIC
release from the pump will induce runaway reaction in the tank and increase the severity of the
accident significantly.
Inherently safer design for ammonia storage system
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3.2
Qualitative evaluation using TIM Tool
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At ambient conditions ammonia exists as a gas phase and it can be liquefied by reducing the
temperature or operating the storage system at high pressure. Anhydrous ammonia storage
system from (Roy et al., 2011) was selected as a base case. In the base case, four units of high
pressure storage were interconnected where each of them operated at 25oC, 1274.86 kPa, and 50
metric tonnes (80% working capacity). Each tank was equipped with two bayonet heaters
operating at 50-90C with water as heating medium and cooling system to avoid overheating
problem. Hazard identification showed that the system posed an immersive danger because
anhydrous ammonia has toxic properties and the system was operated at high pressure. Table 10
shows the results for hazard identification steps of TIM tool based on the data available in a
previous study (Study, 2006). Three alternatives are suggested from typical industrial practice
(Long and Gardner, 2004; UN Industrial Development Organization, 1998; Wiley-VCH, 2003)
to reduce toxic impact based on the ISD approach (Table 11). Capacity and number of tanks
were estimated to fulfill the process requirement and on the basis of the limitations addressed in
previous studies (Chavan, 2012; Lele, 2008; Wiley-VCH, 2003). Alternative 1 offers hazard
reduction chance based on moderation principles, particularly by operating the hazardous system
with less hazardous conditions. The high pressure tank was replaced with a cryogenic storage
system where the liquefied ammonia was stored using refrigerant at ambient pressure.
Alternative 2 also offers hazard reduction via moderation principle. It offers through a dilution
approach in which aqueous ammonia with 29% concentration was stored in a high pressure
vessel. Alternative 3 offers hazard reduction potential using moderation principles. It offers by
replacing the high pressure tank with an atmospheric storage system which stores lower
concentration of ammonia (19%) at ambient temperature.
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This section reviews the impact of ISD modification using TIM Tool in terms of fatalities
potential and environment due to the ammonia release. Environmental contamination will result
in additional consideration for remediation and the ammonia release will give a significant
problem such as soil acidification, water eutrophication, fertilization vegetation, changes in
ecosystems, and smog formation (Lupis et al., 2010). Table 12 shows the results from TIM Tool
where the keywords indicate the deviation of ISD Variables for process alternatives from the
base case. Conflicting ISD principles for process alternatives can be observed from Table 13 to
Table 15. For example, in Alternative 1, the benefits of ISD can be obtained via moderation by
operating at lower pressure as well as by the simplify principle, particularly by eliminating
multiple number of storage tank. However, these measure violates the minimisation principles
that require large inventory of ammonia. More than that, operating at lower temperatures will
increase failure probability due to a brittle rupture problem. In Alternative 2, the positive impact
of ISD implementation can be obtained via moderation particularly by operating at lower
pressure and higher dilution (lower ammonia concentration) but this modification will negatively
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3.2.2
Quantitative hazard potential evaluation using HIRA
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impact minimize and simplify principle. To fulfil the process requirement, a larger amount of
lower concentration ammonia is required, and so is the additional number of storage. Additional
energy is also required to vaporise aqueous ammonia compared to anhydrous ammonia. In
Alternative 3, the benefits of ISD can be obtained via moderation principles which the process
operates at lower pressure and lower concentration, but again the minimisation of inventory and
energy is violated because the process stores large amounts of ammonia and requires higher
energy for vaporisation.
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Based on the review results in Section 3.2.1, the extended HIRA methodology will be used
to identify the impact of toxic release that had caused 50% fatalities and environmental damage
(Table 4). The damage radii calculation for the base case and alternatives are presented in Fig. 6
to Fig. 9 for the impact of toxic release. The release rate used is based on worst case scenario
given by the Environmental Protection Agency (EPA), which considers the release of materials
within 10 minutes. As shown from the results (Fig. 6 to Fig. 9), other that inventory, a
combination of two factorspressure and vapour densityplays an important role for hazard
reduction. Reduction of pressure in process alternatives results in the reduction of pressure
penalty value up to 50% from the base case (from 2.60 to 1.30). For both inventory and pressure,
the reduction of these values will reduce the damage radii, one by reducing the quantity of
material release, the other one by reducing the rate of release. The other factor is vapor density
where the penalty reduced around 87.56 % from 7.72 to 0.96 for Alternative 1, and 92.36% from
7.72 to 0.59 for Alternative 2 and 3. Temperature and material dilution played an important role
in reducing the vapor density. The release of ammonia from high pressure storage (base case) led
to the depressurisation process that resulted in a two-phase flow where part of the fraction
formed a pool and the other part an aerosol. The aerosol then increased the cloud density and it
behaved as heavy gas and slumped to the ground. The heavy gases then caused a buildup of
lethal toxic load closer to the ground and for a longer duration than lighter gas. Combining with
the gravitational impact, the heavy gas that slumped to the ground, spread horizontally, and
increased the hazard zone. By lowering the temperature, the vapor pressure can be reduced, no
initial flash of liquid to vapor in case of a leak when material stored at or below its atmospheric
pressure boiling point and two-phase flashing jet that will cause the rain out of liquid release to
the ground can be eliminated. For material dilution, other than lowering initial atmospheric
concentration, material dilution also give the similar effect where the vapour pressure can be
reduced and will results in the reduction of release rate. Thus, the impact of ISD moderation
principles via dilution and temperature reduction had reduced the dispersion of ammonia gas.
Other than fatalities potential, ammonia release will give a long-term pollution impact
towards the environment. Ammonia release in water will result in nutrient pollution, which will
cause an eutrophication phenomena into natural water source. It will result in excessive plant
growth or the decay of certain species as well as the reduction of water quality. Excessive plant
growth will reduce the oxygen content in water and affect the aquatic life. Release of ammonia
in the soil will change the soil pH to an acidic value. The soil needs to be treated using a leaching
process for plantation. Fertilization of vegetation can occur and will cause the spur of weedy
growth while choking out native flora and wild flower. The above issues will result in the
imbalance of the ecological system. More than that, the combination of ammonia with NOx and
SOx emissions will form fine particulates that will cause the haze problem. The results show that
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the larger area affected by the release will result in higher damage index for the environment.
The damage index value combines the fatality and environmental impact for storage alternatives
(Table 16). As can be seen, by considering the total number of the storage unit the rank of safer
alternatives are Alternative 1>Alternative 3>Alternative 2>Base Case. These results attest that
the hazard potential can be reduced using an ISD approach, which are the moderate and simplify
principles. The positive impacts of these two principles override the negative impact brought by
additional inventory.
Conclusion
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Although ISD philosophy itself is a methodology to achieve fundamentally safer plants,

conflicts between principles can cause divergence from their original intention. Therefore, to
avoid this problem, the potential of hazards associated with alternatives must be understood. In
the previous works we proposed a qualitative review tool with the objective to understand the
trade-off. In this paper, we extend the tool by combining it with a quantitative evaluation. The
results show that by combining these two approaches, the tradeoff can be understood and be
resolved effectively.
A few interesting points can be drawn from the results:
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1. In the first case study, we used the tool to identify the potential conflict between ISD
principles due to a modification done at Bhopal facilities. The impact of changes was
assessed quantitatively using HIRA for fire and explosion impact. The results showed that
the modification conducted to reduce the likelihood of MIC release from the pump can lead
to a runaway reaction in the tank. The damage radii increased around 23% due to the loss of
nitrogen protection and increase of operating pressure. In order to prevent a devastating
consequence as what happened in the Bhopal tragedy, careful judgment has to be done for
every modification.
2. In the second case study, combination of TIM Tool with extended version of HIRA
methodology was used to quantify the impact of accident towards fatalities and environment.
This case study attest the flexibility of TIM Tool in helping the assessors to understanding
the impact of accident towards different criteria. The results showed that the combination of
qualitative review tools and quantitative evaluation techniques has guided the assessor in
understanding the alternatives and subsequently choose the model to quantify the impact of
the ISD implementation. It is important to highlight that the scope of study and the criteria
need to be considered, must be define by assessors prior to the evaluation process.
As a final remarks, while the purpose of ISD is to identify the safest design by eliminating
the root causes of hazards and careful judgment must be made. The potential hazards generated
due to the changes by the ISD principles must be considered. Misuse of ISD philosophy can lead
to a more severe accident as what happened in the Bhopal case. It is important to understand that
ISD is not a stand-alone concept. It is a part of total improvement to achieve friendliness in a
plant that can fulfil a requirement for industries.
5
Nomenclature and Units
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Unit
Factor A
Ambient temperature
Auto ignition temperature
Atmospheric pressure
Damage index for acute
Damage index for air
Damage index for environment
Damage index for fire
Damage index for unit i
Damage index for soil
Damage index for system
Damage index for water
Damage radii that cause 50% fatalities
Damage potential
Physical energy
Chemical energy
Physical energy
Physical energy
Reaction energy
Flash point
Fire point
Factor G
heat of combustion
heat of reaction
Inventory
constant- 3148
Mass
Release rate
NFPA ranking for flammability
NFPA ranking for reactivity
NFPA ranking for health
operating pressure
operating temperature
Penalty for parameter i
Population density
volume of chemical
vapor pressure
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kPa
m
kJ
kJ
kJ
kJ
kJ
o
C
o
C
kJ/kg
kJ/kg
ton
kg
kg/s
-
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AC
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A
AT
AIT
AP
DIac
DIair
DIenv
DIfe
DIi
DIsoil
DIsystem
DIwater
DR
DP
F
F1
F2
F3
F4
FP
FRP
G
Hc
Hrxn
INV
K
M
m
NF
NR
NH
OP
OT
Pni
PD
V
VP
Description
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Symbol
kPa
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thousand/km2
m3
kPa
Acknowledgement
The authors would like to thank Universiti Teknologi PETRONAS for providing the facilities
and the Ministry of Higher Education Malaysia for their sponsorship under MyBrain15 program.
7
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Khan, F.I., Amyotte, P.R., 2002. Inherent safety in offshore oil and gas activities: a review of the
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Khan, F.I., Husain, T., Abbasi, S.A., 2001. Safety Weighted Hazard Index (SWeHI): A New,
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Kidam, K., Hurme, M., 2013. Analysis of equipment failures as contributors to chemical process
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Koller, G., Fischer, U., Hungerbhler, K., 2001. Comparison of Methods Suitable for Assessing
the Hazard Potential of Chemical Processes During Early Design Phases. Process Saf.
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hydrogen storage systems. J. Hazard. Mater. 159, 554566.
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Landucci, G., Tugnoli, A., Nicolella, C., Cozzani, V., 2007. Assessment of Inherntly Safer
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Lawrence, D., 1996. Quantifying Inherent Safety of Chemical Process Routes. Loughborough
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Lele, G.S., 2008. Ammonia Storage: Selection & Safety Issues. Chem. Ind. Dig. 8589.
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Leong, C.T., Shariff, A.M., 2009. Process route index (PRI) to assess level of explosiveness for
inherent safety quantification. J. Loss Prev. Process Ind. 22, 216221.
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Long, B., Gardner, B., 2004. Ammonia storage-a special case, in: Guide to Storage Tanks and
Equipment, European Guide Series (REP). Wiley.
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Mansfield, D., Clark, J., Malmn, Y., Schabel, J., Rogers, R., Suokas, E., Turney, R., Ellis, G.,
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Moradi, F., 2010. An Integrated Framework for Risk and Safety Evaluation and Process Design.
Murdoch University.
Palaniappan, C., Srinivasan, R., Tan, R., 2004. Selection of inherently safer process routes: a
case study. Chem. Eng. Process. Process Intensif. 43, 641647.
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doi:10.1016/j.cep.2002.12.001
Palaniappan, C., Srinivasan, R., Tan, R., 2002a. Expert System for the Design of Inherently Safer
Processes. 1. Route Selection Stage. Ind. Eng. Chem. Res. 41, 66986710.
doi:10.1021/ie020175c
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Palaniappan, C., Srinivasan, R., Tan, R.B., 2002b. Expert System for the Design of Inherently
Safer Processes. 2. Flowsheet Development Stage. Ind. Eng. Chem. Res. 41, 67116722.
doi:10.1021/ie0201765
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inherent safety. Saf. Sci. 70, 438464. doi:http://dx.doi.org/10.1016/j.ssci.2014.06.004
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Roy, P.K., Bhatt, A., Kumar, B., Kaur, S., Rajagopal, C., 2011. Consequence and risk
assessment: Case study of an ammonia storage facility. Arch. Environ. Sci 5, 2536.
Rusli, R., Shariff, A.M., Khan, F.I., 2013. Evaluating hazard conflicts using inherently safer
design concept. Saf. Sci. 53, 6172. doi:10.1016/j.ssci.2012.09.002
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Shariff, A.M., Zaini, D., 2013. Inherent risk assessment methodology in preliminary design
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Shariff, A.M., Zaini, D., 2010. Toxic release consequence analysis tool (TORCAT) for
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Tugnoli, A., Landucci, G., Salzano, E., Cozzani, V., 2012. Supporting the selection of process
ACCEPTED MANUSCRIPT
and plant design options by Inherent Safety KPIs. J. Loss Prev. Process Ind. 25, 830842.
doi:http://dx.doi.org/10.1016/j.jlp.2012.03.008
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Union Carbide Corporation (UCC), 1985. Bhopal Methyl Isocyanate Incident Investigation
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Wiley, R.J., Hendershot, D.C., Berger, S., 2006. The accident in bhopal: observations 20 years
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Yanisko, P., Zheng, S., Dumoit, J., Carlson, B., 2011. Nitrogen:A Security Blanket System for
Chemical Industry. Fluids Solids Handl. 7.
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Zainal Abidin, M., Rusli, R., Mohd Shariff, A., Khan, F.I., 2016. Three-Stage ISD Matrix (TIM)
Tool to Review the Impact of Inherently Safer Design Implementation. Process Saf.
Environ. Prot. 99, 3042. doi:http://dx.doi.org/10.1016/j.psep.2015.10.006
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ACCEPTED MANUSCRIPT
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Fig. 1 Process flowchart for design alternative evaluation
SC
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ACCEPTED MANUSCRIPT
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Fig. 2 Tank 610 before modification (Union Carbide Corporation (Bloch and Jung, 2012; Union
Carbide Corporation (UCC), 1985)
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Fig. 3 Tank 610 after modification (Bloch and Jung, 2012)
ACCEPTED MANUSCRIPT
pn1
fp1
fp2
AC
C
pn2
fp3
Pvac
pn3
pn4
Output
Symbol
pn1
m3
20.00
46.35
C
kPa
Description
Fire point
Temperature
Flash point
Vapour pressure
Processing pressure
Function related to
pressure
Function related to
pressure
Function related to
pressure
Vaccum pressure
M
NF
NR
Quantity of chemical
Description
Effect of temperature
Value
1.75
SC
Value
25748.73
2.40
3.77E-03
3.77E-03
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PT
44.42
Unit
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Symbol
FRP
OT
FP
AIT
VP
AP
OP
Unit
kg
kJ/kg
dimensionless
kPa
EP
Penalty
Input
Penalty
Value
41000.00
19770.00
3148.00
41.36
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Physical and chemical energy

Input
Symbol Description
M
Mass of chemical
Hc
Heat of combustion
K
Constant
OP
Processing pressure
Volume of the
V
chemical
OT
Temperature
VP
Vapour pressure
Output
Symbol Description
F1
Chemical energy
F2
Physical energy
F3
Physical energy
F
Value
-8.00
20.00
-18.00
534.00
46.35
101.33
41.36
Unit
C
C
C
C
kPa
kPa
kPa
0.93
1.05
0.98
1.20
0.04
3.00
3.00
Unit
dimensionless
atm
thousand tons
dimensionless
dimensionless
ACCEPTED MANUSCRIPT
pn3
pn4
Impact of pressure
Weightage due to the
quantity of chemical
handled in the unit
Effect of chemical
characteristics
(reactivity and
flammability)
0.98
dimensionless
1.29
dimensionless
1.80
dimensionless
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PT
pn2
SC
Damage potential
104386.64
Damage radii (DR)
224.12
AC
C
EP
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Fig 4 Input data and results for base case
ACCEPTED MANUSCRIPT
m3
20.00
46.35
1246.83
C
kPa
kJ/kg
AC
C
fp1
pn2
fp2
fp3
Pvac
pn3
pn4
M
NF
NR
SC
Value
25748.73
8.01
1.28
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PT
44.42
Unit
16238.92
1.28
Description
Fire point
Temperature
Flash point
Vapour pressure
Processing pressure
Function related to
pressure
Function related to
pressure
Function related to
pressure
Vaccum pressure
EP
pn1
Symbol
FRP
OT
FP
AIT
VP
AP
OP
Unit
kg
kJ/kg
dimensionless
kPa
M
AN
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Penalty
Input
Penalty
Value
41000.00
19770.00
3148.00
138.20
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Physical and chemical energy

Input
Symbol Description
M
Mass of chemical
Hc
Heat of combustion
K
Constant
OP
Processing pressure
Volume of the
V
chemical
OT
Temperature
VP
Vapour pressure
Hrxn
Heat of reaction
Output
Symbol Description
F1
Chemical energy
F2
Physical energy
F3
Physical energy
Energy released due to
F4
chemical reactions
F
Quantity of chemical
Value
-8.00
20.00
-18.00
534.00
46.35
101.33
138.20
Unit
C
C
C
C
kPa
kPa
kPa
1.40
0.73
1.13
1.20
0.04
3.00
3.00
atm
thousand tons
dimensionless
dimensionless
ACCEPTED MANUSCRIPT
pn9
Type of reaction
pn10
Undesirable side reaction
Polymerization
Autocatalytic
reaction
Description
Value
Unit
pn1
Effect of temperature
1.75
dimensionless
pn2
Impact of pressure
Weightage due to the
quantity of chemical
handled in the unit
Effect of chemical
characteristics
(reactivity and
flammability)
Nature of the reactions
Probability of 'side
reactions' or 'runaway
reactions'
1.13
dimensionless
1.29
dimensionless
pn10
Damage potential
197497.15
Damage radii (DR)
277.20
SC
pn9
1.80
1.50
1.65
dimensionless
dimensionless
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pn4
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pn3
RI
PT
Output
Symbol
dimensionless
AC
C
EP
Fig 5 Input data and result after modification
ACCEPTED MANUSCRIPT
A
m
Output
G
Description
NFPA rank
Physical state
Factor A
Value
3.00
Liquefied gas
0.80
66.67
Unit
kg/s
Factor G
53.33
Symbol
Description
Characteristic
Fire point
Operating temperature
Flash point
Ambient temperature
Vapour pressure
Processing pressure
Vapour density
Air density
Health factor
Person/km2 (thousands)
Constant
Constant
Value
Toxic or corrosive
N.A.
25.00
N.A.
651.00
25.00
999.66
101.33
1274.86
7.79
1.21
3.00
0.09
25.35
0.43
Value
1.10
2.60
7.72
1.80
0.02
Unit
-
SC
Penalty
Input
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pnr2
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AN
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FRP
OT
FP
AIT
AT
VP
AP
PP
pnr1
pnr3
pnr4
pnr5
Description
Temperature
Pressure
Vapour density
Toxicity of chemical
Population density
AC
C
Output
Symbol
pnr1
pnr2
pnr3
pnr4
pnr5
EP
NH
a
b
RI
PT
Factor G
Input
Symbol
NH
Damage radii (DR)

120.60
Damage index (DI)
Input
Unit
o
C
o
C
o
C
o
C
o
C
kPa
kPa
kPa
kg/m3
kg/m3
-
ACCEPTED MANUSCRIPT
B
0.12
12.06
1.21
1.21
12.06
12.06
17.06
68.23
RI
PT
Class
DR (km)
Output
DIair
DIwater
DIsoil
DIen
DIac
DI
DIsystem
AC
C
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Fig 6 Damage radii estimation for ammonia toxic release (base case)
ACCEPTED MANUSCRIPT
Value
3.00
Liquefied gas
0.80
266.67
Unit
kg/s
Factor G
213.33
Symbol
Description
Penalty
Input
pnr2
pnr3
pnr4
pnr5
a
b
AC
C
Output
Symbol
pnr1
pnr2
pnr3
pnr4
pnr5
EP
NH
Description
Temperature
Pressure
Vapour density
Population density
Damage Radii (DR)

66.60
Damage Index (DI)
Value
Toxic or
corrosive
N.A.
-33.40
N.A.
Unit
651.00
25.00
103.38
101.33
101.33
0.96
1.21
3.00
0.09
25.35
0.43
M
AN
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AIT
AT
VP
AP
PP
Characteristic
Fire point
Flash point
Auto ignition
temperature
Ambient temperature
Vapour pressure
Processing pressure
Vapour density
Air density
Health factor
Constant
Constant
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FRP
OT
FP
pnr1
RI
PT
A
m
Output
G
Description
NFPA rank
Physical state
Factor A
SC
Factor G
Input
Symbol
NH
Value
1.10
1.30
0.96
1.80
0.02
Unit
-
o
C
o
C
o
C
C
C
kPa
kPa
kPa
kg/m3
kg/m3
o
ACCEPTED MANUSCRIPT
B
0.07
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PT
6.66
0.67
0.67
6.66
6.66
9.42
9.42
SC
Input
Class
DR (km)
Output
DIair
DIwater
DIsoil
DIen
DIac
DI
DIsystem
AC
C
EP
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Fig 7 Damage radii estimation for ammonia toxic release from storage (Alternative 1)
ACCEPTED MANUSCRIPT
Penalty
Input
Symbol
Value
3.00
Liquid
0.40
159.44
Factor G
63.78
Symbol
Description
Characteristic
Fire point
Flash point
Ambient temperature
Vapour pressure
Processing pressure
Vapour density
Air density
Health factor
Constant
Constant
Value
Toxic or corrosive
N.A.
25.00
N.A.
651.00
25.00
303.82
101.33
108.27
0.60
1.21
3.00
0.09
25.35
0.43
Value
1.10
1.30
0.59
1.80
0.02
Unit
-
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pnr2
M
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FRP
OT
FP
AIT
AT
VP
AP
PP
pnr1
pnr3
pnr4
pnr5
Description
Temperature
Pressure
Vapour density
Population density
AC
C
Output
Symbol
pnr1
pnr2
pnr3
pnr4
pnr5
EP
NH
a
b
Unit
kg/s
RI
PT
A
m
Output
G
Description
NFPA rank
Physical state
Factor A
SC
Factor G
Input
Symbol
NH
Damage radii (DR)

32.59
Damage index (DI)
Input
Unit
o
C
o
C
o
C
o
C
o
C
kPa
kPa
kPa
kg/m3
kg/m3
-
ACCEPTED MANUSCRIPT
B
0.03
3.26
0.33
0.33
3.26
5.00
5.97
35.82
RI
PT
Class
DR (km)
Output
DIair
DIwater
DIsoil
DIen
DIac
DI
DIsystem
AC
C
EP
TE
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M
AN
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SC
ACCEPTED MANUSCRIPT
A
m
Output
G
Description
NFPA rank
Physical state
Factor A
Value
3.00
Liquid
0.40
1468.53
Factor G
587.41
Symbol
Description
Characteristic
Fire point
Temperature
Flash point
Ambient temperature
Vapour pressure
Processing pressure
Vapour density
Air density
Health factor
Constant
Constant
Value
Toxic or corrosive
N.A.
25.00
N.A.
651.00
25.00
201.27
101.33
101.33
0.60
1.21
3.00
0.09
25.35
0.43
Value
1.10
1.30
0.59
1.80
0.02
Unit
-
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pnr2
M
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FRP
OT
FP
AIT
AT
VP
AP
PP
pnr1
pnr3
pnr4
pnr5
Description
Temperature
Pressure
Vapour density
Population density
AC
C
Output
Symbol
pnr1
pnr2
pnr3
pnr4
pnr5
EP
NH
a
b
SC
Penalty
Input
Unit
kg/s
RI
PT
Factor G
Input
Symbol
NH
Damage radii (DR)

83.74
Damage index (DI)
Input
Unit
o
C
o
C
o
C
o
C
o
C
kPa
kPa
kPa
kg/m3
kg/m3
-
ACCEPTED MANUSCRIPT
B
0.08
8.37
0.84
0.84
8.38
8.37
11.84
11.84
RI
PT
Class
DR (km)
Output
DIair
DIwater
DIsoil
DIen
DIac
DI
DIsystem
AC
C
EP
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Table 1 Accident in CPI (Crowl and Louvar, 2002; Wilcutt and Whitmeyer, 2013; Wiley et al.,
2006)
Causes
Losses
Leakage of cyclohexane at the No of deaths :28
nylon plant
No of injuries :36 on-site, 53 off-site
Property damage: 821 nearby houses
and 167 shops
Released of highly toxic No of deaths:3000
methyl
isocyanate
(MIC) No of injuries: more than 300,000
vapors from the storage tank
lifelong suffering
Liability settlements: USD 470
million plus other considerations
Leakage of gas condensate No of deaths: 167
during maintenance
Losses:USD340 million
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Accident
Flixborough (1974)
Bhopal (1984)
AC
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EP
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Piper Alpha (1987)
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Table 2 ISD principles and definitions (Center for Chemical Process Safety, 2009; Hendershot et
al., 2006)
Substitute
Moderate
AC
C
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SC
Simplify
Descriptions
Use small quantities of hazardous materials; reduce the size of equipment
operating under hazardous condition such as high temperature or pressure
Use less hazardous materials, chemistry, and processes
Reduces hazardous by dilution, refrigeration, and process alternatives that
operate at less hazardous conditions
Eliminates unnecessary complexity; designs user-friendly plants
RI
PT
ISD principles
Minimize
ACCEPTED MANUSCRIPT
Table 3 ISD quantitative evaluation tools

Tools
Prototype Index of
Inherent Safety (PIIS)
Inherent Safety Index
(ISI)
(Heikkil, 1999)
al.,
2004, i-Safe Index
M
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(Palaniappan et
2002a, 2002b)
Dows Index
SC
(Etowa et al., 2002)
(Gentile et al., 2003)
Fuzzy
Logic-Based
Inherent Safety Index
(Leong and Shariff, 2009)
Process
(PRI)
Index
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Route
Process Stream Index

(PSI)
EP
(Shariff et al., 2012)
Inherent
Evaluation
(INSET Toolkit)
SHE
Tool
AC
C
(Mansfield et al., 2001)
(Khan and Amyotte, 2005, Integrated

Inherent
2004)
Safety Index (I2SI)
(Rusli et al., 2013)
Inherent Risk Design

Index (IRDI)
(Eini et al., 2014; Shariff and Consequence analysis

Wahab, 2013; Shariff and
Descriptions
Development of inherent safety
index for process route selection
index for chemical and process and
adoption of case-based reasoning
method for inherently safer design
selection
assessment tools using Dow Fire &
Explosion Index and Dow Chemical
Index
Development of intelligent system to
identify safety issues and suggest
inherently safer design that can be
quantify using indexing approach
that improved from PIIS and ISI
Development of fuzzy index that
aims to tackle the over/low
sensitivity issues due to the lack of
continuity in discrete function index
such as PIIS and ISI
index for process route selection
based on process parameter for
explosion hazard
index for process stream using
relative ranking principle for
explosion hazard
Development of inherent safety,
health and environmental aspect
using separate index and adopt the
AHP technique for decision making
process
Development of an integrated index
to consider the life cycle of the
process with economic evaluation
and hazard potential identification
Development of index to rank the
process options considering the
severity and potential of hazard
transfer
Development of framework to
evaluate of the impact of inherently
RI
PT
Authors
(Lawrence, 1996)
ACCEPTED MANUSCRIPT
AC
C
EP
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(Abuswer et al., 2013;

Bernechea and Viger, 2013;
Bernechea et al., 2013; Gmez
et al., 2012; Moradi, 2010;
Rathnayaka et al., 2014;
Shariff and Leong, 2009;
Shariff and Zaini, 2013; Storti
et al., 2013)
RI
PT
(Landucci et al., 2008, 2007;

Tugnoli et al., 2012, 2009,
2007)
safer design based on the severity of

accident for fire, explosion and toxic
release
Key
Performance Development of inherent safety
Indicator (KPIs)
index using consequence analysis
technique as a basis with the
objective to produce more reliable
and acceptable index
Risk based
Development of the framework
using
risk-based
methodology
(considering both severity and
probability of accidents) for fire,
explosion and toxic. Severity of
accident was determined using
consequence
analysis
and
Multivariate Hazard Identification
and Ranking System (HIRA)
methodology. Several methods were
used for accident probability
evaluation such as event tree, fault
tree, bow tie and probabilistic risk.
F&N curve, risk matrix, index
approach and optimization were
used to identify the best options.
SC
Zaini, 2010; Shariff et al.,

2006)
ACCEPTED MANUSCRIPT
Table 4a HIRA methodology (Khan and Abbasi, 1998)

Fire & Explosion
Energy factor
Chemical energy
Physical energy
F2 = 1.304 10 3 OP V
Physical energy
F3 = 1.0 10 3 1 /(OT + 273) (OP VP) 2 V
Reaction energy
Physical energy
Penalty
Temperature
Pressure
Capacity
F4 = M H rxn / K
Consequences
Damage potential
Damage radii
Damage index
RI
PT
SC
M
AN
U
pn1 = IF (OT > FP, IF (OT < FRP,1.45, IF (OT < 0.75 AIT ,1.75,1.95)),1.1)
pn 2 = IF (VP > AP , IF (VP < OP ,1 + 0.6 (OP VP ) / OP ,1 + 0.4 (OP VP ) / OP ),1 + 0.2 (OP VP ) / OP )
pn 3 = IF ( MAX ( NR , NF ) = 4,0.01 INV 1000 + 1, IF ( MAX ( NR , NF ) = 3,0.007 INV 1000 + 1, IF ( MAX ( NR , NF ) = 2,

0.005 INV 1000 + 1.05,0.002 INV 1000 + 1.02)))
pn4 = MAX (1,0.3 ( NR + NF ))
=
pn10=
Oxidation:1.60, Electrolysis:1.20, Nitration:1.95, Polymerization:1.50, Pyrolysis:1.45,

Halogenation:1.45, Aminolysis:1.40, Esterification:1.25, Hydrogenation:1.35, Sulfonation:1.30,
Alkylation:1.25, Reduction:1.10
Autocatalytic reaction:1.65, Non-autocatalytic reaction (above normal):1.45, Non-autocatalytic
reaction (below normal):1.20
TE
D
pn9
EP
Side reaction
F = IF ( pn 2 = fp1 , F2 + F3 , IF ( pn 2 = fp 2 , F2 , F3 )) where fp1 and fp2 is a function for pn2
DP = (F1 pn1 + F pn2 + F4 pn9 pn10 ) pn3 pn4
DR = 4.76DP 1 / 3
AC
C
Chemical
characteristic
Type of reaction
F1 = 0.1M H c / K
DR
DI fe = MAX 5, MIN 100,
ACCEPTED MANUSCRIPT
Table 4b HIRA methodology (Khan and Abbasi, 1998)

Toxic
G = Am
A = IF ( AND( NH = 4, State =" Liquid ",4, IF ( AND ( NH = 3, State =" Liquid ",0.4, IF ( AND( NH = 2, State =" Liquid ",0.2,
IF ( AND( NH = 1, State =" Liquid ",0.07, IF ( AND( NH = 4, State =" Liquefiedgas",8, IF ( AND( NH = 3, State =" Liquefiedgas",0.8,
RI
PT
Factor G
Factor A
IF ( AND( NH = 2, State =" Liquefiedgas",0.4, IF ( AND ( NH = 1, State =" Liquefiedgas",0.1, IF ( AND ( NH = 4, State ="Gas",13.40,
IF ( AND( NH = 3, State ="Gas",1.34, IF ( AND( NH = 2, State ="Gas",0.67, IF ( AND ( NH = 1, State ="Gas",0.25,
IF ( AND( NH = 1, State =" Solid ",0.0025, "" ))))))))))))))))
pn1 = IF ( AND (Characteri stic =" Flammable" , OT > FLP , FLP < FP ),1.45, IF ( AND (Characteri stic =" Flammable" , OT > FP,
M
AN
U
Penalty
Temperature
SC
IF ( AND( NH = 4, State =" Solid ",0.1300, IF ( AND( NH = 3, State =" Solid ",0.0130, IF ( AND( NH = 2, State =" Solid ",0.0060,
FP < 0.75 AIT ),1.75, IF ( AND (Characteri stic =" Flammable" , OT > 0.75 AIT ),1.95, IF ( AND (Characteri stic =" Toxic / corrosive" ,
OT > 4 AT ),1.55, IF ( AND (Characteri stic =" Toxic / corrosive " , OT > 2 AT ),1.35,1.1)))))
pn2 = IF(VP > AP, IF(OP > 3AP,1.0731 LN(OP) 5.0711,1.3), IF(OP < VP, IF(OP < 0.3AP,0.0022OP2 0.1262OP+ 2.9773,1.2)))
pn3 = 1.2(VP / AP)
DR = a(G pn1 pn2 pn3 pn4 pn5 )b
Damage
index
DI ac = IF ( AND ( DR 0.05, DR 1), DR * 100, IF ( DR > 1,100,5))

DI air = IF (Class =" A", MAX (0.001, DR / 0.1), IF (Clas =" B", MAX (0.01, MIN (100, DR / 0.01)), IF (Class ="C", MAX (0.1, MIN (100, DR / 0.001)))))
pn4 = MAX(1,0.6 NH)
TE
D
Pressure
Vapour
density
Toxicity
Population
density
Consequences
Damage radii
EP
pn 5 = IF ( PD < 6.5,0.156 * PD + 0.0043,1)
AC
C
DIwater = IF(Class =" A", MAX(0.001, DR /1), IF(Class =" B", MAX(0.001, MIN(100, DR / 0.1)), IF(Class ="C", MAX(0.01, MIN(100, DR / 0.01)))))
DI soil = IF (Class =" A" , MAX (0.001, DR / 1), IF (Class =" B" , MAX (0.001, MIN (100 , DR / 0.1)), IF (Class =" C " , MAX (0.01, MIN (100 , DR / 0.01)))))
DI env = MIN100, (DI air ) + (DI water ) + (DI soil )
DI = (DI ac ) + (DI env )

a
3 1/ 3
2 1/ 2
Symbols in equations have been defined in the nomenclature section
ACCEPTED MANUSCRIPT
Table 5 (Bloch and Jung, 2012; Union Carbide Corporation (UCC), 1985).
Descriptions
Liquid MIC
High toxicity level exposure of vapors or liquid has the
potential to cause serious injury or fatality
Material
properties,
system, Material properties
process, and plan characteristics
Colour: colourless
Standard: liquid
Density: 0.9230 g/cm3@27C
Boiling point: 38.3C
Solubility in water: 10%
Vapor pressure: 46.35 kPa
Flash point: -18C
Autoignition temperature: 534C
Explosive limits: 5.3-26%
Immediately dangerous to life and health (IDLH): 3ppm
NFPA rating: flammable: 3, reactive: 3 and toxic: 4
System/Process
Stainless steel storage tank
Carbon steel for smaller equipment; relief valve vent header
(RVVH), process vents header (PVH) and vent line
Two centrifugal pumps;
1) Transfer pump to export MIC to the derivative units for
pesticide production
2) Circulation pump that processes MIC through a
fluorocarbon-based refrigeration system in order to keep
MIC at 0C
Nitrogen blanketing system
AC
C
EP
TE
D
M
AN
U
SC
RI
PT
Hazards identification
Materials
Undesirable consequences
ACCEPTED MANUSCRIPT
Table 6 ISD conflict for modification done in Bhopal facilities

Value
2 pumps
Nitrogen
41.36kPa
1 pump
138.20kPa
Keyword
-
AC
C
EP
TE
D
M
AN
U
SC
Alternative 1
ISD Variable
No of unit/utilities
Resistant material
Pressure
Resistant material
Pressure
Lower
Lower
Higher
RI
PT
Options
Base case
ACCEPTED MANUSCRIPT
Table 7 Review of ISD Modification using TIM Tool

Deviation of ISD Variable
Lower no of unit
Impact towards safety

Minimize the potential
leaking at the pump
Lower resistant
Loss of excess nitrogen flowloss of corrosion and moisture

protection
AC
C
RI
PT
of
SC
M
AN
U
TE
D
Higher pressure
EP
TIM tool
Input: ISD Heuristic
Likelihood Reduction
Stage 1: ISD Guideword
Simplify
Stage 2: ISD Indicator
Complexity
Stage 3: ISD Variable
Simplify
Loss of containment
Resistant material
Consequence Reduction
Moderation
Process Condition
Pressure
Higher pressure difference

between the storage system
and the outside environment,
increase the rate of release in
case of a leak
ACCEPTED MANUSCRIPT
Table 8 Reaction step in MIC polymerization process in Bhopal tragedy

Reaction
CHCl3 + [O] COCl2 + HCl

UV / air
hydrochloric
acid
phosgene
chloroform
Fe+ 2 HCl FeCl 2 + H 2
iron
hydrochloric
acid
iron ( ii )
chloride
Rust formation
hydrogen
12 FeCl 2 + 3O2 2 Fe 2 O3 + 8 FeCl 3

iron ( ii )
chloride
oxygen
iron ( iii )
oxide
iron ( iii )
chloride
Fe 2O3
3C 2 H 3 NO
C 6 H 9 N 3 O3
MIC polymerization
MICtrimer
AC
C
EP
TE
D
M
AN
U
SC
MIC
Description
Hydrochloric acid formation
RI
PT
Step
1
ACCEPTED MANUSCRIPT
Table 9 Hazard assessment results

Options
Base case
Modification (normal condition)
Damage radii (m)

224.12
277.20
Increment (%)
23.68
AC
C
EP
TE
D
M
AN
U
SC
RI
PT
No
1
2
ACCEPTED MANUSCRIPT
Table 10 Hazard identification results for the base case

Description
Anhydrous liquid ammonia
High toxicity level
Exposure of vapors or liquid has the potential to cause serious
injury or fatality
Material properties, system, Material properties
process,
and
plant Colour-colourless
characteristics
Standard-gas
Relative density, gas-0.6 (air=1)
Relative density, liquid-0.7 (water=1)
Vapor pressure-124psi at 20oC (68oF)
Boiling point--33oC
Solubility in water-Completely soluble
Percent volatility-100%
Lower explosive limit (LFL) -15%
Upper explosive limit (UFL) -30%
Immediately dangerous to life and health (IDLH)-300ppm**
Acute Exposure Guideline Levels (AEGL) for 10-min exposure
durations
AEGL-1-30ppm
AEGL-2-270ppm
AEGL-3-2700ppm
System/Process
High pressure storage
AC
C
EP
TE
D
M
AN
U
SC
RI
PT
Hazards identification
Material
Undesirable consequences
ACCEPTED MANUSCRIPT
Table 11 Alternatives design for ammonia storage tank

Substance
Anhydrous ammonia
Anhydrous ammonia
Aqueous ammonia (29%)
Aqueous ammonia (19%)
Pressure (kPa)
1274.86
101.33
108.27
101.33
Temperature (C)
25.00
-33.40
25.00
25.00
RI
PT
Types of storage
Atmospheric storage
Atmospheric storage
AC
C
EP
TE
D
M
AN
U
SC
Options
Base case
Alternative 1
Alternative 2
Alternative 3
Mass (kg)
40 000.00
160 000.00
95 663.00
881 118.00
No of unit
4
1
6
1
ACCEPTED MANUSCRIPT
Table 12 Deviations of ISD variables from the base case
Alternative 2
AC
C
EP
Alternative 3
Keyword
RI
PT
Value
40 000.00
27.07
25.00
1274.86
4
160 000.00
124.78
-33.40
101.33
1
95 663.00
100.32
108.27
29.00%
6
881 118.00
948.92
101.33
19.00%
-
SC
Alternative 1
M
AN
U
Base case
ISD Variable
Volume (Inventory)
Volume (Energy)
Temperature
Pressurize storage
Pressure
Strength of equipment
Min no of unit/utilities
Process layout
Volume (Inventory)
Volume (Energy)
Temperature
Atmospheric storage Pressure
Process layout
Volume (Inventory)
Volume (Energy)
Pressure
Pressurize storage
Dilution
Process layout
Volume (Inventory)
Volume (Energy)
Atmospheric storage Pressure
Dilution
TE
D
Options
Higher
Higher
Lower
Lower
Lower
Lower
Lower
Higher
Higher
Lower
Higher
Higher
Higher
Higher
Higher
Lower
Higher
Lower
ACCEPTED MANUSCRIPT
Table 13 Review of the impact of ISD modification towards safety and environment for Alternative 1
Higher energy volume
High pressure steam for vaporization poses higher hazard with higher
driving force for a leak to outside environment
TE
D
Lower temperature
Lower pressure
M
AN
U
SC
RI
PT
Impact towards safety and environment

Higher inventory, larger hazard zone of material release that cause
fatalities and soil/water/air contaminations
EP

Moderation
Process Condition
Temperature

Higher material volume
AC
C
TIM tool
Minimization
Inventory
Volume
Minimization
Energy
Volume
Lowering temperature via refrigeration will reduce the magnitude of the

consequences of a release that cause fatalities and soil/water/air
contaminations in three ways:
1) Reduction of vapor pressure via refrigeration will reduce the driving
force for a leak to the outside environment
2) There will be no initial flash of liquid to vapor in case of a leak when
material stored at or below its atmospheric pressure boiling point
3) Elimination of two-phase flashing jet that will cause the rain out of
liquid release to the ground
Reduction of pressure will reduce the driving force for a leak to outside
environment that cause fatalities and soil/water/air contaminations

Moderation
Process Condition
Pressure
RI
PT
ACCEPTED MANUSCRIPT
Reduction of storage number-lower failure probability that cause


Simplification
Complexity
Lower complexity of
process layout
Reduction of piping requirement-lower failure probability that cause


Simplification
Complexity
Process layout
Lower strength of
equipment
M
AN
U
TE
D
EP
AC
C

Simplification
Loss of containment
SC
Lower no of unit
Additional failure potential due to under pressure problem that cause

Additional failure potential due brittle rupture because of operating at
low temperature that cause fatalities and soil/water/air contaminations
ACCEPTED MANUSCRIPT
AC
C
EP
TE
D
M
AN
U
SC
RI
PT

ACCEPTED MANUSCRIPT

Moderation
Process Condition
Pressure
Lower pressure
M
AN
U
SC
RI
PT

High pressure steam for vaporization poses higher hazard with higher
driving force for a leak to outside environment
TE
D
EP

Minimization
Inventory
Volume
Minimization
Energy
Volume

AC
C
TIM tool
Reduction of pressure will reduce the driving force for a leak to

outside environment that cause fatalities and soil/water/air
contaminations
ACCEPTED MANUSCRIPT

Simplification
Complexity
Process layout
RI
PT
SC
Lower initial atmospheric concentration of the hazardous material,

smaller hazard zone downwind of the spill that cause fatalities and
soil/water/air contaminations
Additional number of storage number-higher failure probability that

causes fatalities and soil/water/air contaminations
M
AN
U
Higher no of unit
TE
D

Simplification
Complexity
Lower pressure difference between the storage system and the outside
environment, reducing the rate of release in case of a leak that cause
Higher complexity of process

layout
EP

Moderation
Process Condition
Dilution
Higher dilution
AC
C

Additional of piping requirement-higher failure probability that

causes fatalities and soil/water/air contaminations
ACCEPTED MANUSCRIPT

Moderation
Process Condition
Pressure
High pressure steam for vaporization poses a higher hazard with higher
driving force for a leak to the outside environment
M
AN
U
SC
RI
PT
TE
D
Minimization
Energy
Volume

fatalities and soil/water/air contamination
EP

Minimization
Inventory
Volume

Lower pressure
AC
C
TIM tool
Reduction of pressure will reduce the driving force for a leak to outside
environment that cause fatalities and soil/water/air contamination
ACCEPTED MANUSCRIPT

Higher dilution
Lower pressure difference between the storage system and the outside
environment, reducing the rate of release in case of a leak that cause
Lower initial atmospheric concentration of the hazardous material,
smaller hazard zone downwind of the spill that cause fatalities and
soil/water/air contamination
Lower no of unit
Reduction of storage number-lower failure probability that causes

SC
M
AN
U
Moderation
Process Condition
Dilution
RI
PT
Simplification
Complexity
Process layout
EP
Lower complexity of
process layout
AC
C
Simplification
Complexity
TE
D
Reduction of piping requirement-lower failure probability that causes

ACCEPTED MANUSCRIPT

Lower strength of
equipment
Additional failure potential due to under pressure problem that cause

RI
PT
AC
C
EP
TE
D
M
AN
U
SC
Simplification
Loss of containment
ACCEPTED MANUSCRIPT
Table 16 Inherent safety level evaluation of ammonia storage alternatives

DR
DIair
DIwater
DI soil
DIen
DIac
Base case
Alternative 1
Alternative 2
Alternative 3
120.60
66.60
32.59
83.74
12.06
6.66
3.26
8.37
1.21
0.67
0.33
0.84
1.21
0.67
0.33
0.84
12.06
6.66
3.26
8.38
12.06
6.66
5.00
8.37
DI
17.06
9.42
5.97
11.84
SC
M
AN
U
TE
D
EP
AC
C
DI system
RI
PT
Options
68.23
9.42
35.82
11.84
Hazard reduction
(%)
86.19
47.51
82.64
ACCEPTED MANUSCRIPT
Highlights
AC
C
EP
TE
D
M
AN
U
SC
RI
PT
We combine qualitative and quantitative approach to evaluate ISD options

We evaluate the impact of ISD modification for fire & explosion, toxic and
environmental impact
The combination of these two approaches can help the assessor to understand and resolve
the trade-off

DR Risza Paper

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Accepted Manuscript

Resolving inherent safety conflict using quantitative and qualitative technique

Journal of Loss Prevention in the Process Industries

Received Date: 15 May 2015

Accepted Date: 28 August 2016

Mardhati Zainal Abidin

Azmi Mohd Shariff

Faisal Irshad Khan

Quantitative evaluation (HIRA methodology)

Results and Discussion

Modification of storage system (Bhopal accident)

Qualitative evaluation using TIM Tool

Qualitative evaluation using TIM Tool

Quantitative hazard potential evaluation using HIRA

Although ISD philosophy itself is a methodology to achieve fundamentally safer plants,

Nomenclature and Units

Fig. 1 Process flowchart for design alternative evaluation

Fig. 3 Tank 610 after modification (Bloch and Jung, 2012)

Physical and chemical energy

Fig 4 Input data and results for base case

Physical and chemical energy

Undesirable side reaction

Fig 5 Input data and result after modification

Damage radii (DR)

Damage Radii (DR)

Damage radii (DR)

Damage radii (DR)

Piper Alpha (1987)

Table 3 ISD quantitative evaluation tools

2004, i-Safe Index

(Etowa et al., 2002)

(Gentile et al., 2003)

(Leong and Shariff, 2009)

Process Stream Index

(Shariff et al., 2012)

(Mansfield et al., 2001)

(Khan and Amyotte, 2005, Integrated

(Rusli et al., 2013)

Inherent Risk Design

(Eini et al., 2014; Shariff and Consequence analysis

(Abuswer et al., 2013;

(Landucci et al., 2008, 2007;

safer design based on the severity of

Zaini, 2010; Shariff et al.,

Table 4a HIRA methodology (Khan and Abbasi, 1998)

F3 = 1.0 10 3 1 /(OT + 273) (OP VP) 2 V

pn 3 = IF ( MAX ( NR , NF ) = 4,0.01 INV 1000 + 1, IF ( MAX ( NR , NF ) = 3,0.007 INV 1000 + 1, IF ( MAX ( NR , NF ) = 2,

Oxidation:1.60, Electrolysis:1.20, Nitration:1.95, Polymerization:1.50, Pyrolysis:1.45,

F = IF ( pn 2 = fp1 , F2 + F3 , IF ( pn 2 = fp 2 , F2 , F3 )) where fp1 and fp2 is a function for pn2

DP = (F1 pn1 + F pn2 + F4 pn9 pn10 ) pn3 pn4

DI fe = MAX 5, MIN 100,

Table 4b HIRA methodology (Khan and Abbasi, 1998)

DR = a(G pn1 pn2 pn3 pn4 pn5 )b

DI ac = IF ( AND ( DR 0.05, DR 1), DR * 100, IF ( DR > 1,100,5))

pn4 = MAX(1,0.6 NH)

pn 5 = IF ( PD < 6.5,0.156 * PD + 0.0043,1)

DI env = MIN100, (DI air ) + (DI water ) + (DI soil )

DI = (DI ac ) + (DI env )

Symbols in equations have been defined in the nomenclature section

Table 6 ISD conflict for modification done in Bhopal facilities

Table 7 Review of ISD Modification using TIM Tool

Impact towards safety

Loss of excess nitrogen flowloss of corrosion and moisture