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Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 389–403

Contents lists available at SciVerse ScienceDirect

Process Safety and Environmental Protection

journal homepage: www.elsevier.com/locate/psep

Developments in inherent safety: A review of the progress


during 2001–2011 and opportunities ahead

Rajagopalan Srinivasan a,b,∗ , Sathish Natarajan a


a Department of Chemical and Biomolecular Engg, National University of Singapore, 10 Kent Ridge Crescent, Singapore, 119260,
Singapore
b Process Sciences and Modeling, Institute of Chemical and Engineering Science, 1 Pesek Road, Jurong Island, Singapore, 62783, Singapore

a b s t r a c t

This paper reviews the progress in inherent safety. A summary of the historical developments up to the year 2000 is
first presented which sets the stage for a review of the key developments during the first 11 years of the 21st century.
A landscape of inherent safety is developed by mapping publications on two coordinates. The first coordinate, the
risk coordinate, indicates if the focus of a paper relates to inherent hazard or to the likelihood of events. The second
coordinate, the management coordinate, focuses on the ways and means to understand and assess inherent safety.
Out of the 187 papers that have appeared over this 11-year period, 131 pertained to developments in inherently safer
design; these have been organized on the proposed landscape. The rest introduce the basic concepts of inherent
safety and address its incorporation into regulation, education and accident investigation. These along with the
application of inherent safety in industry are also discussed. We conclude with a discussion on recent trends in
industry and suggest directions for future research.
© 2012 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords: Principles; Metrics; Risk management; Human factors; Education; Sustainability

1. Introduction inherent safety literature over the first 11 years of the 21st
century. We conclude with a discussion of recent trends and
“What you don’t have can’t leak”, said Trevor Kletz (Kletz, 1978) suggest directions for future research.
and laid the foundation of a new approach for risk manage-
ment in chemical processes. Since then, the concept called 1.1. Risks in chemical processes
inherent safety has been the subject of much attention, with
an explosion of ideas, methods, and examples as described Any accident in a chemical process is a product of three fac-
in several books and publications (Bollinger and Crowl, 1996; tors – an inherent hazard in the technology for converting
CCPS, 2009; Kletz, 1998). It is now also incorporated into safety raw materials to products, one or more events that instan-
regulations (McKeon-Slattery, 2010; Sawyer, 2010). The key tiate a failure mode which leads to the undesired outcome. A
principles of inherent safety are now well described. This hazard is a condition or practice that has the potential to
paper seeks to review the major developments over the last cause harm, including human injury, damage to property,
11 years and suggest some topics requiring further attention. damage to the environment, or some combination of these
This review of inherent safety is organized around process (Sutton, 2010). The keyword in the definition is ‘potential’.
risk management. The risks involved in chemical processes Hazards exist in all human activities but rarely result in an
are discussed next. The evolution of inherent safety in the incident. An event defined as any occurrence in the process,
20th century is summarized in Section 2. Next, in Section 3 such as an error, caused by equipment performance or human
we describe a risk management based framework for analyz- action or an occurrence external to the process (e.g. tsunami,
ing inherent safety. We use this framework for reviewing the earthquake, etc.) is necessary to translate a hazard into an


Corresponding author at: Department of Chemical and Biomolecular Engg, National University of Singapore, 10 Kent Ridge Crescent,
Singapore, 119260, Singapore. Tel.: +65 65168041.
E-mail address: chergs@nus.edu.sg (R. Srinivasan).
Received 12 March 2012; Received in revised form 15 May 2012; Accepted 14 June 2012
0957-5820/$ – see front matter © 2012 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.psep.2012.06.001
390 Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 389–403

accident. The first event in an accident sequence is called Until the mid-20th century, risk management in chemical
the initiating event. Examples include equipment or software plants was performed only after the detailed design of the
failures, human errors, etc. A series of events link an initiat- plant had been established, by which time it is too late to
ing event to the outcome. These intermediate events could be make changes to the process technology (materials, reactions,
responses from engineered safety features and administra- unit operations, etc.), the key determinants of overall risk.
tive controls to an initiating event or knock on effects such as Moreover, risk management primarily focused on reducing the
secondary explosions. It is important to view an accident as likelihood of events by providing layers of protection.
a discrete sequence of events because each individual event
represents an opportunity to terminate the accident sequence.
The likelihood of each event is a measure of the probability or 2. The early years of inherent safety:
frequency of its occurrence. The undesired outcome is an uncon- principles and metrics
trolled release of material or energy that results in damage
to humans, the plant and the environment. Fire, explosion, On December 14, 1977, inspired by the Flixborough disaster,
and release of toxic chemicals are common examples of out- Dr. Trevor Kletz, presented the Annual Jubilee Lecture to the
comes in the refining and petrochemical industries (Marsh, Society of Chemical Industry in Widnes, England. His lec-
2001). ture titled “What You Don’t Have, Can’t Leak” was the first
Consider the accident in the BP Texas City refinery (CSB, clear and concise discussion of the concept of inherently safer
2007). The outcome of the accident were two explosions that design in chemical processes. Kletz proposed to change or
resulted in 15 deaths, injury to 180 others, and losses of about alter the process to either eliminate the hazard completely or
$1.5 billion. The hazard in this case was the presence of a large sufficiently reduce its magnitude or likelihood of occurrence,
amount of flammable material in the isomerization tower. rather than controlling them. He argued that the greatest
During startup, operations personnel pumped flammable liq- potential opportunities for impacting the risk profile occur
uid hydrocarbon into the isomerization tower for over 3 h early during process design as there is a great deal of freedom
without removing any liquid out. This is the initiating event in the selection of chemistry, solvents, raw materials, interme-
in this accident. Critical alarms and control instrumentation diates, unit operations, plant location and process parameters.
failed to alert the operator of the high level in the tower. Con- For instance, during the research stage significant reduc-
sequently, unknown to the operators liquid overflowed from tion in risk can be achieved using benign raw materials and
the top of tower and formed a flammable vapor cloud. The reaction chemistry, thereby eliminating hazards inherent in
failure of the instruments and mistakes from operators were the process. Risk reduction during the process development
the intermediate events in this accident. The flammable vapor stage can be achieved by using forgiving or robust unit opera-
cloud was ignited by backfire from an idling truck that resulted tions. In the detailed design stage, opportunities to eliminate
in two explosions. the hazards are minimal. But likelihood of events can be min-
Risk management is the term given to the collective efforts imized using layers of protection. Risk reduction during the
to manage risks in order to prevent accidents. Risk is defined operation stage can be achieved using administrative controls,
formally as the probability that an exposure to a hazard would emergency planning, evacuation procedures, etc. to reduce the
lead to an undesired outcome. Risk management involves a severity of an undesired outcome. The effectiveness of the
variety of techniques to (a) minimize the hazards, (b) decrease various risk reduction strategies in the different stages of the
the likelihood of events, and (c) minimize the severity of the process is shown in Fig. 1. Kletz enumerated certain princi-
undesired outcome. Hazards can be eliminated or minimized ples that can be followed to design inherently safer processes,
by choosing less hazardous materials, benign reaction chem- key among which are minimize, substitute, moderate and simplify
istry and forgiving process design. The likelihood of an event (Kletz, 1985).
can be decreased by providing layers of protection using safety Minimize, also called intensification, means to reduce the
devices or work processes. The severity of the outcome can be quantity of material or energy contained in a manufactur-
minimized using operating procedures, training, emergency ing process or plant. Substitute, as the name implies, means
response, etc. to replace a hazardous material or process with an alterna-
Different risk management strategies are suitable in differ- tive that eliminate or reduces the hazard. Examples include
ent stages of the plant lifecycle. The lifecycle of a chemical solvents, materials of construction and heat transfer media.
plant can be divided into the following stages (CCPS, 2009): Moderate, also called attenuate, means using materials under
research, process development, detailed design, operations, less hazardous conditions. Moderation of conditions can be
maintenance and modifications and finally decommission- accomplished by strategies that are either physical (i.e., lower
ing. During the research stage, process chemists choose the temperatures) or chemical (i.e., development of a reaction
raw materials, intermediates, synthesis routes and specify the chemistry which operates at less severe conditions). Simplify,
basic operating parameters for producing the product. In the as the word suggests, is to design the process to elimi-
process development stage, process engineers use the infor- nate unnecessary complexity making it robust and forgiving,
mation provided by chemists to design unit operations in thereby reducing the opportunities for error and wrong opera-
which necessary chemical transformations are realized. The tion. While the above four strategies are the major ones, others
process flowsheet is also developed at this stage. During the such as Limitation of effects, Avoiding incorrect assembly and Mak-
detailed design stage, process engineers develop P&IDs, lay- ing status clear were also proposed (Kletz, 1998). It is often
out of the plant and specify the operating procedures to be argued that these are sub-categories of the main principles
followed for startup, shutdown, etc. Meanwhile, control engi- described above.
neers design the control system along with suitable safety Application of inherent safety principles helps gener-
instrumented systems (SIS). In the operations stage, the oper- ate modified process designs. However, design modifications
ating procedures are created or updated based on experience rarely result in a monotonic reduction of risk. Design options
and retrofits to the plant. with alternate chemistries, materials and unit operations will
Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 389–403 391

Hazard
elimination or
reduction

Effectiveness of risk
reduction
Safety systems

Procedures

Research Operations,
Process Detailed design maintenance and
Development
modifications

Fig. 1 – Effectiveness of various risk reduction strategies across process lifecycle.

likely pose different hazards, as well as different degrees of During 1990s, inherent safety also started receiving some
the same hazard. For example, consider substitution of a toxic attention from both industry and regulatory organizations,
but non-volatile solvent with a non-toxic but volatile one. The especially in the United States and Europe (Ashford, 1993).
risks in handling the solvent are eliminated by replacing the A survey across the European process and chemical sector
toxic solvent. But the new volatile solvent could cause high in the early 1990s revealed that the awareness of these con-
pressures in the reactor and the potential for the reaction to cepts and the benefits they offered was primarily restricted
have a runaway is greater. Hence, it was recognized during to safety specialists. As a result, few organizations actually
the mid-1990s that some form of quantification was necessary recognized, promoted, or used the concept in process develop-
to evaluate the trade-offs among various design options. This ment and design. Good examples of inherently safer processes
led to the development of metrics for measuring the inherent had generally risen from economic pressures or as a result
safeness of design options. of accidents or near-misses in the past, rather than a sys-
Edwards and co-workers (Edwards and Lawrence, 1993; tematic application of the inherent safety principles (Schabel,
Lawrence, 1996) proposed the Prototype Index for Inherent Safety 1997). Hence, the Inherent SHE in Design (INSIDE) project was
(PIIS) primarily for use in the research and process develop- established in 1994 to promote inherently safer chemical pro-
ment (route selection) stages of design. Their index considers cesses. The result of this project was a collection of tools and
reaction conditions and material properties through seven methods, called the INSET toolkit, to assist process designers
parameters of the process route – inventory, temperature, incorporate inherent safety principles during chemistry route
pressure, yield, toxicity, flammability, and explosiveness. The selection, route evaluation, process design optimization and
first four parameters are considered to reflect the ‘process’ plant design (Mansfield, 1997; Schabel, 1997). As the decade
and the last three the ‘chemical’. The total range for each of progressed, companies such as Bayer (Falke and Kuschnerus,
these parameters was divided into 10 sub-ranges and numer- 1994), Dow (Scheffler, 1996), and Exxon Chemicals (French
ical scores assigned for each of these sub-ranges. The score et al., 1996) recognized the importance of inherent safety and
of the worst chemical in terms of flammability, toxicity, and developed internal standards for their use within their safety
explosiveness was chosen for each route and added together management program. Against this backdrop, the develop-
to form its ‘chemical score’. Similarly, the scores for pressure, ments in the field of inherent safety in the 21st century are
temperature and yield were combined as the ‘process score’. reviewed next.
These two scores were added together to derive a score for
each route. The route with the highest numerical value was 3. Developments in inherent safety during
considered to be the worst route. PIIS primarily focusses on 2001–2011
the risks posed by materials and reactions. Hurme and co-
workers (Heikkila, 1999; Heikkila et al., 1996) extended the PIIS A survey of the literature in the 21st century was conducted,
to consider a wider range of factors including layout, type aimed at understanding the issues, concepts, methodologies,
of equipment, process structures, side reactions and other and applications receiving attention under the broad moniker
chemical interactions. Their index, called the inherent safety of inherent safety. The survey involved a search for the terms
index (ISI), is therefore applicable during detailed design (flow- ‘Inherent Safety’ or ‘Inherently Safe’ in the title, abstract or
sheet development) stage as well. The Dow Fire & Explosion keywords of publications in the Scopus database appearing
(F&EI) index is widely used for evaluating the hazard cate- from 2001 to 2011. Inherent safety, as a concept, has broad cur-
gory of a process plant (Dow, 1994). Kletz (1998) suggested rency today ranging from agricultural and biological sciences,
that the F&EI can also be used for inherent safety assess- medicine, and nuclear industry. This review focuses primar-
ment. ily on the chemical process industry; hence the search was
392 Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 389–403

Table 1 – Journals that publish developments in inherent


safety. Material

Name of Journal Number of


publications
Chemistry
Journal of Loss Prevention in Process Industries 31
Process Safety Progress 24
Process Safety and Environmental Protection 23
Hazard Unit operaon
Journal of Hazardous Materials 15
Industrial and Engineering Chemistry Research 10
Chemical & Engineering News 9
Flowsheet &
Chemical Engineering Progress 6
Layout design
Chemical Engineering Science 6
Institution of Chemical Engineers Symposium 4
Inherent safety
Series Storage &
Chemical Engineering Transactions 4 Transportaon
Organic Process Research & Development 4
AIChE Journal 3
Process control &
Computers & Chemical Engineering 3 Safety systems
Others 45
Likelihood
Total 187 Human factors &
Management
Systems
further restricted to the field of chemical engineering, chem-
istry, and environmental science. Where multiple versions Fig. 3 – Taxonomy of risk coordinate.
(for example, conference proceedings and journal) of a paper
appeared, we only consider the extended version of the paper. outcomes. Inherently safer strategies can be applied toward the
Conference papers for which only the abstract was available elimination of the hazard, referred to as the first order view
were also ignored. This resulted in a total of 187 papers. or for its minimization, referred to as second order view (CCPS,
Table 1 lists the sources of these publications. The distri- 2009). Hence, the first coordinate, the risk coordinate, indicates
bution of the papers across the timeline is shown in Fig. 2 and if the focus relates to the inherent hazard or to the likelihood
points to a healthy and continued interest. These papers cover of events. A taxonomy of this coordinate is shown in Fig. 3.
a broad theme, ranging from fundamentals and applications, The inherent hazards in a process could arise from: materials
to regulations, accident investigation and education. 27 papers used, chemistry of the process, unit operation design, flowsheet
(14%) introduce the concepts and explain the principles of and layout design, storage and transportation, or operating regimes.
inherent safety in general (Hansson, 2010; Hendershot, 2006, Inherently safer strategies can also be applied to the design
2010). These are not covered in detail in this review. Another 29 of layers of protection to reduce the likelihood of events. This
papers (16%) cover aspects such as inherent safety regulations, includes robust or reliable designs of process control and safety
education and its use in performing accident investigation. instrumented systems and simpler, procedures that are easier
These are discussed in Section 4. Here, we review the advances to understand and execute, with proper training, safety cul-
in the design of inherently safer processes as reported in 131 ture, and management systems that minimize human factors
papers. (Sawyer, 2010).
We mapped the landscape of developments in inherent The second coordinate focuses on the ways and means
safety by analyzing these papers based on two coordinates. to understand and assess inherent safety. A taxonomy of
The developments in inherent safety can be analyzed by this management coordinate is shown in Fig. 4. In this man-
taking a risk management view. As discussed in Section 1, agement coordinate, we mark the nature of the reported
risk management involves (a) elimination or minimization of development as applicable to fundamental aspects of haz-
inherent hazards in the process, (b) reduction of the likelihood ards, illustrative applications in industry, safety systems or
of events and (c) minimization of the severity of the undesired human factors; and methods to assess inherent safety of
design options. Approaches to assess inherent safety include
30 models, qualitative reviews and quantitative metrics. Models,
either experimental or computational, provide information
25 for performing inherent safety assessment in the form of

20
Inherent
safety
15

Praccal
Fundamentals Assessment
10 applicaons

Qualitave
0 Metrics Models
reviews
2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011

Fig. 2 – Distribution of papers over the years. Fig. 4 – Taxonomy of the management coordinate.
Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 389–403 393

Storage & with standardized test protocols (ASTM 93B) to experimen-


Transportaon tally determine the flash point of partially miscible mixtures
7% of flammable solvents. They also developed a mathematical
model using these experimentally determined values. But,
experimental determination of the flash point is expensive,
Material tedious, time-consuming, and sometimes even impossible.
29% Therefore, simulations using quantitative structure property-
Flowsheet & activity relationships (QSPR/QSAR) to predict the flash point
Layout design are gaining popularity. Patel et al. (2010) proposed a molecular
28% simulation based technique for predicting the flash point of
solvents. They studied the acetic acid–water separation pro-
cess where ethyl acetate is normally used as the solvent. Using
computer-aided molecular design, they identified three other
Unit Operaons Chemistry solvents with lower flammability that are inherently safer.
14% 22% Unlike flammability, toxicity is a more complex property
of a material. The effect can be acute or chronic, affecting
humans or other living organisms either through contact or
Fig. 5 – Distribution of publications based on hazard ingestion. Usually the various factors of toxicity are lumped
addressed. into a single value (LC50 or LD50). Cordella et al. (2009) pro-
posed a new approach to screen the toxic profile of unwanted
properties of materials, behavior of unit operations, etc. materials formed as a result of process deviations due to loss
Qualitative reviews are techniques that use guidewords, brain- of control. They took into account acute and long-term hazard
storming, HAZOP, checklist, etc. for hazard evaluation. Metrics for humans, damage to ecosystems and environmental media
are used to quantify the hazards associated with a particular contamination by unwanted materials.
process. Each paper was categorized based on both the coor- Understanding the explosiveness of materials, particularly
dinates. For instance, the paper by Liaw et al. (2008) discusses of dusts, has also received attention recently. Eckhoff (2009b)
the determination of flash point of materials by using quan- describes the role of powder science in dust explosiveness
titative simulations. This paper was hence classified under and Amyotte and Eckhoff (2010) provide a general overview of
material in the risk coordinate and under model in the manage- the mechanisms by which dust explosions originate, and the
ment coordinate. Papers with significant coverage of multiple methodologies by which they can be prevented. Di Benedetto
topics were classified under all the respective categories. For et al. (2010) report on the effect of that particle sizes have on
example, Palaniappan et al. (2002a), study the material and dust explosiveness, represented as a dust explosion regime
chemistry hazards of process options using a metric. Hence diagram. Amyotte et al. (2010) also quantify the effects of
this paper was classified under both material and chemistry dust particle size and flammable gas admixture on the explo-
in the risk coordinate and under metric in the management siveness of dusts. Amyotte et al. (2009) explicitly link the
coordinate. inherent safety principles of minimize, substitute, moderate
Hazards received the most attention with 87% of the and simplify to strategies for dust explosion prevention and
papers. The distribution of papers across the hazards is shown mitigation.
in Fig. 5. We only describe illustrative publications that reveal In summary, the estimation of material properties, espe-
the key trends rather than all the papers that have appeared cially flammability and explosiveness, has received significant
on the topic. attention in the last 10 years. This knowledge can aid chemists
and engineers in understanding the inherent hazards in a pro-
3.1. Material cess and subsequently choose benign materials. Table 2 lists
all the papers under the material coordinate.
Materials used in the process have certain intrinsic char-
acteristics such as flammability, toxicity and explosiveness. 3.2. Chemistry
Knowledge of these allow for substitution of hazardous
materials with less hazardous ones or to provide sufficient The materials used in the process undergo chemical trans-
protection. For commonly used materials, these properties formations to form the final product. Chemical Reactivity in
are available in material safety data sheets (MSDS). In the terms of exothermicity and the potential for runaway pose
early part of the new millennium, these properties from MSDS significant hazards if not properly understood and controlled.
were used to quantify the inherent hazards. But properties It is therefore imperative to develop methods capable of pre-
reported in the MSDS are obtained using standardized tests dicting the onset of runaways. Hydrogen peroxide, one of most
under predefined conditions. The actual conditions in which powerful oxidizers known, plays an important role in industry.
a material is used can be significantly different, which would Hence the study of runways during peroxide decomposition
influence its properties. Moreover, the properties of mixtures has received attention. Papadaki et al. (2005) developed a
are not readily available. Hence, in the last few years, the model using the kinetics of hydrogen peroxide decomposition
focus has shifted to predicting properties of materials and to study the potential for runaways based on peroxide initial
mixtures under process conditions. The prediction of flash concentration, initial temperature, amount of catalyst, and so
point of substances, which serves as a simple measure of on. Unlike hydrogen peroxide, the kinetics of decomposition of
flammability, has received particular attention. Chen (2004) organic peroxides vary significantly depending on the organic
studied the effect of an inerting component, in particular, groups present. Hence, Lu et al. (2011) used QSPR to predict
water during cyclohexane oxidation, to moderate the flamma- the onset temperature and heat of decomposition of organic
bility of the mixture. Liaw et al. (2008) use flash point analyzers peroxides to determine thermal stability. In general, the
394 Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 389–403

Table 2 – Classification of papers discussing material Table 3 – Classification of papers addressing chemistry
hazards. hazards.
Paper Management Paper Management
coordinate coordinate

Eckhoff (2009b) Hassim and Edwards (2006)


Fundamentals
Eckhoff (2009a) Palaniappan et al. (2002a)
Koller et al. (2001)
Hassim and Hurme (2010c)
Leong and Shariff (2009)
Cordella et al. (2009)
Abedi and Shahriari (2005) Metric
Hassim and Edwards (2006)
Khan and Amyotte (2004)
Palaniappan et al. (2002a)
Gentile et al. (2003)
Koller et al. (2001)
Khan et al. (2003)
Leong and Shariff (2009)
Shah et al. (2003)
Abedi and Shahriari (2005) Metric
Khan and Amyotte (2004) Chou et al. (2011)
Gentile et al. (2003) Wu et al. (2011)
Khan et al. (2003) Lin et al. (2010)
Shah et al. (2003) Lu et al. (2010)
Srinivasan and Nhan (2008) Patel et al. (2010)
Tugnoli et al. (2009) Schweitzer et al. (2010)
Lin and Shu (2009)
Di Benedetto et al. (2010)
You et al. (2009)
Liaw et al. (2010a)
Cheng et al. (2008)
Liaw et al. (2010b)
Dermaut et al. (2007) Model
Chang et al. (2009)
Papadaki et al. (2005)
Chang et al. (2008)
Westerterp and Molga (2004)
Liaw et al. (2008)
Bruggink et al. (2003)
Liaw et al. (2008)
Maestri and Rota (2007)
Dahl et al. (2007)
Molga et al. (2007)
Stolte et al. (2007)
Yuan et al. (2009)
Chen (2004)
Lu et al. (2011)
Arai (2003)
Model Shah et al. (2005)
Palaniappan et al. (2002c)
Palaniappan et al. (2004)
Myers (2008)
Amyotte et al. (2003) Zwetsloot and Ashford (2003) Practical application
Lu et al. (2011)
García-Serna et al. (2007)
Shah et al. (2005) Qualitative
Carpenter and Ogle (2003)
Palaniappan et al. (2004) review
Gupta and Edwards (2003)
Mohd Shariff et al. (2006)
Eckhoff (2005)
Abuswer et al. (2011)
Amyotte et al. (2007) summary, the focus has been on prediction of reactivity haz-
Amyotte et al. (2010) ards, particularly the onset of runaways (Table 3).

Koban and Herrmann (2011)


Practical application 3.3. Unit operation
Zwetsloot and Ashford (2003)

Limbach et al. (2009)


Gupta and Edwards (2003)
Qualitative The design of unit operations in which the chemical or
review physical transformations are realized also provides opportuni-
Amyotte et al. (2009)
ties for hazard reduction. Different types of equipment have
different inherently safer characteristics, such as inventory,
methods to determine the boundaries of runaway reactions operating techniques and self-regulation. One approach to
consist of: safety boundary diagrams and parametric sensitiv- decrease the inventory is to decrease the size of the unit oper-
ity. The safety boundary diagram is a plot of two dimensionless ation and at the same time increase efficiency. This can be
numbers, the reactivity number and the exothermicity num- achieved using microreactors or novel multifunctional reac-
ber. Regions with low exothermicity are inherently safe as tors such as heat integrated or reactive separation units.
the potential for runaway is low. Westerterp and Molga (2004) Microreactor systems are inherently safer because of lower
describe methods to develop safety boundary diagrams for inventory levels. Other advantages include increased mass
single and multiple reactions both in homogeneous and het- and heat transfer capabilities, flow uniformity and poten-
erogeneous systems and discuss the inherently safer reaction tial for high throughput. They ensure a smaller plant size,
conditions in continuous and dispersed phases. Parametric lower cost of production, and more flexible response to mar-
sensitivity refers to the study of the effect that changes in a ket demand. Kestenbaum et al. (2002) designed and built a
parameter has on the variables in the process. A high sen- microreactor system for ethylene oxide synthesis and demon-
sitivity indicates that a small change in an input parameter strated comparable performance to an industrial process, with
results in a large change in the process variable like tempera- the added advantage of improved safety. Microreactors are
ture. Schweitzer et al. (2010) developed a dynamic model of the particularly useful for fine chemicals production. With con-
hydrotreatment of gasoils to quantify the effect that variation trolled residence times and temperatures, the desired product
in heat transfer coefficient has on the stability of the reactive can be generated without unwanted byproducts or side reac-
system. Effects of other parameters such as feed composi- tions, resulting in higher selectivity and yield. Numerous
tion and reactant flow rates could also be similarly studied. In reactions for fine chemicals productions have been reported
Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 389–403 395

design stage. Fluctuations occur in market demands for vari-


Table 4 – Classification of papers addressing unit
operation hazards. ous products. Process scheduling is used to adjust to the type
and quantity of products based on market conditions. For
Paper Management
instance, oil refineries continuously adjust the product slate to
coordinate
account for seasonal changes in product demand (e.g., gaso-
Tugnoli et al. (2009) Metric line, diesel, heating oils, etc.). Hence it is beneficial to include
Amyotte et al. (2007) process scheduling expectations during design. Al-Mutairi
Koc et al. (2011) et al. (2008) presented a method for including scheduling
Liebner et al. (2011) expectations during design and retrofitting. They use the Dow
Klais et al. (2009) F&EI as a safety metric to evaluate the NOx removal options
Liu et al. (2009) Model
in a refinery, accounting for various crude grades and mode of
Benaïssa et al. (2008)
operation.
Steyer et al. (2008)
Kestenbaum et al. (2002) The length of piping carrying hazardous materials can be
Ebrahimi et al. (2009) minimized by suitable layout design. On the other hand, suffi-
cient separation distance between unit operations should also
Zwetsloot and Ashford (2003)
D’Aquino and Mavridis (2007) be provided to ensure that a problem in one section of the plant
Thayer (2005) Practical application does not propagate to other sections, i.e. to prevent domino
Rogers and Hermann (2004) events. A domino event (also known in the literature as esca-
Lopez et al. (2005) lation or knock-on event) is an accident in which a primary
Amyotte et al. (2009) incident propagates to nearby equipment, triggering one or
Chiappetta et al. (2006) Qualitative more secondary incidents. Hence a trade-off between piping
Rusli and Mohd Shariff (2010) review length and prevention of domino events is necessary. Khan
Khan and Amyotte (2002) et al. (2002) present the various inherently safer layout con-
siderations available for offshore oil and gas installations. For
in microreactors (Thayer, 2005). Novel designs of more con- example, the distance between gas compression and sepa-
ventional reactor systems have also received attention in ration facilities which operate at very high pressures should
the new millennium. For instance, Li et al. (2009) designed be maximized. BP uses inherently safer design principles
a spray reactor for p-xylene oxidation to terephthalic acid. for the layout of hydrocarbon systems on offshore facilities
They showed that compared to conventional process for (Considine et al., 2010). Cozzani et al. (2007) applied the inher-
terephthalic acid, the spray process minimizes acetic acid oxi- ent safety principles, qualitatively, to determine effective ways
dation which improves safety. Similarly, Subramaniam (2010) to prevent domino events. The ‘moderate’ principle was found
proposed a one-step spray reactor for inherently safer produc- to be the most effective and simple rules-of-thumbs were
tion of polymer grade terephthalic acid. Reactive distillation proposed for preliminary assessment of safety distances and
designs reduce the number of pieces of equipment required critical inventories. Fragment projection is among the most
thus making it inherently safer. Steyer et al. (2008) propose a frequent causes of domino events in industrial accidents. The
new cyclohexene to cyclohexonol reactive distillation design fragments become airborne and act as missiles. Pula et al.
for improving safety and efficiency compared to the conven- (2007) developed a model to quantify the probability of mis-
tional process. Benaïssa et al. (2008) proposed an intensified sile impact on a particular equipment for missiles originating
heat exchanger/reactor for the esterification process. Koc et al. from bursting of a vessel. These probability measures can help
(2011) developed a dynamic model of a catalytic water-gas- in selection of safe separation distances. The study of domino
shift membrane reactor to determine the dynamic behavior accidents and inherently safer layout of chemical plants is
of the system at various operating conditions. They evalu- rather recent, predominantly in the last five years. Table 5
ated the effect that variations in feed temperature, flow rate, lists all the papers classified under flowsheet and layout design
catalyst loading and purity of feed had on the process in the coordinate.
form of possibly adverse deviations. Eckhoff (2009a) provides
example of inherently safer design options of dust handling 3.5. Storage and transportation
equipment using mass flow silos and hoppers. In summary,
the focus in unit operation has been on designing novel reactor The inventory of hazardous materials stored in a plant poses
systems such as micro-reactors and reactive-distillation units. serious hazards which should be minimized. Reisch (2009)
Table 4 lists all the papers classified under the unit operation proposed an inherently safer water purification system by
coordinate. transporting sodium hypochlorite bleach instead of chlorine.
Landucci et al. (2008) proposed storage of hydrogen in the form
3.4. Flowsheet and layout of metal hydrides, thus making it inherently safer. Hendershot
et al. (2006) reports on the modifications made to a bromine
The flowsheet and layout design of the plant also offer oppor- raw material handling facility in which existing bulk storage
tunities for minimizing hazards. Falcke et al. (2011) studied tanks were replaced by cylindrical vessels. Table 6 lists all the
the integrated gasification combined cycle (IGCC) process for papers under the storage and transportation coordinate.
power generation and found that this process has poorer
inherent safety characteristics as compared to the conven- 3.6. Process control and safety system
tional process since the gasifier unit and gas turbine in the
IGCC process had high F&EI values and the presence of large Inherent safety principles can also be applied to the design of
quantities of CO posed toxicity hazards. Tugnoli et al. (2011) layers of protection in order to reduce the likelihood of events.
defined key performance indicators to study multiple impacts Process control and safety instrumented systems are provided
(environment, safety, costs, health, etc.) during the flowsheet in almost every chemical plant today. The design logic of the
396 Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 389–403

interact with the dynamics of the process and result in larger


Table 5 – Classification of papers discussing flowsheet
and layout hazards. than expected disturbances (Luyben and Hendershot, 2004).
Chemical processes constitute strongly nonlinear systems
Paper Management
with multiple steady-state solutions. Controllability analy-
coordinate
sis can offer insights for identifying the inherent properties
Clark (2008) Fundamentals, practical application of a process and how they limit control performance. Wang
Tugnoli et al. (2011) et al. (2011) argue that the different operating conditions of
Hassim and Hurme (2010b) the chemical plants have different stability and controllability
Hassim and Hurme (2010d) characteristics which should be studied first prior to con-
Khan and Amyotte (2005) trol system design. For example, the liquid phase catalytic
Rahman et al. (2005)
oxidation of toluene for producing benzoic acid is strongly
Koller et al. (2001)
exothermic, highly nonlinear and exhibits poor controllabil-
Leong and Shariff (2009)
Abedi and Shahriari (2005) ity characteristics. Yuan et al. (2011) explore the open and
Metric closed-loop controllability of this process and identify various
Khan and Amyotte (2004)
Gentile et al. (2003) sub-regions with different controllability characteristics to aid
Khan et al. (2003) in control system design.
Shah et al. (2003) Usually, chemical plants are also designed with additional
Hassim and Hurme (2010a)
layers of protection apart from the basic process control sys-
Tugnoli et al. (2010)
Tugnoli et al. (2008b)
tem. The protection layers can be composed of prevention
Tugnoli et al. (2007) devices such as pressure safety valves (PSV), safety instru-
mented systems (SIS), fire and gas systems (F&G) and other
Li et al. (2011) Metric,
emergency systems. A safety instrumented system (SIS) is a
Palaniappan et al. (2002b) model
protection layer, which shuts down the plant, or a part of it,
Banimostafa et al. (2011)
when a pre-specified condition occurs. The essential charac-
Falcke et al. (2011)
teristic of SIS is that it is composed of instruments, which
Shariff and Zaini (2010)
Takriff and Bahnuddin (2010) detect that process variables are exceeding pre-set limits, a
Shah et al. (2009) logic solver that processes this information and makes deci-
Shariff and Leong (2009) sions, and final control elements that take necessary action on
Leong and Shariff (2008) the process to achieve a safe state (Mannan and Lees, 2005).
Model
Moradi and Bahri (2008) Inherently safer SIS should be fully independent of the process
Al-Mutairi et al. (2008)
control system. Common-mode failure can result if the basic
Shah et al. (2005)
process control system and SIS share components, includ-
Palaniappan et al. (2004)
Ebrahimi et al. (2009) ing power supplies. The safety integrity level (SIL), defined as
Huser et al. (2009) the relative level of risk reduction provided by a safety func-
Pula et al. (2007) tion, is commonly used to classify the design criteria for PSV.
Study (2007) On the contrary, specific risk reduction requirement for the
Zwetsloot and Ashford (2003) Practical application SIS, F&G and other emergency systems are usually not spec-
Lopez et al. (2005) ified and standardized methods to quantify its risk reduction
Rusli and Mohd Shariff (2010)
level are lacking. Hence, Tanabe and Miyake (2011) proposed a
Qualitative methodology to apply the SIL concept to emergency systems
Cozzani et al. (2007)
review
Khan and Amyotte (2002) in order to provide risk reduction criteria and establish the
design requirements for these. Meel and Seider (2008) estimate
Tugnoli et al. (2008a) Qualitative review, metric
the frequencies of occurrence of abnormal events and failure
probabilities of safety systems. A review of passive and active
basic process control system can be used to make it inherently engineered systems that prevent dust explosions is reported
safer. For instance, when a disturbance occurs the control sys- by Pekalski et al. (2005) and Amyotte et al. (2010). Table 7 lists
tem design can allow for adequate time for controls to function the papers classified under the process control and safety system
before operating limits are reached. Process control systems coordinate.
are sometimes affected by process intensification, which
3.7. Human factors and management systems

Table 6 – Classification of papers discussing storage and


Human factors and management systems also play a signif-
transportation.
icant role in reducing the likelihood of events. Plant upsets
Paper Management coordinate
and accidents often involve some sort of human error (Sutton,
Nair (2009) Fundamentals 2010). These include failure to follow procedures, taking a
shortcut, or making an (incorrect) assumption about the valid-
Landucci et al. (2008)
Suardin et al. (2007) Model ity of an instrument reading. Errors of intent occur when
Etowa et al. (2002) supervision or management knowingly decide to over-ride
the normal operating or safety procedures. Human–human
Boeh and Christy (2011)
Johnson (2011) interaction and human–machine interaction influence the
Practical application
Reisch (2009) likelihood of events. Hendershot (2007) argues that the proper
Hendershot et al. (2006) documentation of the design basis could help in avoiding
Sharratt et al. (2003) Qualitative review
human error. Particularly, why a design option was chosen
must be well documented in addition to what is the design.
Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 389–403 397

Table 7 – Classification of papers discussing process Table 9 – Citation counts for some inherent safety
control, safety systems and human factors. indices.
Paper Management Metric Citations
coordinate
PIIS (Edwards and Lawrence, 1993) 70
Luyben and Hendershot (2004) ISI (Heikkila, 1999; Heikkila et al., 1996) 85
Murphy (2011) Fundamentals i-Safe (Palaniappan et al., 2002a,b) 53
Pekalski et al. (2005) I2SI (Khan and Amyotte, 2004) 52

Meel and Seider (2008)


Abuswer et al. (2011) discussed here. Palaniappan et al. (2002a,b) developed expan-
Wang et al. (2009)
sions over the PIIS and ISI indices. They added five other
Wang et al. (2011)
Yuan et al. (2011)
supplementary indices: Hazardous Chemical Index (HCI), Haz-
Model ardous Reaction Index (HRI), Total Chemical Index (TCI), Worst
Meel et al. (2006)
Rathnayaka et al. (2011) Chemical Index (WCI) and Worst Reaction Index (WRI) and
First (2010) hazards due to Chemical Reactivity. The benefits of the supple-
Meel and Seider (2006) mentary indices accrue in situations where PIIS or ISI indices
Meel and Seider (2008)
of competing routes are close to one another and cannot
Hendershot (2011) adequately differentiate between them. Usually indices treat
Summers and Zachary (2008) Practical application the chemicals in the process system as individual compo-
Leffler (2007) nents and not as a mixture. Hence Leong and Shariff (2009)
Dowell (2001) Qualitative proposed a new index called process route index (PRI) that
Bennett (2006) review accounts for mixture properties. Metrics to assess the impacts
Tanabe and Miyake (2011) Qualitative review, Model on health and the environment have also been proposed in
recent years. Hassim and Hurme (2010c) developed an index
called the Inherent Occupational Health Index for evaluat-
This would enable the operators to understand the rationale
ing health hazards in the research stage of the plant lifecycle
for a particular procedure. Without proper documentation,
based on material properties. Subsequently, they also pro-
inherently safer designs are vulnerable to modifications that
posed indices for the flowsheet development stage (Health
reduce their efficacy. Ergonomics should be applied in the lay-
Quotient Index) and the engineering design stage (Occupa-
out of equipment, valves, controls, and anything else that
tional Health Index) for assessing occupational health (Hassim
operating and maintenance personnel need to access. The
and Hurme, 2010a,b).
effectiveness of risk management systems is dependent on a
However, these index based approaches have a number
company’s implementation and support for operational disci-
of shortcomings. They are based on subjective scaling and
pline (OD)-related programs to ensure that the process safety
weighting, with limited coverage and often unclear granular-
requirements are followed consistently at all levels of the
ity. Gentile et al. (2003) have attempted to improve on some
organization. Vaughen and Klein (2011) describe how poor OD
of the subjective factors in the inherent safety index by using
increases process safety risk and provide a tool to help monitor
fuzzy set theory. The modifications were essentially aimed at
and improve OD. Papadaki (2008) also reports on the motiva-
improving the sensitivity (either excessive or insufficient) in
tional factors necessary for improving operator commitment
the ranges selected for each of the various index parameters.
and involvement toward safety. In conclusion, despite the role
In this approach each factor is described by a linguistic variable
that human factors have played in major accidents, there is
whose range of interest is divided into fuzzy sets. For each set,
scant literature on understanding this from an inherent safety
a membership function is defined which has a specific shape
perspective. Table 8 lists the papers classified under human
describing the physical behavior of the set. This eliminates the
factors and management systems coordinate.
problems presented by the traditional interval approach for
parameter ranges. Khan and Amyotte (2004) proposed an Inte-
3.8. Assessment techniques
grated Inherent Safety Index (I2SI) that comprised of two main
sub-indices, the hazard index and an inherent safety poten-
As discussed earlier, design modifications rarely result in
tial index. The hazard index measures the damage potential of
a monotonic reduction of risk. Some form of quantifica-
the process, taking into account the hazard control measures.
tion is necessary to evaluate the trade-offs among various
The inherent safety potential index addresses the applicability
design options. This led to the development of a number of
of inherent safety principles to the process. The two sub-
metrics for measuring the inherent safeness of design options.
indices are combined to produce the I2SI value. Srinivasan and
Some of the major indices introduced in the last 11 years are
Nhan (2008) proposed a multivariate approach called inherent
benign-ness indicator to overcome these shortcomings. This
Table 8 – Classification of papers discussing human method uses principal component analysis to analyze various
factors. factors affecting the hazards in the process and to identify the
Paper Management most benign route. This methodology can also bring out the
coordinate similarities and differences between the routes. Using the con-
tributing factors, major hazards could be identified and proper
Bridges and Revondatew (2009)
Papadaki (2008) Fundamentals
safeguards taken. Table 9 lists the citation count of some of the
Hendershot (2007) major metrics available for inherent safety evaluation.
In summary, the focus of research on inherent safety in
Meel and Seider (2008) Model
Vaughen and Klein (2011) Qualitative review
the 21st century has remained on hazards with 87% of the 131
papers. This is in line with the philosophy of inherent safety,
398 Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 389–403

compound in Roche. They discovered an inherently safer sub-


Table 10 – Companies discussing inherent safety in the
new millennium. stitute, dimethyl sulfoxide, which provided equivalent yields
and purities and developed and demonstrated the new safer
ABB
process.
ABS International, Inc.
Acu Tech Consulting Group The many hazards in offshore oil and gas production have
Air Products and Chemical Inc. been brought out by the various accidents over the years, rang-
Arthur D. Little Inc Global Environ. ing from Piper Alpha (1988), to PetroBras P-36 (2001), Bombay
Baker Engineering and Risk Consultants, Inc. High (2005), and Deepwater Horizon (2010). Twinned with this
BASF is the fact that, because of increasing demand for energy, and
BNFL PLC
most new oilfield discoveries are offshore, a large number of
BP Refining and Logistics Technology
new rigs and platforms are built every year. Further, different
BP Safety and Operations
BP Exploration projects offer unique challenges that preclude copy-and-paste
Cabot Corporation of traditional, well-known designs. Hence, the offshore pro-
Chilworth Technology Inc. duction industry offers an excellent test bed for applying
Consolidated Edison Company of New York, Inc. inherent safety principles. Many companies in this industry,
Croda, Inc. ranging from Kellogg Brown and Root (Chia et al., 2003), to BP
Det Norske Veritas (DNV)
(Considine et al., 2010) and Shell (Gilmour and Deveney, 2010)
Dow Chemical
DuPont
have reported proactive applications of inherent safety princi-
Flour Corporation ples in the design of new oil and gas platforms. The interested
INBUREX Consulting GmbH reader is referred to the review by Khan and Amyotte (2002).
Siemens AG Inherent safety principles have also been used by the
IONIK Consulting United States Chemical Safety and Hazard Identification Board
Kellogg Brown and Root (KBR)
(CSB) to propose recommendations after accident investiga-
PPG Industries
tions. Amyotte et al. (2011) studied the possibility of applying
Eastman Chemical Company
Rohm and Haas Company various risk reduction measures in 63 accident investigations
S2V Consulting conducted by CSB and concluded that inherent safety based
Saudi Arabian Fertilizer Co. controls were applicable to 36% of 200 total examples. All the
Shell Upstream International four main principles – minimize, substitute, moderate and
SIS-Tech Solutions simplify – were nearly equally applicable.
Solutia Inc.
Subsequent to the events of September 11, 2001, chemical
TBS Major Hazard Consultants
plant security has received increasing attention. As in pro-
cess safety, chemical plant security is also concerned with
i.e. elimination or minimization of the hazards, rather than large inventories of flammable, explosive, and toxic materi-
controlling them. als. Unlike process safety however, process security seeks to
prevent adverse events caused by factors of harmful intentions.
4. Applications of inherent safety during In such cases, since the frequency of the initiating event is
2001–2011 beyond the control of plant designers, the inherent vulnerabil-
ity of a process is in focus and can be reduced by using designs
Progress has also been reported in the use of inherent safety that minimize or eliminate hazardous (flammable, explosive,
over the last 11 years. Here, we review its adoption in indus- toxic) materials. This would make the plant safer against acci-
try, regulations and accident investigation, and for chemical dents and also an unlikely target for the intentional creation of
plant security analysis. Our survey of the literature revealed disaster. Thus, inherently safer design can directly incorporate
that the authors of 78 papers had an industrial affiliation. considerations of security. Several authors have identified this
Table 10 lists the 32 companies involved. Although this is benefit of inherent safety (Bajpai and Gupta, 2005; Dunbobbin
an imperfect measure, it reveals a two-fold increase in the et al., 2004; Hansson, 2010).
number of companies discussing inherent safety, compared to Since process safety related regulations such as the OSHA
the 1990s. Information on the specific nature of the inherent 1910 CFR in USA and Seveso II directives in Europe came into
safety intervention adopted by the companies is sparse given effect in the 1990s, there has been speculation that inherent
the sensitivity often associated with such developments. Here, safety would also find pride of place in regulatory texts. How-
we highlight a few published cases. Beverage bottling plants ever, regulating inherent safety is not easy because inherently
are required to maintain high standards for sanitation and safer design and implementation is a function of site and pro-
have to clean preparation tanks and lines to prevent contam- cess specific conditions. Contra Costa county in California is
ination, flavor carryover and corrosion. This cleaning often the first to enact a safety ordinance specifically discussing
requires high temperatures and hazardous chemicals (such as inherent safety in 1999. This ordinance explicitly requires
chlorine). Miox corporation (Boeh and Christy, 2011) reported facilities to ‘consider the use of inherently safer systems in
the adoption of an electro-chemically activated clean-in-place the development and analysis of mitigation items resulting
method that produces chlorine and other oxidant species from a process hazard analysis’ (CCPS, 2009). The Contra Costa
in situ by applying electricity to a solution of salt and water. Health Service (CCHS) reported in 2007 that the number and
This inherently safer design thus generates the disinfectant severity of chemical accidents have been decreasing since the
on-site and on demand using non-toxic consumables thus implementation of this ordinance (CCPS, 2009). However, the
minimizing hazards. As another example (Lopez et al., 2005), small number of incidents makes it difficult to establish a
discuss the hazards associated with the use of sodium chlo- clear causal relationship between the ordinance and the num-
rite (and the formation of hypochlorite as a byproduct) during ber of incidences. More recently, New Jersey implemented the
the oxidation step while manufacturing a pharmaceutical Toxic Catastrophe Prevention Act and Prescriptive order for
Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 389–403 399

Chemical Plant Security (CCPS, 2009) and the US congress integrated, with subtle cause-and-effect, and non-apparent
enacted the Chemical Facilities Anti-Terrorism Act (Hess, temporal effects). New processes based on bio- and nano-
2009). Both called for consideration of full range of inherent technologies are entering the process industry. These are often
safety options for chemical plant. characterized by insufficient process and safety knowledge.
The applicability of inherent safety to these has to be demon-
strated. The detail and dynamic complexity of modern-day
5. Discussion plants also pose challenges to the human, who is simul-
taneously both the weakest and the strongest link, in the
The above reviews of the state of inherent safety, both from loop. Ensuring that human actions would be inherently safe
new developments point-of-view as well as from the appli- through holistic consideration of human factors in every
cations point-of-view, lead to the following conclusions. The aspect of design (from occupational health, to control system
primary foundation of the field, the principles first expounded schematics and plant layout) is also necessary for a sustain-
by Kletz, is well understood. They are widely accepted as pro- able plant, that is friendly to people, planet, and profit.
viding a sound philosophy for making better design decisions.
Numerous examples abound, many simple and easy-to-
understand ‘toy’ problems, and some of applications to real,
large-scale plants exist. References
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