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Article history: A study of runaway incidents involving thermal chemical reactions in the UK over the past
Received 19 September 2014 25 years (1988–2013) has been carried out. The objective of this study is to determine possi-
Received in revised form 9 January ble causes of thermal runaway incidents. A statistical analysis of the underlying problems
2015 that led to thermal runaway incidents has been provided. A comparison of the current study
Accepted 4 February 2015 on thermal runaway incidents with those identified prior to 1988 has been carried out. This
Available online 12 February 2015 study clearly shows that lessons have not been learnt from thermal runaway incidents
caused by operator errors, management failures and lack of organised operating proce-
Keywords: dures. These factors have been the possible causes of about 77% of all the thermal runaway
Inherent safety incidents analysed in this study. The number of fatalities and injuries as a result of thermal
Hazard identification runaway incidents has increased by ∼325% and ∼279%, respectively, in the last 25 years even
Health and environment though the number of incidents was significantly less. On the basis of this analysis, several
Process design recommendations have been proposed that could help to minimise the risks associated with
Risk assessment any thermal runaway incidents in the future.
Thermal runaway reactions © 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
∗
Corresponding author. Tel.: +44 0 20 7815 7190; fax: +44 0 20 7815 7699.
E-mail address: b.saha@lsbu.ac.uk (B. Saha).
1
Present address: School of Engineering, University of Hull, Cottingham Road, Hull HU6 7RX, UK.
http://dx.doi.org/10.1016/j.psep.2015.02.005
0957-5820/© 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
110 Process Safety and Environmental Protection 9 7 ( 2 0 1 5 ) 109–115
2.3.2. Human and organisational causes (LPB, 1994a), failure to follow standard operating procedures
A number of human and organisational causes have been con- (SOPs) (Lindley, 2001) and incorrect opening/closing of the
tributed to thermal runaway incidents in the last 25 years as valves (LPB, 1993b) have each contributed to one incident in
illustrated in Fig. 1. It is apparent from Fig. 1 that operator the current study. The findings in this study are in agreement
errors have contributed to the majority of the incidents (13 with a study carried out by Mannan (2012). It was reported that
incidents). It was not possible to identify the exact error due large losses in the process industries were caused due to oper-
to the lack of information in four incidents (FACTS, 1988, 1989, ator errors that contributed about 17% of the causes (Mannan,
1990, 1992b). The lack of understanding of the chemistry by 2012).
the operator was found to be responsible for thermal run- Appropriate management and supervision are essential for
away incident in one instance (LPB, 1992). In another incident, smooth running of a chemical plant. Poor management was
the operator failed to realise that using butene instead of a blamed for an incident in 2008 where monomer mixtures were
mixture of butene with other compounds was a modification left static for prolonged period and the electrical installation
to the existing process that should have been systematically was not fully repaired from the previous day thus causing a
approached (Kletz, 1995). Similarly, in another incident the thermal runaway (Fishwick, 2008).
operator thought that water was completely removed from Organised procedures must be followed with safe practice
the process unit and did not double check whether the water at all times when dealing with chemical reactions. SOPs
was removed or not (Kletz, 1991; Van Reijendam et al., 1992). should be checked and amended on regular basis in order to
Operating outside the safety limits of the reactor vessel has minimise the risks and hazards associated with a plant opera-
contributed to one incident where the responsibility rested tion. Failure to follow these procedures may result in failure to
with the operator and not with the technical advisor (LPB, control the reaction. Managers should take into account that
1996). Inadequate training (Sachdev and Todd, 2005), absence adequate staffing could help in identifying early signs of ther-
of supervision (Pinsky et al., 1990), an increase in work load mal runaway and could possibly act to prevent it. Enough staff
0.00
Metallurgy and metal processing 6.88
3.33 3. Discussions
Refinery 0.00
Inorganics
6.67 3.1. Statistical analysis of the current work
0.00
10.00
Laboratory 0.00 In this study, 30 incidents have been examined. The possible
6.67 causes of the runaway incidents from this study have been
Pharmaceuticals 6.88
compared with those studied by Barton and Nolan (1991) and
0.00
Miscellaneous 12.17
they are as follows:
30.00
It is apparent that a similar trend occurred in the technical
Plastics, rubbers and resins 21.69 and physical causes of runaway incidents for both pre-1988
Fine, intermediate and heavy 43.33 and post-1987 studies. Barton and Nolan (1991) reported that
organics 37.57
the main physical and technical causes of the incidents were
0 20 40 60 80 100 mischarging (35 incidents), reaction chemistry/development
Incidents (%)
not conducted beforehand (34 incidents) and agitation (17 inci-
dents). Similar trends could be seen for the current study
Fig. 2 – Comparison of the incidents in different
where the possible physical and technical causes are mis-
manufacturing industries as reported by Barton and Nolan
charging (5 incidents), plant design (4 incidents) and agitation
(1991) with the current research.
(4 incidents). One of the similarities in the trend was the
mechanical failure (such as stirrer blades shearing off), which
contributed to three incidents for pre-1988 and post-1987 stud-
should be available at all times to operate and monitor a given ies. On the other hand, failure due to temperature (i.e. loss of
chemical plant, however, many operators are made redun- process control) decreased from thirty two incidents occurred
dant in order to cut cost and generate more profit. Educating in the pre-1988 study to five incidents for the current research.
managers, supervisors and operators about the safe operation Leakage, venting and power loss have contributed to six inci-
of the chemical plant is essential in order to avoid incidents dents. This study has reported six incidents due to technical
and minimise losses (Fishwick, 2012). Cleaning of chemical failures, but not enough information is available to identify
reactors and equipment should be conducted appropriately the actual reasons for these failures.
to ensure that it is suitable for the process materials. Human and organisational errors are one of the possible
causes of the incidents in the chemical industries as shown
in Fig. 1. The operators have contributed to thirteen incidents
2.4. Industries involved
studied in this work as compared to eleven incidents reported
for pre-1988 study. The major reduction was found to be in
Batch reactors are ubiquitous in the chemical industry due to
the maintenance department, where twenty five incidents
their convenience and flexibility (Vasanthi et al., 2012). How-
were reported between 1962 and 1987 as compared to only
ever, the pattern of incidents shows preponderance to certain
one incident in the last 25 years. Incorrect labelling, clean-
specific industries as reflected in Fig. 2. Fig. 2 shows that ∼43%
ing, inappropriate staffing are all new causes which have not
of the incidents occurred in fine, intermediates and heavy
been reported in pre-1988 study. Hence, it could be concluded
organics industries, while ∼30% of the incidents took place
that apart from runaway caused by maintenance and process
in plastics, rubbers and resins industries.
control, lessons have not been learnt from previous incidents.
Fig. 2 shows thermal runaway incidents in various man-
2.5. Consequences ufacturing industries for pre-1988 study and the current
research. It can be seen from Fig. 2 that fine, intermediate and
The results from runaway incidents ranged from a simple heavy organics followed by plastics, rubbers and resins are the
foam-over of the reaction mass to a substantial increase in main industries involved in the thermal runaway incidents
temperature and pressure leading to a violent loss of contain- as reported by both pre-1988 study and the current research
ment and a release of large quantities of flammable, hazardous (1988–2013). Fig. 2 highlights that there has been no relief for
and toxic materials. In one incident 45 kg of vinyl acetate was industries associated with plastics, rubbers and resins, where
released to the atmosphere (LPB, 1994b). In a couple of cases, the thermal runaway incidents have increased by ∼8%. Sim-
flammable materials were released that caused fire and a sec- ilarly, the thermal runaway incidents across the industries
ondary explosion followed (Kletz, 1991; LPB, 1994b). This study associated with fine, intermediate and heavy organics have
realised that 17 fatalities and 311 injuries occurred during the increased to ∼6% in the last 25 years. An increase in incidents
period 1988–2013 (see Table 2). A large number of the injuries in these industries could be due to more sophisticated nature
occurred due to release of toxic fumes and their subsequent of the chemical reactions.
inhalation (Gakhar and Carr, 2003). These incidents generally It can be seen from Table 2 that the number of deaths
occurred when the operators were attempting to regain con- and injuries are a lot higher in this study as compared to
trol of the reaction. pre-1988 study even though the previous study had covered
Process Safety and Environmental Protection 9 7 ( 2 0 1 5 ) 109–115 113
189 incidents as compared to only 30 incidents that are cov- (SDS) or from computer-based modelling of reactions. A vari-
ered in this work. The incidents occurred in the last 25 years ety of laboratory techniques such as adiabatic calorimetry and
must have been more serious in order for the number of fatal- accelerating rate calorimetry are available for use to acquire
ities to be this high. In the past, there were many operators knowledge about the thermal behaviour of different reaction
working on a site, whose main job was to look and identify components.
for any sign of incidents. Currently, the situation in the indus-
try has been quite different. Many operators have been made 3.3. Protective measures
redundant in order to minimise cost and generate more profit.
Managers have failed to take into account the vital role the The Health and Safety Executive (HSE) reported that the basis
operators used to play in identifying early signs of runaway of safety of a chemical reaction is the combination of measures
incidents. This could be one of the reasons why explosions that are relied upon to ensure safe operation (HSE, 1998). The
after 1987 were more serious and caused greater fatalities. measures that are chosen for a particular case will depend
Managers should be aware that safe operation and sustainable on a number of factors including the probability of runaway
business success could not be separated (Travers and Smith, reactions occurring, the applicability of various methods and
2012). On the other hand, some types of the earlier runaway the compatibility of the measures with the plant operation.
incidents reported by Barton and Nolan (1991) do not occur In practice, it is not possible to eliminate all hazards by
now because engineers, operators and managers could have inherently safer methods, but additional control measures
taken necessary preventive measures to avoid such causes of could be added to minimise the risk and back up the con-
thermal runaway incidents as reported by Barton and Nolan trol measures with protection, such as process control along
(1991). with the use of inhibitors, emergency relief systems, quench-
ing or containment. Such combination of methods is common.
3.2. Lessons learnt Runaway incidents may also affect the environment. Hence,
it is also important to consider whether measures taken are
The analysis indicates that incidents occurred due to lack adequate to comply with the environmental regulations.
of basic understanding of the process chemistry, inadequate
engineering design for heat transfer, inadequate control sys-
3.4. Process control
tem, no safety back-up systems (including venting) and
inadequate operational procedures, including training.
According to the HSE, process control includes the use of sen-
In order to deal with a hazard, it is necessary to first iden-
sors, alarms, trips and other control systems that either take
tify it using various hazard identification techniques as shown
automatic action or allow for manual intervention to prevent
in Fig. 3. Hazards should be checked on how likely they could
the conditions for uncontrolled reactions. The specification
occur and how serious the consequences could be. It is evident
of such measures requires a thorough understanding of the
that in order to avoid conditions for runaway arising in the
chemical process involved, especially the limits of safe opera-
first place, it is necessary to have the knowledge of both the
tion (HSE, 1998).
chemistry, associated thermo chemistry of the desired reac-
tions, thermal stability and physical properties of reactants,
intermediates and products. Some of this important informa- 3.5. Process control and inhibition
tion could be obtained from the literature, safety data sheet
In batch operations, a failure in the cooling and stirrer drives
are problematic since the heat produced by the reaction can-
Project Stages not always be removed sufficiently. In order to avoid the
release of the reaction mixture into the atmosphere, an
Chemicals testing inhibiting agent could be injected as a first line of defence. A
Impurities testing
Research and Development chemical inhibitor is usually applicable only to intermolecu-
Reactions testing
Reactivity and explosibility lar reactions rather than decomposition reactions (Barton and
Rogers, 1997). In the polymerisation of vinyl compound when
Hazard studies a runaway is detected, reaction inhibitors, e.g., tert-butyl cat-
Pre-Design Insurance assessments
Pilot plant echol could be fed to stop the reaction by removing the free
radicals that propagate it. The right choice of the inhibiting
Failure modes and effects analysis agent for each specific reaction system and the rapid homo-
HAZOP studies
geneous mixing of the inhibiting material with the reaction
Design Process design checks
Risk and reliability assessments mixture is a basic requirement for a successful termination of
Task analysis and operating instructions the reaction. Laboratory studies should be carried out in order
to determine the inhibitor concentration, rate of addition and
Checks against design
Emergency planning the temperature of the chemical reaction. The reliability of the
Commissioning Inspection examination monitoring inhibition system must be quantified and demonstrated to be
Plant safety audits acceptable if inhibition is used as the ultimate basis of safety.
Pre-startup and safety review
chemical reactor in order to cope with an exothermic runaway accidents. Process risks could be managed using either inher-
reaction or if the reactor is engulfed in fire (Hellemans, 2009). ent or passive strategies.
One of the biggest problems in sizing vents is the avail-
ability and accuracy of physical property data for the reaction 4. Conclusions
components. It is a good practice when sizing a relief system
to utilise several design methods to achieve consistency in A critical analysis of thermal runaway reactions in the UK
design. It is crucial that the vent system for a reactor should has been carried out for the last 25 years (1988–2013) and
be designed for the worst case scenario which is reason- the results have been compared with the earlier publications.
ably foreseeable. The scenarios considered should include fire The findings from the current research clearly indicated that
engulfment as well as reaction runaway (Mannan, 2012). lessons have not been learnt as a consequence of runaway
reactions. Even though the number of incidents has been
3.7. Process control and quenching reduced in the last 25 years, the consequence of runaway
reactions has become more serious leading to an increased
Quenching is a method of inhibiting runaway reactions. A cold number of fatalities and injuries. These revelations are in
inert diluent is inserted into the reaction mixture that stops complete contrast to the amount of money and resources all
the reaction by cooling it. The ideal substance is water, assum- industries have been spending in terms of gaining advanced
ing that it could be applicable to particular system as it is knowledge in technical knowhow of operating a chemical
cheap, readily available and has a high specific heat capacity. plant on a day-to-day basis to avoid incidents caused by
However, in some processes water may react exothermically thermal runaway. It is evident that teaching in the aca-
with the reaction mixture and therefore alternative diluents demic institutions as well as training in the industries lack
should be used. in polymerisation and decomposition reactions. This study
In an industry, the most common method of addition of highlights that similar trends have been observed over the
diluent is by quenching, where the diluent is added rapidly past five decades for thermal runaway incidents caused by
to the reactor from a storage vessel mounted above it. When mischarging, agitation and quality control. This study also
a runaway reaction is detected in the reactor (indicated by a indicates that operator errors, management failures and the
temperature indicator), a valve opens automatically and the absence of organised procedures have been the major con-
quench liquid runs rapidly into the reactor under gravity. The tributors for runaway incidents. It is recommended that all
quench valve should be opened and should not fail during industries should introduce systematic assessment proce-
runaway reactions. In some cases, where adequate quantity dures for chemical reaction hazard and follow it in order to
of diluent could not be introduced into the reactor because assist in reducing the most common types of errors attributed
of less space within the reactor, dumping should be used to thermal runaway reactions. It is essential that operators
(Prugh and Johnson, 1988). The advantages of quenching or have a thorough training including a thorough understand-
dumping include no environmental pollution since nothing is ing of the process chemistry and thermochemistry, ensuring
discharged to the environment, the quenched mixture could adequate engineering design for heat transfer, adequate con-
be easily disposed off and the recovery of expensive reactants trol systems (temperature control), safety back-up systems
is possible. and adequate operational procedures. Managers should not
neglect the safety by reducing the number of operating staff,
3.8. Process control and containment thereby increasing the likelihood of an incident, to generate
more profit. In fact, managers should discuss and consider
Containment of the products of a runaway reaction has the probability and consequences of an increase in the risk by
been an attractive option that prevents toxic, flammable and reducing the number of operating staff. It is also advised that
corrosive decomposition products from escaping to the envi- managers should be aware that safe operation and success of
ronment causing environmental hazards. A reactor vessel for sustainable business could not be separated.
total containment should be designed to resist the maximum
pressure produced during the runaway reaction. Particular
Acknowledgements
consideration has to be given to weaker parts of the reactor
system, e.g., associated plant item such as a glass condenser.
Rim Saada and Dipesh Patel gratefully acknowledge the finan-
cial support provided by London South Bank University, UK.
3.9. Assessment strategy
The authors acknowledge the support and guidance provided
by the late Professor Philip Nolan of London South Bank Uni-
Runaway reactions occur in a batch reactor in an industry
versity.
due to the loss of thermal control. A thermal hazards assess-
ment strategy has been used to identify the materials and
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