Case Histories and Recent
Developments to Improve Safety
Assessments during Process
Development
A.A. Khan
Emeritus Scientist, Chemical Engineering Division, Indian Institute of Chemical Technology, Hyderabad, India;
aakhan_iict@rediffmail.com (for correspondence)
Published online 31 May 2006 in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/prs.10137
Prevention of chemical processing disasters largely
depends on assessment of thermal stability, mutual
compatibility, and decomposition characteristics of
materials used in the process. Such studies also facili-
tate a priori evaluation of vulnerability in operations
and can be conveniently organized in the “process
development studies” phase of the selected process.
However, investigations conducted after the accidents
invariably reveal that almost all the major incidents
could have been avoided. This suggests an inadequate
safety assessment and the vulnerability of a chosen
process.
Recent literature indicates that, in addition to the
areas previously discussed, specific attention should be
paid to the behavior of process materials under critical
conditions.
Quantification of a potential hazard, before an ac-
cident, often leads to modifications in design of the
equipment and operating conditions, for example, to
avoid serious accidents. © 2006 American Institute of
Chemical Engineers Process Saf Prog 25: 245–249, 2006
Keywords: disaster prevention, material incompat-
ibility, thermal stability, runaway reactions, reactant
accumulation
INTRODUCTION
A recent analysis of major accidents shows that more
than half take place in fixed facilities, slightly less in
transportation, and 5% in loading and unloading oper-
ations. Chemical plants under normal operation are
thus the most probable sites of chemical accidents such
© 2006 American Institute of Chemical Engineers
Process Safety Progress (Vol.25, No.3)
as fires, explosions, and release of hazardous materials
such as ammonia, chlorine, and hydrocarbons [1].
Hazard analysis of incidents in the chemical industry
is presently based on relevant tools and techniques,
such as event tree analysis (ETA) and fault tree analysis
(FTA). Simulation and modeling of release scenarios, in
terms of frequency of occurrence and the conse-
quences, are used to quantify risk. In spite of these
developments and implementation of process safety
management systems (PSMSs) the prevailing frequency
of accidents is alarming. The results of a comprehen-
sive analysis indicated that the accidents are continuing
to increase because the elements of PSM are not yet
used as intended, given the lack of communications
and administrative controls [2]. Explosions account for
two thirds of the losses, although the incident injury
rate appears to be decreasing. Some of the reasons for
the situation are (1) failure to learn from past accidents,
(2) a reluctance to reveal/share details, and (3) a ten-
dency to underplay mistakes. These data indicate that
PSMSs in place are somewhat effective but additional
levels of control and mitigation measures are required
[3].
Another important aspect that can effectively atten-
uate the frequency of mishaps is the understanding of
the chemistry of process development, which requires
the selected innovative process route to be studied
comprehensively and the specifications and character-
istics of raw materials, intermediates, and recycle
streams be evaluated. The influence of contaminants,
thermal stability of raw materials and intermediates,
and compatibility of components in process streams
must be thoroughly investigated by calorimetric tech-
September 2006 245
niques. Identification of major hazards and measures to
mitigate their consequences form part of this phase of
technology development.
EARLY DETECTION AND PREVENTION OF ACCIDENTS
The opportunity to study the selected process at an
early stage is unique with respect to its effectiveness in
terms of economic and technical benefits. For example,
extensive financial damage and injury to 91 persons
could have been averted, at the agricultural chemicals
factory, if the consequences of introducing potassium
hydroxide instead of potassium carbonate had been
evaluated [4]. Similarly, an explosion arising from the
overcharge of caustic to a phenolic compound could
have been avoided when a halogenated aromatic com-
pound was added in the next step [5]. Thus, the efficacy
of an early understanding of hazards associated with a
chemical process cannot be overemphasized. How-
ever, at this stage the assessment is usually confined to
the desired reaction pathway, whereas hazard analysis
demands evaluation of all the possible reaction path-
ways. Other advantages of early detection of hazards
during the process development are the following:
• As the process goes through its life cycle, it be-
comes more difficult to make radical changes in
the chemistry.
• Changing the route of chemical synthesis after
commercialization of the process may affect the
product performance, thereby forcing customers
to do additional characterization.
• Highly regulated chemicals, such as pharmaceu-
ticals and agricultural products, may have to be
reevaluated by regulatory authorities through
time-consuming and expensive toxicity tests.
In addition to desktop data searches for hazardous
characteristics, chemical structures of all the relevant
compounds and their specific incompatibility with cer-
tain groups of chemicals can be determined. Azides,
diazo and diazonium, halo and nitro compounds, oxi-
dizing agents, various nitrogen-containing molecular
structures, and some inorganic compounds should be
identified for a detailed study at the preliminary stages
of process development [6].
Selection of reaction media (in the form of solvent)
and reactants can be based on their respective proper-
ties. For example, the wider the range of concentra-
tions within the flammable limits for a solvent, the more
hazardous it is. However, the minimum ignition energy
(MIE) and minimum ignition temperature (MIT) deter-
mine the vulnerability of solvents in operations.
In the case of toxic chemicals the criteria are based
on lethal dose, threshold limit value (TLV), immediately
dangerous to life and health (IDLH) considerations,
and LD50 and LC50 concentrations.
PRINCIPLES OF CHEMICAL PROCESS SAFETY
Thermal stability of operations—specifically those
involving chemical reactions—is a major cause for con-
cern for the chemical processing industry. An excellent
review of this topic is provided by Hoffman [6], who
advocates improvement of communications between
safety experts and process chemists. For all exothermic
246 September 2006 Published on behalf of the AIChE
reactions a suitable cooling system must be provided to
maintain the reaction at its optimum temperature by
dissipating the excess energy. Reducing the hazard of
exothermic reactions by changing the chemistry is an-
other option [7, 8]. Stepwise removal is another ap-
proach that is used in processes involving nitration.
Unexpected variations in operational parameters can
cause a “runaway ” reaction, which involves a rapid
increasing of the reactor temperature and pressure,
resulting in hazardous consequences. Reactor failure is
often followed by fire, explosion, and release of toxic
materials. Experience suggests that such loss of control
may be caused by
• Reactant accumulation in the reactor
• Presence of undesirable and incompatible impu-
rities
• Accidental mixing of reactants
• Inadequate evaluation of reaction mechanism
• Reactor design based on erroneous perception of
reaction kinetics and mechanism
Reactant Accumulation
Free-radical chain reactions are usually character-
ized by an induction period. Initiation of the reaction is
therefore performed by specific “initiators”. Induction
periods are controlled by selecting the type of the
initiator, its concentration, and the temperature and
pressure of the initiation step. Careful optimization of
these parameters is necessary, particularly in industrial
operations. An inadequate understanding of the pro-
cess of initiation can result in accumulation of reactants
and a subsequent sudden large release of energy. Re-
actions that require initiation need to be studied thor-
oughly before specifying the “start-up” procedure.
Undesirable Impurities
Nitration, halogenation, and some other reactions
are extremely sensitive to certain types of impurities.
For example, trace quantities of peroxides, oxides of
transition metals, and corrosion products can trigger
unexpected polymerization reactions, thereby initiating
a rapid release of energy and an increase in reaction
temperature to very high levels. Thus, it is important to
identify the probable impurities that can initiate unde-
sirable exothermic reactions before commercialization
of the process.
The literature suggests that commercial vinyl acetate
monomer (VAM) does not polymerize in normal stor-
age conditions. Assessments of the isothermal induc-
tion period at 573, 563, and 553 K clearly indicated that
the thermal stability of recovered VAM is adversely
affected by temperature. At 553 K the polymerization
process initiates at 70 – 80 min, whereas at 573 K the
process is initiated after 30 –35 min. This study ex-
plained the unexpected rupture, in the summer time, of
a 35-m3 storage vessel containing recovered VAM [9].
Accidental Mixing
Chemical hazards arising from the interaction of
various ingredients can be avoided only by prior
knowledge of the accidental mixing of a likely unex-
pected combination of materials. Prevention of acci-
DOI 10.1002/prs Process Safety Progress (Vol.25, No.3)
dents that result from incompatible chemicals therefore
requires identification of all likely combinations of haz-
ardous chemicals used in a process. A more crucial
step, which follows, is the identification of process
steps where such combinations can occur.
Aluminum powder and sodium hydrosulfite react
rapidly with water. In a blending operation, water-
cooled jackets were used to avoid any accidental rise in
temperature. During a routine operation, reported from
Germany, the jacket failed, water came in contact with
the two chemicals, and the resulting violent reaction
extensively damaged the plant, killing five workers and
injuring many [10].
Reaction Mechanism, Kinetics, and Calorimetric
Assessment
Efficient dissipation of excess energy of exothermic
reactions depends on the reactor design. If the rate of
release is accurately estimated, a reactor can be de-
signed to ensure that no accumulation of heat takes
place. However, any imbalance in heat dissipation re-
sults in an increase in reaction temperature. As the
process of heat accumulation continues the rate of
reaction increases exponentially, thereby enhancing
the rate at which heat is generated, whereas the rate of
heat dissipation increases linearly as the temperature
differential increases. This sequence ultimately leads to
a thermal runaway causing unforeseen damages to
plant and personnel. Thus, a thorough characterization
of reactions is advisable at the initial stages of process
development. The temperature dependency of a kinet-
ically controlled reaction, for example, is quite different
from that of diffusion-controlled processes; that is,
whereas in the former case the reaction rate is an
exponential function of temperature, in the latter case it
largely depends on the mass transfer rates prevalent in
the vicinity of the reacting mass. For example, in a
gas–liquid exothermic reaction the rate at which the
temperature of the reactor increases is dependent on
the solubility of gas in the liquid phase. As the temper-
ature increases the solubility of the gas invariably de-
creases, that is, the availability of gas in the liquid phase
decreases, resulting in reduction of the reaction rate.
Similarly, the dominance of side reactions and consec-
utive reactions determines the complex relationship
between temperature and reaction rates. Further, ad-
sorption-controlled and equilibrium-limited reactions
can be expected to exhibit rates that are inversely
proportional to temperatures. For example, the rate of
a catalytic gas–solid reaction depends on the amount of
gaseous reactants adsorbed on the catalyst. As the tem-
perature of the catalyst increases the quantity of gas
adsorbed on the catalyst decreases, thereby reducing
the rate of reaction. For each one of the reactions
enumerated above the heat dissipation rates in an
emergency will be quite different. Thus, to safeguard
against heat accumulation and emergencies, specific
unexpected events have to be identified and their effect
on the stability of operations assessed in a process
safety laboratory.
Process Safety Progress (Vol.25, No.3) Published on behalf of the AIChE
Example
Oxidation of nitrotoluenes with dilute nitric acid in
liquid phase yields the corresponding nitro-aromatic
acids that are important intermediates in the drug and
dye industries. A quantitative indication of the role of
operating parameters has been assessed for the pro-
duction of 4-nitrobenzoic acid by an extensive investi-
gation using an accelerated rate calorimeter (ARC) [11].
Two characteristics that render this nitration process
hazardous and a source of possible thermal explosion
are: exothermic reactions and simultaneous evolution
of gases. Additionally, the product 4-nitrobenzoic acid
is known to undergo decomposition at 573 K.
Quasi-isothermal experiments clearly showed that
excess nitric acid reacts with the substrate and raises
the reaction temperature from 558 to 593 K. This find-
ing was also verified on an ARC with an initial temper-
ature of 433 K.
From the above results, it was concluded that the
addition of 20% w/w nitric acid up to molar excess of
50% does not guarantee safe operating conditions.
Reaction Runaway Scenario
It is obvious from the above example that thermal
imbalance culminates in an exponential rise in reactor
temperature resulting from limited heat dissipation ca-
pacity. A series of probable scenarios can be visualized
against which specific precautions have to be taken to
avoid a runaway reaction. To quantify and control a
chemical reaction hazard the processes/operations for
generation and dissipation of heat have to be evaluated
through kinetic and thermodynamic analysis of the
reacting system.
Example
Acrylic monomers undergo free-radical polymeriza-
tion to produce acrylic resins. Organic peroxides are
used as initiators that are thermally decomposed to
provide the primary radicals. In 2001 as the result of a
runaway reaction in an acrylic resin reactor a major fire
and explosion accident occurred at the Fu-Kau plant in
Taiwan. One person died, 112 were injured, and a total
loss of 10 million US dollars was incurred. Investigation
of the incident to identify the possible causes of failure
and to estimate blast overpressure were subsequently
carried out using a differential scanning calorimeter
(DSC) and a vent size package (VSP) [12]. DSC exper-
imental data of all the ingredients in use and a normal
recipe were characterized with respect to normal onset
temperature and both exothermic and peak exothermic
power. Additionally, a normal recipe with half the
quantity of solvent and another with double the quan-
tity of initiator were also evaluated to identify the most
probable causes of the accident. Runaway reaction
risks in all three cases were high, given that the time to
maximum reaction rate (TMR) was much shorter than
8 h and the final temperature recorded was much
higher than the boiling points of all the reactants. In the
case of increased quantity of initiator this time is re-
duced to 1.5 h, which implied that there was not
enough time available to organize an emergency re-
sponse. Availability of such insight helps not only in the
design and operation of the reactor and its instrumental
DOI 10.1002/prs September 2006 247
control system but also in devising safe operating sys-
tems for emergency action. The VSP data clearly indi-
cate the variation in reactor pressure with time and the
temperature profile showing the increase in reaction
temperature with time. DSC with the reactants and
products as well as overall reaction mass is used to
predict their thermal stability [13].
RECENT DEVELOPMENTS
Of late, various sources of information are exten-
sively addressing issues related to process safety in
synthesis and processing of fine chemicals and inter-
mediates for the chemical industry. Extracts of a few
relevant aspects are provided in this section.
Assessment of Decomposition Hazard
Changes in operating conditions in the final recov-
ery of product are often considered. Separation of
products, downstream of the reactor, is therefore the
area amenable to such alterations to enhance produc-
tivity. However, the consequences of adopting alterna-
tive operating parameters have to be thoroughly eval-
uated before implementation to ensure safety in
operation. Extensive calorimetric studies were carried
out to define safe operating parameters of the wiped-
film evaporator (WFE) that separates a high boiling
product from a heavy tar stream.
During a typical exercise of establishing safe oper-
ating conditions an accelerating rate calorimeter (ARC)
and an isothermal calorimeter were judiciously de-
ployed [14]. The study was initiated with comparison of
thermal stability of a sample generated several years
ago with the current product. These two samples were
found to be similar in their characteristics. A “jump-
start” approach was then adopted where the ARC is
preheated to the required temperature before introduc-
ing the sample. The exotherm recorded in this case
indicated the “heat history” of a high self-heat rate,
suggesting several simultaneous exothermic reactions.
To analyze this situation, an isothermal calorimeter was
used where the reactions taking place at various tem-
peratures could be individually distinguished. Finally,
preliminary analysis of isothermal calorimetric data was
used to assess the percentage decomposition occurring
at different time intervals. These data, extrapolated to
the anticipated residence time of the WFE (⬍2 min),
indicated much less than 1% decomposition, thus sug-
gesting that the use of WFE at the required higher
operating temperatures is a safe approach for enhanc-
ing production.
Hazardous Compounds
The primary decomposition pathway of borane–
THF complexes proceeds by a THF ring-opening
mechanism, ultimately forming tributyl borate. Users of
borane–THF complexes were recently alerted to new
information for the 2 M borane–THF complex that
describes it as self-reactive hazardous material with a
self-accelerating decomposition temperature (SADT) of
40° C [15]. This precaution had to be announced after a
400 L cylinder of 2 M borane–THF exploded during
storage at the Pfizer research campus at Groton, CT,
resulting in injuries and property damage.
248 September 2006 Published on behalf of the AIChE
Incidents that happen during the operation of chem-
ical plants help to identify the hazardous nature of
specific compounds. This is another way of identifying
hazardous compounds. Doubly lithiated bis(dimethyl-
amino)methane is one such example. The compound
exploded while being dried in vacuum. It is therefore
advised that the material and related compounds
should be regarded as potentially explosive and treated
accordingly [16].
Aqueous Solutions of Organics
Aqueous solutions of flammable and combustible
organics are often used in manufacturing processes.
The fact that the composition of an aqueous solution
determines the proportion of volatile component in the
vapor phase is well known. However, it is the latter that
promotes ignitability (or otherwise) of the vapor. Thus
for safety in operation it is important to assess whether
the aqueous solutions in processing are liable to gen-
erate a vapor composition that is combustible. Appro-
priate measures have to be devised during the scale-up
to prevent such vapor streams from being released and
coming in contact with sources of ignition. Their com-
positions, minimum ignition energy (MIE), and mini-
mum ignition temperature (MIT) have to be carefully
examined to ensure safety in design and operation of
the plant/equipment. Alternately, a system that effec-
tively contains such hazards should be installed [17].
CONCLUSIONS
Numerous major incidents that occurred globally in the
chemical industry have been successfully investigated,
particularly over the past few decades. It was also possi-
ble in most cases to identify the major events and their
sequence that led up to the disaster. The consequences in
each of the disasters—in terms of overpressure developed
as a result of explosions, heat radiation caused by fires,
and the population exposed to toxic material released—
could be explained with quantitative analyses. As a result
of these exhaustive efforts it is now possible to design and
confidently operate the safety systems required to prevent
such accidents, provided the potential hazards are iden-
tified during the initial stages of process development.
However, in spite of these advances the frequency of
“mishaps ” and their consequences remain unabated. It is
therefore necessary to make full use of the opportunities,
at the conceptual stages of process development and
design, to reduce the frequency of accidents in chemical
process industries. Process Safety Management systems
are required to ensure that hazards are identified and
evaluated in the early stages of process development.
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DOI 10.1002/prs September 2006 249