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# 2006 Institution of Chemical Engineers
www.icheme.org/cherd Trans IChemE, Part A, July 2006
doi: 10.1205/cherd.05221 Chemical Engineering Research and Design, 84(A7): 543– 552

REVIEW PAPER

SAFETY AND RUNAWAY PREVENTION IN BATCH

AND SEMIBATCH REACTORS—A REVIEW
K. R. WESTERTERP1 and E. J. MOLGA2

1
Ramon Llull University, Institut Quimic de Sarriá, Barcelona, Spain
2
Warsaw University of Technology, Chemical and Process Engineering Department, Warsaw, Poland

I
n this paper a review of recent developments on safety and runaway prevention in batch
and semibatch reactors is given. To prevent thermal runaways in chemical reactors
usually three lines of defense have to be considered: choice of the right operating con-
ditions, early warning detection system and system to handle running away reactions. Because
of its too specific nature, the last line of defense is not discussed in this review, while the
former two are considered in detail. Firstly the capability and applicability of the reaction
calorimeter for safety assessments are reviewed, then fundamental safety criteria for safe
operation of batch and semibatch reactors are reported and discussed. A review of the most
useful and efficient methods for a correct choice of safe operating conditions is split into
two cases: one, when the reaction kinetics are known, and when kinetic information is not
available. Also several promising recent developments of an early warning detection
system for the on-line detection of unexpected situations leading to a thermal runaway are
presented.

Keywords: safety of chemical reactors; criteria of thermal runaway; reaction calorimetry;

early warning detection of runaway; batch and semibatch reactors.

INTRODUCTION of the reactions executed daily do not have a heat effect

In this paper we will review the developments in the last
25 years in the study of safety and runaway prevention of
batch and semi-batch reactors. We will do so from the
view point of the science of reaction engineering and there-
fore, we will leave a number of relevant studies untouched
that belong to the fields of chemistry, mechanical engineer-
ing and/or organizational sciences. In Table 1 we give stat-
istical data on the prime causes of batch reactor incidents as
they have been reported in three different studies (Verwijs,
1994). We can observe that at least more than 60% of the
incidents could probably be avoided, if a proper design of
the reactor plant and choice of the safe operating conditions
has been performed. The number of incidents per month
seems to increase in time according to Table 1, this is not
the case in reality: the numbers of reports and methods of
reporting have increased and improved very much over
the period from 1960 to 1990. We may feel that a
number of two incidents per month for a few thousands
of reactors considered in the surveys leads to a rather
small percentage of incidents. However, more than 80%


Correspondence to: Professor E. J. Molga, Warsaw University of Tech-
nology, Chemical and Process Engineering Department, ul. Warynskiego
1, 00-645 Warsaw, Poland.
E-mail: molga@ichip.pw.edu.pl
large enough to cause a runaway, so that the chance of a
runaway, nevertheless, is not hypothetical.
To prevent reactor incidents and runaways in general
three lines of defense have to be considered in the design
and operation of a (semi-)batch reactor. The first line of
defense is the choice of the right operating conditions.
This refers to the degree of mixing, the cooling capacity,
the choice of the coolant temperature, the dosing rate of
the reactant(s) and so on. In the course of the years many
papers have been written on the choice of the operating
conditions; moreover, we should realize that the studies
on tubular reactors also can be translated to batch reactors.
Most recommendations are based on the knowledge of the
kinetics of the reaction. Regretfully batch reactors are
almost exclusively used in the fine chemicals industry,
where usually time and money are serious constraints for
the costly and time-consuming study of reaction kinetics.
For highly exothermic reactions the use of inaccurate kin-
etic information often leads to a too prudent selection of
operating conditions with low reactor productivities. In
the last decennia the Reaction Calorimeter has become
widely accepted as a tool for the selection of operating con-
ditions, so that we will also dedicate some space to the dis-
cussion of this piece of very useful laboratory equipment.
The second line of defense is an early warning detection
system. As is clear from Table 1, a correct choice of

543
544 WESTERTERP and MOLGA
Table 1. Prime causes of batch reactor incidents (Verwijs, 1994).
1962–1984 1962–1987 1986–1990
References

Nolan and Barton and
Incident cause Barton (1987) Nolan (1989) Etchells (1993)
Thermo-reaction 21.4% 20.1%
chemistry
Raw material quality 7.9% 8.9%
Maintenance/other 22.3% 21.3%
factors
Temperature control 22.2% 18.9%
Loss of 9.5% 10.1%
mixing/agitation
Mischarging of 16.7% 20.7%
reactants
Incident rate 0.46 0.54
(#/month)


Data obtained from Health and Safety Executive records (HSE, UK).
operating conditions is not enough for the safe running of a
reactor section in the plant. Human errors like mischarging
of reactants, maintenance troubles, agitator break down and
so on always may occur. Therefore, it would be a god send
if we could provide industry with a piece of equipment or a
procedure, that can give an early warning to the operator to
anticipate a runaway to occur within a shorter period, say
for example, 20 to 200 min in advance of reaching the
maximum runaway temperatures. In this field in the last
ten years great advances have been made.
The third line of defense is a suitable system to handle
running away reactions. Such systems depend on the reac-
tants and reactions at hand. If vapors are developed, we
need a blow down system with catch tanks; or in another
case, reactor contents must be discharged to refrigerated
cellars loaded with ice to stop the reaction by freezing. In
practice, many different approaches can be found. We will
not discuss this aspect in this paper, because the measures
to be taken to handle a reaction mass, that is heating up
towards a runaway, are too specific for each particular case.
In this paper we will discuss first the capabilities of the
reaction calorimeter, then the criteria based on known kin-
etics to operate a batch reactor safely and after that the
methods developed to achieve safe operation without
knowing reaction kinetics. At the end we will dedicate
some space to the promising recent developments of an
early warning detection system.
THE REACTION CALORIMETER
The reaction calorimeter has been developed and now is
in full use at almost every process development laboratory
in fine chemicals industry. In commercial applications of
reaction calorimetry the operation of batch and semibatch
reactions is supported in many ways apart from controlled
heating and cooling, stirring and mixing, distillation and
refluxing, dosing of reactants and measurement and control
of process parameters (pressure, pH, turbidity, chemical
content by FTIR analysis and so on).
An extensive review of the application of the reaction
calorimetry is given in the special issue of Thermochimica
Acta 289, 1996, edited by R.N. Landau. In this issue
Trans IChemE, Part A, Chemical Engineering Research and Design, 2006, 84(A7): 543– 552
entitled Reaction Calorimetry, in a series of contributions
the expanding role of reaction calorimetry is demonstrated
and its theoretical principles, methods of modelling as
well as areas of application are indicated and widely
discussed—see a.o. Landau (1996), Rowe (1996) and
Zaldivar et al. (1996). Following Landau (1996), three
basic areas of application of reaction calorimetry can be
14.8% distinguished: Process Safety, Process Development and
Basic Research. All of them contribute significantly to
9.8% the evaluation of safety aspects of batch and semibatch
22.2% reactors by thermal and kinetic analysis of chemical reac-
13.9% tions. In a more recent review by Zogg et al. (2004), the
13.1% most important calorimetric principles are presented and
discussed—including heat flow, heat balance, power
26.2% compensation and the Peltier principle—as well as a
classification and a comparison of the available reaction
2.03
calorimeters. Among numerous relevant papers on the
contribution of reaction calorimetry to safe operation of
chemical reactors, e.g., the following publications should
be mentioned: Ubrich et al. (2001) and Gesthuisen et al.
(2005). A few commercial applications of standard heat-
flow reaction calorimeters are available on the market for
both laboratory and research purposes. To avoid promoting
any particular producer the reader is referred to the papers
cited above as well as to the webpage HarsNet (HarsBook).
In principle each heat-flow reaction calorimeter
measures the heat evolution with time of a reaction under
isothermal, isoperibolic or adiabatic conditions. A sche-
matic diagram of a typical bench-scale reactor is shown
in Figure 1.
The principles of reaction calorimetry are based on the
determination of mass and energy balances carried out
over the reaction vessel. In the general case—taking into
account the behaviour of a semi-batch reactor, even with
evaporation of solvent or reactants—the molar balance
for each reactant in the reacting mixture has to be formu-
lated, including the molar flow rates due to evaporation
and refluxing of certain components. Their flow rates
have to be determined from a heat balance around the con-
denser as well as from a mass balance around the reflux
collector (see Figure 1).
The reaction heat-flow rate qR(t) can be found easily
using only temperatures measured inside the reactor and
in the coolant jacket. Values of parameters such as the
overall heat transfer coefficient U and the specific heat
capacity of the reaction mixture CP, can be determined in
a separate series of calibration experiments.
An accurate estimation of heat flow through the reactor
wall is essential for this type of reaction calorimeters and
can be found from the following relationship:
qflow ¼ UAðTR  TA Þ (1)
where TA is a corrected jacket temperature, Tc, to take into
account the heat capacity of reactor walls (Zaldivar et al.,
1996; Molga, 1997).
Having determined the power generated due to the reac-
tion progress, qR(t), the total heat effect, QT, can be calcu-
lated as well as the reaction enthalpy:
Ð tF
QT 0 qR (t)dt
DHA ¼ ¼ (2)
DnA DnA
 SAFETY AND RUNAWAY PREVENTION
Figure 1. Schematic diagram of a typical bench-scale (semi-)batch reactor or a reaction calorimeter: 1—basic unit containing reactor control and regulation
systems, 2—reactor vessel with jacket, head assembly and stirrer, 3—dosing pumps, 4—electronic weights, 5—computer for controlling the system and
acquisition of data, 6—cryostat, 7—distillation and reflux set.
Then, for a single reaction, the conversion rate of the com-
pound A can be estimated as a function of the reaction
time:
qR ð t Þ
RA ð t Þ ¼ (3)
DHA
and further the conversion of the compound A as:
Ðt
qR ðtÞdt
XA ð t Þ ¼ 0 (4)
QT
Based on the mass balance and the stoichiometric reaction
equation as well as using the conversion rate, the concen-
tration of the ith reactant in the reacting mixture can be
found as a function of the reaction time.
So, based on data for the reaction rate and the reactant con-
centrations, both as a function of time, the reaction kinetics
can be studied and the safety of the process can be analysed.
As can be seen from equations (2) – (4), even with a single
run the reaction enthalpy can be determined, while by carry-
ing out the reaction at isothermal conditions at least at two
different temperatures, the activation energy can be
obtained. So, with the reaction calorimeter the parameters
DHR, E, DTad and Cp, required for process safety assessment,
can be estimated. They can be directly used for safe design-
ing of the reactor performance on an industrial scale.
Apart from the references mentioned before in this
section, some other representative examples of practical
applications of reaction calorimetry are listed below.
They have been here arbitrarily grouped according to the
categories proposed by Landau (1996), although all of
them can be directly related to safety of processes:
. Process Safety (Zaldivar et al., 1992; Schuler and
Schmidt, 1992; Regenass, 1997a, b; Serra et al., 1997;
Lerena et al., 1996; De Filippis et al., 2002; Molga
et al., 2004).
Trans IChemE, Part A, Chemical Engineering Research and Design, 2006, 84(A7): 543 –552
545
. Process Development (Schmidt and Reichert, 1988; am
Ende et al., 1996; Ferguson and Puga, 1997; Erwin
et al., 2001; Clark et al., 2001).
. Basic Research (Nomen et al., 1997; Stoessel, 1997;
Singh, 1997; LeBlond et al., 1996; Ubrich et al., 1999;
Nogent and Le Tacon, 2002).
CRITERIA FOR SAFE OPERATION AND RUNAWAY
PREVENTION OF (SEMI-)BATCH REACTORS, BASED
ON KNOWN KINETICS
Runaway prevention has drawn the attention of chemical
engineers for many decennia. We refer to the early work of
Semenov and others already before the Second World War,
specially in the field of combustion engineering, and also to
the work of Barkelew (1959). He demonstrated that for first
order reactions in a batch reactor the reactor remains ther-
mally stable provided the temperature difference between
coolant and reacting mixture is not higher than:
TR  Tc  RTc2 =E.
Provided this condition is fulfilled a runaway will not
occur. Later Van Welsenaere and Froment (1970) demon-
strated this also holds for a temperature difference smaller
than RTR2/E and that an even somewhat higher (TR 2 Tc)
can be applied without a runaway. In the period under con-
sideration Balakotaiah et al. (1995) demonstrated that the
above criterion must be corrected for the heat taken up
by the mass of the reactor vessel. They introduced the
ratio of the heat capacity of the reactor vessel and its con-
tents compared to that of the reactor mixture only and
called this arbitrarily a Lewis number
ðmcp ÞR ðm cp Þw
Le ¼ ¼1þ
ðmcp Þf ðm cp Þf
This factor, called also thermal inertia, had been used ear-
lier—e.g. see the paper by Townsend and Tou (1980),
546 WESTERTERP and MOLGA
where its influence on runaway trajectories as well as on
thermal stability is also discussed. So, the acceptable adia-
batic temperature rise for the batch wise executed reaction
can be a factor Le higher. In practice it is difficult to esti-
mate the value of Le: for instance the agitator will have
the same temperature as the reaction mixture, but the
wall of the reactor not so, because it will have a tempera-
ture somewhere in between TR and Tc. These authors con-
sidered a well mixed batch reactor with a homogeneous,
single and irreversible, exothermic reaction A ! B, with
a rate given by r ¼ k(T)cAn . Assuming that the reaction
heat generated is removed only by cooling, they gave the
following operation equation, which can be easily derived
from the set of general mass and heat balance equations
after introducing dimensionless variables and parameters:
Le du að u  u c Þ
¼1 (5)
B dX Bð1  X Þn exp½u=1 þ u=g
It holds for the reactant conversion 0  X , 1 and after
integration with u ¼ 0 at X ¼ 0 gives the reaction paths
in the temperature-conversion plane. Particularly useful
can be an observation of the reactor temperature trajectory
at assumed operating conditions in relation to the adiabatic
trajectory. A typical plot is shown in Figure 2.
Because in many practical cases the adiabatic tempera-
ture is unacceptably high as the limiting temperature, Bala-
kotaiah et al. (1995) referred to the work of Adler and Enig
(1964) to have a sharp and realistic criterion for the preven-
tion of runaway. At some special conditions—i.e., for uc ¼
0 and g ¼ 1—the results are presented in an operating dia-
gram, in which the lines separating runaway and safe
regions are plotted in a plane with the coordinates a/B
and B/Le (see figure 2 in the cited paper).
Heiszwolf and Fortuin (1996) executed an experimental
study with a first order reaction and demonstrated that the
predictions of Adler and Enig (1964) are on the dot to pre-
dict for a certain set of operating and design conditions at
what reactant concentration in the feed a runaway will
occur in a batch reactor with a homogeneous reaction
mixture.
Figure 2. Temperature trajectories calculated with the operation equation
[Equation (5)] according to the criterion by Balakotaiah et al. (1995). Cal-
culations carried out at: Le ¼ 1, B ¼ 2, n ¼ 1, uc ¼ 0, g ¼ 20 for different
values of dimensionless external heat transfer coefficient a.
Trans IChemE, Part A, Chemical Engineering Research and Design, 2006, 84(A7): 543– 552
In general the batch reactor can be applied only for reac-
tions with a low adiabatic temperature rise. For more
exothermic reactions the semi-batch reactor is used, in
which one or more reactants are loaded into the reactor
and the balance of the recipe items are fed with a desired
mass rate profile (usually but not always linear with time)
over a defined period. Doing so, we can keep the heat evol-
ution by a very exothermic reaction in hand by the dosing
rate of the second reactant.
After the Seveso incident in 1976 much research was
started to understand what the real cause of the runaway
in a semi-batch reactor may have been. The authors Hugo
and Steinbach (1985, 1986) deserve the honour for the
observation that an accumulation of the dosed component
at too low reactor temperatures is the cause of the runaway
in homogeneous semi-batch reactors. They presented a line
in a diagram, which separates the region with a runaway
from the region with a smoothly operating semi-batch
reactor with only a small harmless accumulation of the
dosed reactant. They did so for modified Stanton numbers
of 5, 10 and 15, where this number reads as
St ¼ (U A tdos =V r cP ). They also determined empirically
from their calculations that—in their range of Stanton
numbers—in the boundary between the two regions the
Damköhler number Da ¼ kcBo tdos must be equal to or
higher than the modified Stanton number.
In their paper Hugo and Steinbach (1986) derived
empirical relations for the operating conditions in a homo-
geneous semi-batch reactor. They found that the thermal
reaction number B ¼p DTad =R TR2 ) must
(Effiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 2 be smaller than
the limit value B ¼ St þ 2G þ 1:2 , where G ¼ mA/m
is the ratio of the mass of the reactant A to the final mass
of the reactor content, which represents the volume
increase due to the dosage of the second reactant, and
that the coolant temperature must be higher than the
limit value Td, which can be found from the following
equation:
DaðTd Þ ¼ St (6)
Specially their last relation is very simple.
Hugo et al. (1988) studied the danger of a runaway after
an agitator breakdown, because after a breakdown the reac-
tion proceeds adiabatically. They demonstrate that the most
dangerous situation prevails if the breakdown occurs at the
moment of just reaching the stoichiometric dosage of the
second reactant, because at that condition the concen-
trations of the two reactants reach such values that the reac-
tion rate of a second order reaction just has its highest
value, that is the highest value of the product cA
cB.
They found that the final temperature of the adiabatic reac-
tion mixture will exhibit a minimum value as a function of
the reaction temperature chosen in a particular case, pro-
vided the value for B is larger than 2.
Steensma and Westerterp (1990, 1991) developed full
safety diagrams for the same range of cooling numbers
for heterogeneous liquid –liquid semi-batch reactions and
for reactions both in the dispersed phase as well as in the
continuous phase. They have studied slow reactions and
also fast reactions, where the mass transfer is enhanced
by the chemical reaction. They show that also for chemi-
cally enhanced reactions, where the supplied reactant is
 SAFETY AND RUNAWAY PREVENTION
already consumed in the film around the drops, still a
dangerous accumulation can occur in its own phase, caus-
ing a runaway.
In their safety diagrams they plotted the Reactivity, Ry,
as a function of the Exothermicity, Ex, and surrounded
the region of runaways by a boundary line. These dimen-
sionless groups are defined as:
DTad,o E=R
Ex ¼ 2
Tc ðRH þ U
Da=1Þ1
(nA =nB )mDac
Ry ¼
ðRH þ U
Da=1Þ1
Further regions with no accumulation, harmless reactions
and insufficient ignitions are distinguished. The boundary
diagrams (see Figure 3) depend on the value of the cooling
number—which is similar to the modified Stanton number
of Hugo and Steinbach (1986)—and on whether the reac-
tion takes place in the continuous phase or in the dispersed
phase in the reactor.
Van Woezik and Westerterp (2000, 2002) publish exper-
imental work on a very exothermic nitration reaction
system with consecutive reactions and with a secondary
heat effect, which is 3.25 times higher than that of the
desired reaction. They determined very accurately the kin-
etics of their consecutive reaction scheme. They also deter-
mined the interfacial areas in the reactor. They conclude
that the set of differential equations as used by Westerterp
and coworkers to describe the behaviour of such reactors
are confirmed accurately by their experiments. For safe
operation much higher Cooling numbers are required than
in the previous work (Steensma and Westerterp, 1990,
1991) and they introduce the concept of the inherently
safe operating region, in which the heat evolution is still
harmless and the accumulation of the dosed reactant
remains very small (see Figure 3).
Maestri and Rota (2005a and 2005b) calculate safety dia-
grams for kinetics different from those used by Hugo, Wes-
terterp and coworkers. The diagrams are influenced indeed
by a difference in kinetics, regretfully they do not discuss
when and where their kinetics occurs in practical semi-
batch reactor operations. Hugo (1990) determined that a
description by second order reaction always gives satisfac-
tory results, except for autocatalytic reactions. A special
Figure 3. Inherently safe operating conditions for slow reaction in the con-
tinuous phase.
Trans IChemE, Part A, Chemical Engineering Research and Design, 2006, 84(A7): 543 –552
547
caution about blindly applying of each safety criteria to
reactions that may be autocatalytic, is very important.
SAFE OPERATION OF (SEMI-)BATCH REACTORS
WITHOUT KINETIC INFORMATION
Gygax (1988, 1990) discusses in two concise papers the
available methods to determine the danger of runaways in
(7) batch and semi-batch reactors and how we can use chemi-
cal engineering principles to cope with these dangers.
Stoessel and Ubrich (2001) for homogeneous reactors
(8)
demonstrate how the operation of a semi-batch reactor
can be improved by modulating the feed rate to a semi-
batch reactor, proving that the reactor productivity can be
sharply increased. They also demonstrate how in their
case the appropriate information can be obtained with a
reaction calorimeter and without knowing the kinetics of
the reactions involved. They illustrate their method with
an example of a set of consecutive reactions.
Westerterp and Molga (2004a) demonstrate that the
Cooling number is the key parameter, that determines the
difference in behavior of the large scale, industrial reactor
and the laboratory reactor. The Cooling number is defined
as:
ðU AÞo tdos
Co ¼ (9)
1ðV rcP Þo
They indicate how this Co number must be determined
for laboratory reactors as well as for industrial reactors.
Further they elaborate on the concept of inherently safe
reactor operation and how this must be achieved in prac-
tice. See Figure 3 for the indication of the inherently safe
operation region in a safety diagram for a slow liquid –
liquid reaction in the continuous phase.
They determine the full range of values of Cooling num-
bers for all liquid – liquid reactors of all sizes in a laboratory
or in an industrial plant. They also determine the maximum
of the Exothermicity values below which, and the mini-
mum values of the Reactivity above which, never a run-
away can occur. They state that the necessary information
can be obtained in a few days in a laboratory in a reaction
calorimeter, provided the calorimeter is used in the
semi-batch mode. They argue that their method for
liquid –liquid reactions can be used for single as well as
for multiple reactions of any reaction scheme with the
exception of autocatalytic reactions. They also discuss
how incidents like agitator breakdown can be handled with-
out any danger of a runaway. The elaborated practical pro-
cedure to determine the inherently safe operating
conditions in semi-batch reactors is summarized in
Table 2 (Westerterp and Molga, 2004b). Westerterp and
Molga (2004a) in their paper give data on the practical
values of the dimensionless groups of the Reactivity, the
Exothermicity and the Cooling numbers for both laboratory
and industrial reactors. We should realize that laboratory
reactors usually have much higher Cooling numbers than
industrial reactors. Specially, for heterogeneous liquid –
liquid and gas – liquid reactions Cooling numbers necess-
arily are high in order to achieve good dispersions with
large interfacial areas. In order to simulate industrial
conditions often reaction calorimeters are equipped with
548 WESTERTERP and MOLGA

Table 2. Procedure for the determination of safe operating conditions

Method used to determine

Value (or group) determined In laboratory reactor In industrial reactor

I. The Exothermicity criterion for a single reaction

DTad,o Measured or calculated
E Measured in reaction calorimeter
or DSC
RH Calculated
1 Calculated
Co Measured (cooling curve for Measured (cooling curve for
originally loaded batch) originally loaded batch)
Ex Calculated as a function of tdos, and
at realistic Tc
Yield For Ex  Exmin check for the reactor
productivity at the chosen tdos

II. The Reactivity criterion for a single reaction

Co Measured (cooling curve for batch originally loaded)
Tta ¼ f (t) Calculated Calculated
RyQFS,min Calculated Calculated
Tc Tc,ind - see below Eq. T1

III. Multiple reactions

See original article. The following holds:
(a) for parallel reactions an apparent activation energy should be determined, then the procedure above can be directly applied;
(b) for consecutive reactions the following method should be applied:
Heat evolution curves Measured as a function of T
Yield Measured
Ex For the first reaction, the second reaction or for the sum of heat effects
E1/E2 Estimated
Ex criterion Calculated
RyQFS criterion Calculated Calculated
"  #
2
RTc,lab RyQFS, min ind
Tc,ind ¼ Tc,lab þ ln   (T1)
E RyQFS, min lab

stirrers with low agitation speeds to reduce the Cooling
numbers. This helps indeed for homogeneous reactions,
but is unacceptable for heterogeneous reactions leading to
phase separations.
EARLY WARNING DETECTION SYSTEMS
As has been mentioned before, even a correct choice of
reactor operating conditions does not totally protect the
plant against a thermal runaway. So, apart from the off-
line activities, which help to define safe operating
conditions, also on-line prevention measures are necessary
to detect any unexpected situation leading to a runaway
scenario (see Figure 4). Among others under the on-line
safety measures as listed in Figure 4, an early warning
detection system (EWDS) is indispensable to detect
and evaluate unexpected dangerous situations, which
may occur in batch and semibatch reactors e.g., due to a
failure of the cooling or stirring systems or to a human
mistake.
The development of an efficient and robust EWDS for
batch and semi-batch reactors is very difficult due to the
complexity of the processes carried out in such reactors
and their strongly nonlinear dynamics. The main problem
of a detection of dangerous situations in discontinuous
reactors is the fast recognition of deviations from safe
operation, because we must provide sufficient time for the
plant operator or an automatic protection system to take
appropriate protective countermeasures to stop a thermal
excursion. Such countermeasures may be a pressure
relief, full cooling or quenching (i.e., addition of inhibitor
or cold inert liquid as well as dumping of the reactor
content into a cold catch tank). At the same time to
avoid false alarms, a warning system must be able to pre-
cisely distinguish between dangerous and non-dangerous
reactor states. So, an essential element of any EWDS is
a robust safety criterion, which works on-line and is
practically independent of the actual process carried out
in the reactor.
Numerous criteria for the safe operation of batch and
semibatch reactions have been developed and can be
found in literature, some of them are discussed in this
paper in the sections above. The sensitivity towards the
initial and the operating parameters has been extensively
studied—(see Varma et al. 1999)— and a new series of
safety criteria based on parametric sensitivity has been
developed (e.g., see Morbidelli and Varma, 1986, 1988,
1989; Vajda and Rabitz, 1992; Shukla and Pushpavanam,
1994). Unfortunately, these criteria can not be used for an
on-line early warning detection of a runaway. A detailed
discussion of the applicability of the existing safety criteria
for an early detection system can be found in a series of

Trans IChemE, Part A, Chemical Engineering Research and Design, 2006, 84(A7): 543– 552
 SAFETY AND RUNAWAY PREVENTION
Figure 4. Prevention measures developed to avoid situations that may lead
to loss of thermal control and runaway scenario, see also Zaldivar (1991a)
as well as Westerterp and Molga (2004a).
papers by Strozzi and Zaldivar (e.g., see Strozzi et al.,
1999; Zaldivar et al., 2003). The general conclusion arising
from this analysis indicates that most of the existing safety
criteria can not be directly used for an EWDS, because
either they work off-line or they are model-based; so
expensive and time consuming kinetic studies are required,
which are seldom applied to processes carried out in batch
and semi-batch reactors.
A simple on-line safety criterion has been based on
measurements of the reactor and cooling jacket tempera-
tures and some their derivatives: for the recognition of a
dangerous situation it is enough to check the following
expressions (Hub and Jones, 1986):
d2 TR
.0 (10a)
dt2
and
dðTR  Tc Þ
.0 (10b)
dt
This criterion does not require any detailed information on
the process carried out in the reactor and it can be also
applied for the detection of thermal runaway in other equip-
ment, e.g., in storage tanks. Its main disadvantage is that
the noise, always measured in experimental signals, is
amplified and significantly affects the results of evalu-
ations, so false alarms may be triggered. A very useful dis-
cussion of practical tests of this method as well as the
results obtained is given by (Zaldivar, 1991b).
Strozzi and Zaldivar developed a new method for asses-
sing the thermal stability of batch and semibatch chemical
reactors (e.g., see Strozzi and Zaldivar, 1994a; Strozzi
et al., 1994b; Alos et al., 1996a,b). In their method the
Lyapunov exponents were used to calculate the sensitivity
and to formulate a new safety criterion. An essential advan-
tage of this method, in comparison to the previous ones, is
that it can be applied for on-line runaway detection. This
was made possible by applying a phase-space reconstruc-
tion technique and resulted in the fact that the divergence
of the system can be evaluated from the measurement of
one system variable only. The background of this method
Trans IChemE, Part A, Chemical Engineering Research and Design, 2006, 84(A7): 543 –552
549
can be found in the paper by Strozzi et al. (1999), while
further theoretical developments as well as practical appli-
cations and considerations are published in a series of
papers by Strozzi, Zaldivar and their coworkers, which
report on the results obtained in an EU funded project
AWARD (2001 – 2005) (see Zbilut et al., 2002; Bosch
et al., 2004c; Zaldivar et al., 2005, 2003; Bosch et al.,
2004 a, b, d), respectively. Based on the results of the
studies carried out within the frame of the AWARD
project, several prototypes of an Early Warning Detection
System for batch and semibatch reactors have been
produced (for details see AWARD, 2001 – 2005).
In the mentioned method a new runaway criterion has
been defined and the onset of loss of control has been ident-
ified at the point where the divergence of the reactor beha-
vior becomes positive on a segment of the reaction path:
div Fðu, X1 , X2   Þ . 0 (11)
The research group led by Strozzi and Zaldivar developed a
method to calculate the divergence on-line, using one
representative measurable variable of the system. State
reconstruction techniques and a theory of embedding
have been applied for this purpose. The method based on
a delayed temperature vector turned out as the most
robust one with respect to noised experimental data, but
also pressure measurements have been successfully tested
(e.g., see Bosch et al., 2004d and a). The divergence cri-
terion developed has been tested and successfully validated
for different types of reactors (batch, semibatch and CSTR),
different operating modes (isothermal, isoperibolic and
adiabatic) as well as for different schemes of reaction
kinetics—a.o. for simple and complex (parallel, consecu-
tive, mixed and equilibrium) reactions, homogenous liquid
and heterogeneous liquid –liquid reactions, polymerization
reactions and so on (see the references cited above).
Several methods employing the state reconstruction tech-
nique with use of one or more temperature sensors have
been developed and successfully tested for early detection
of runaway (see Bosch et al., 2004b; Zaldivar et al.,
2005). It has been found that for all considered batch and
semi-batch runs only one temperature sensor is usually suf-
ficient to reconstruct the divergence with a reasonably
accuracy, so to detect runaway.
The developed method of runaway detection, employing
only one temperature sensor, simplifies considerably an
application of the EWDS in industrial practice. In case of
one single temperature sensor we have to be sure that the
measured temperature is representative for the entire reac-
tor, i.e., that perfect mixing has been achieved. In case of
failure of the stirring system significant non-uniformities
of temperature and reactants concentrations inside the reac-
tor will occur, so a proper location of the required number
of the temperature sensors is essential. Computational fluid
dynamics (CFD) have been used to investigate this EWDS
method and to identify ‘hot-spots’ appearing in the reaction
mass (see Rudniak et al., 2004; Molga et al., 2004;
Milewska et al., 2005). The CFD models of stirred tank
reactors for bench and industrial scale reactors and also
for both homogeneous and heterogeneous reaction systems,
enable a determination of local and instantaneous values of
reactor temperatures and reactant concentrations in badly
mixed vessels.
550 WESTERTERP and MOLGA
In off-line applications the results from CFD simulations
can be directly converted into a spatial map of the local
divergence of the system so, a detection of local ‘hot
spots’ and their propagation into a global runaway may
be indicated. It can be particularly important for a so-
called ‘computer experimentation’, during which different
types of failures occurring in industrial reactors can be
safely investigated. However, it must be clearly distin-
guished, that for industrial reactors of complex geometry
local CFD predictions are difficult for experimental verifi-
cations, so the results of CFD simulations should be treated
as preliminary indications.
SUMMARY AND CONCLUSIONS
From statistical data, which report on the prime causes of
incidents in batch and semibatch chemical reactors carrying
out strongly exothermic reactions, the general conclusion
arises that a thermal runaway in these reactors is still a pro-
blem of great importance. So, a robust safety assessment is
always indispensable. Usually three lines of defense have
to be considered to prevent thermal runaways in chemical
reactors: choice of the right operating conditions, application
of early warning detection system and methods to handle
running away reactions. Because of its too specific nature,
the last line of defense was not discussed in this review,
while the former two have been considered in detail. The
choice of safe or inherently safe reactor operating conditions
is usually performed in an off-line analysis. Two main
approaches can be here distinguished: the model-based
analysis in which a detailed knowledge of the reaction kin-
etics is indispensable and the most recent approach based
on the boundary diagram, which is particularly useful for
the reacting systems with unknown reaction kinetics. In
the last approach, based on the work of Westerterp and his
collaborators which are published in the series of cited
papers, safety boundary diagrams are employed to dis-
tinguish the inherently safe operating conditions for batch
and semibatch reactors with liquid and liquid –liquid react-
ing systems, respectively. In these safety diagrams in a
plot of the coordinates Reactivity versus Exothermicity
numbers, runaway and non-runaway regions can be easily
distinguished (see Figure 3). In these safety diagrams the
boundary lines are still a function of the Cooling number.
The most relevant advantage of this approach is that even
for the case, when a detailed reaction kinetics is not know,
the problem of safety assessments can be tackled in a few
days with use of the reaction calorimeter.
Also the capability and applicability of the reaction calori-
meter for safety assessments have been reviewed. Several
applications, useful particularly for direct process safety
improvement as well as for supporting assessments based
on the use of boundary diagrams, have been indicated.
Due to a failure of the cooling/stirring systems or a
human mistake, different unexpected dangerous situations,
which can lead to a runaway scenario, may occur even in a
reactor operated along a safe trajectory. Taking into
account that even a correct choice of safe operating con-
ditions does not totally protect the reactor against a thermal
runaway, the recent developments of early warning detec-
tion system have been reported. Such a warning detection
system makes possible an early on-line prediction of the
reactor states, which may lead to the uncontrolled rise of
Trans IChemE, Part A, Chemical Engineering Research and Design, 2006, 84(A7): 543– 552
reactor temperature. In this area a very promising approach,
developed and tested by Zaldivar, Strozzi, Westerterp and
their collaborators, must be noticed. From this approach,
initially based on the divergence criterion and then sub-
jected to several modifications, a universal and robust
EWDS has been developed. In these transformations the
state space reconstruction has been employed, so the detec-
tion of runaway with the developed EWDS has become
possible by on-line measurement of one single operating
parameter such as the reactor temperature or the reactor
pressure, provided the latter can be considered as a variable
representing the state of the reactor.
The presented review can be concluded with the follow-
ing corroborations, which are particularly useful and sig-
nificant for the fine chemicals industry:
. Off-line safety assessments for batch and semibatch
reactors, to determine inherently safe operating
conditions, should be carried out on the basis of the
boundary diagram. This approach does not demand for
detailed kinetic investigations, only a few measurements
with a laboratory reaction calorimeter are needed.
. For on-line runaway detection in reactors operated
according to the state of the art, the EWDS system ela-
borated by Zaldivar, Strozzi and their collaborators
should be employed. It is a robust early warning detec-
tion system, for which only an on-line, single point
measurement of the reactor temperature (and/or the reac-
tor pressure) is needed.
NOMENCLATURE
A E DHcAo VRo heat exchange surface area, m2
B¼   dimensionless adiabatic
RTc mcp f Tc temperature rise
ci concentration of the ith
component, mol m23
cp mass specific heat capacity, J kg21
K21
Cp molar specific heat capacity, J
mol21K21
Co Cooling number, see equation (9)
for definition
Da ¼ kc cBotdos Damköhler number
E activation energy, J mol21
Ex exothermicity number, see equation
(7) for definition
k reaction rate constant, m3 mol21
s21
m mass, kg
m distribution coefficient (liquid–
liquid system)
n number of moles, reaction order
q heat flow, W
Q amount of energy, J
r reaction rate, mol m23 s21
R conversion rate, mol s21
R gas constant, J mol21 K21
RH ¼ (rcP )d =(rcP )c ratio of heat capacities of the
dispersed and the continuous phase
Ry reactivity number, see equation (8)
for definition
St ¼ UAtdos =V rCp modified Stanton number
tdos dosing time, s
T temperature, K
Tta ¼ Tc þ
1:05DTad,0
target temperature, K
1½RH þ Coð1 þ 1tÞ
U overall heat transfer coefficient,
W m22K21
 SAFETY AND RUNAWAY PREVENTION
U
¼ (U A)0/(r cP VR k cB)0 dimensionless cooling capacity
V volume, m3
X conversion
Greek symbols
UA dimensionless external heat transfer
a¼ n1
ðmcP Þf kðTc ÞcAo coefficient
g ¼ E=RTc dimensionless activation energy
DH reaction enthalpy, J mol21
DTad adiabatic temperature rise, K
1 relative volume increase
E T  Tc
u¼ dimensionless temperature
RTc Tc
n stoichiometric coefficient
t ¼ t=tdos dimensionless time
Subscripts
0 initial
c jacket, cooling, at cooling
temperature
f fluid (liquid reactor content)
F final
flow flow through the reactor wall
QFS quick onset, fair conversion, smooth
temperature profile
R reactor, reaction
w reactor walls and inserts (stirrer and
baffles)
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The manuscript was received 30 September 2005 and accepted for
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