J. Loss Prev. Process Ind. Vol. 10. No. 4. pp.

211-215, 1991
0 1997 Ekvier Science Ltd
All tights reserved. Printed in Great Britain
PII:SO!XO-4230(97)00004-1 095@4230/97 $17.00 + 0.00

Maximum temperature attainable by

runaway of synthesis reaction in semi-
batch processes*

Eduard Serra, Rosa Nomen and Julia Sempere

Institut Ouimic de SartiB, Universitat Ramon Llull, Via Augusta, 390, E-0801 7
Barcelona, Spain

A new scenario for the calculation of the adiabatic temperature increase for semi-batch pro-
cesses is presented. In the safety assessment of chemical reactions it is necessary to determine
the value of the Maximum Temperature attainable by runaway of the Synthesis Reaction for
the worst case. We demonstrate that the batch scenario is not always the most dangerous way
to carry out a reaction. In addition, an improvement in the calculation of the MTSR is presented
in order to obtain more realistic scenarios. 0 1997 Elsevier Science Ltd. All rights reserved

Keywords: MTSR; risk assessment; runaway scenario; semi-batch process; reaction calorimetry

Introduction value, solidification or precipitation of part of the

There are mainly two ways to carry out a reaction pro-
cess in Fine Chemistry: batch and semi-batch. In a batch
process, all the reactants are charged into the reactor at
room temperature and then the reaction mixture is
brought to the reaction temperature. In a semi-batch pro-
cess, one or more of the reactants are charged after the
initial reaction mass is already at reaction temperature.
In a safety assessment the level of risk of a chemi-
cal reaction depends on the relative values of five charac-
teristic parameters [ 11:
Process temperature, Tp,
Maximum Temperature attainable by runaway of the
Synthesis Reaction, MTSR.
Maximum Safe Temperature, MAXST. This is usu-
ally the temperature which the Time to Maximum
Rate of the decomposition is 24 or 8 h (TMRZ4 or
TMR,).
Boiling point of the reaction mixture, bp.
Minimum Safe Temperature [2], MINST. If the tem-
perature of the reaction mixture gets below that limit
*This paper has been presented partially in the 7th RCI Users
Forum, lnterlaken (Switzerland), October 1995 and in the 2nd
European Meeting on Chemical Industry and Environment,
Alghero (Italy), September 1996.
reaction mixture could occur. If a runaway reaction is
detected and a cooling medium with a temperature
lower than MINST is used to rapidly reduce the tem-
perature, solidification might occur on the heat
exchange area, thus reducing significantly the heat
transfer coefficient. In this case the heat transfer rate
is reduced dramatically, the reaction temperature
increases quickly and a runaway is inevitable.
Traditionally, it is considered, from the point of
view of the risk assessment of chemical reactions, that
the batch process is the most dangerous way to carry out
any reaction. We demonstrate here that this statement is
not always true.
In this paper we assume that the reaction heat
release is the heat due to the reaction evolution plus all
heats related to any physico-chemical phenomena: crys-
tallizations, dilutions, etc.
Adiabatic temperature increase
We study the consequences of a thermal runaway of an
exothermic reaction performed in a jacket-cooled reac-
tor. We examine the temperature increase from the
moment that the reacting mixture reaches adiabaticity as
a result of a failure of the cooling system, for instance.
The adiabatic temperature increase is first calculated, for

211
212 Maximum attainable temperature: E. Serra et al.

both batch and semi-batch processes, assuming that the

addition of all the reactants and the catalyst takes place
instantaneously at the beginning of the reaction [3,4].
Moreover we assume that it is not possible to remove I,-

A
‘I
the heat generated during the process. But, if the process ’I
/
is carried out in a semi-batch mode three different scen- ,
/
arios are considered depending on the dosing evolution /
after adiabaticity is attained: the batch scenario [3,4], if / / 4,
//
I
the addition of all reactants is instantaneous; the stop i/
, I
scenario [4] if the dosing is stopped immediately; and
I
the non stop scenario [2] if the dosing continues at its I

set rate after adiabaticity is reached. 0 1 2

For each case a method has been developed for the
t 1 ttolch.dos.
calculation of AtiT. The results are expressed as a func-
tion of the reaction time that the incident occurs, tad,The Figure 1 Ideal reaction heat release
maximum attainable value in each case is also presented.

Batch scenario
order to determine the accumulated heat, which is the
If the addition of the remaining reactant is instantaneous
most important factor in this scenario, we chose to nor-
at the moment that adiabaticity is reached, the adiabatic
malize the reaction time to the time in which the stoi-
temperature increase depends on the heat of reaction that
chiometric amount of reactant has been added according
has to be generated from this time. It is calculated as a
to equation (4).
function of time by equation (1).

We should point out here that the accumulated heat

The maximum value obtained for this function,
equation (2), is always at the beginning, when the total
heat of the process will be generated.
(2)
depends on the amount of reactants that can react and
not on the reactants added.
The adiabatic temperature increase, as a function of
time, according to this method is presented in equation
(5).

In these equations, because the addition is so fast,

the heat capacity of the reaction mass is taken to be equal
to the heat capacity of the final mixture at the end of
the reaction.
Stop scenario
It is necessary at this point to consider some important
aspects of this scenario. If the rate of the reaction is
orders of magnitude higher than the dosing rate, a rec-
tangular profile for the reaction heat release is
obtained-ideal reaction heat release, Qr,ideai*The value
of Qr,ia is calculated from equation (3) and is shown
in Figure 1.
(3)
It is worth mentioning that the length of this rec-
tangle on the dimensionless time axis is equal to 1,
which is the time that the quantity of the added reactant
has reached the stoichiometric proportion assuming that
only one reaction, the main reaction, takes place. In
The maximum of this function is usually at the time
of the stoichiometric addition, but nevertheless the
maximum value of this curve can be easily specified
because it depends on the kinetics of the reaction.
Non stop scenario
A third scenario, never considered before, results when
the dosing is not stopped after the adiabaticity is reached.
In that case the maximum possible heat is produced, but
is generated in an almost controlled rate by the addition.
The heat capacity of the reaction mass changes dur-
ing dosing because of two main reasons: (i) the changes
in the specific heat; (ii) the increase of the reaction mass.
The adiabatic temperature increase can be calculated by
equation (6).
(6)
 Maximum attainable temperature: E. Serra et al. 213

Table 1 Comparison between the values obtained applying the batch scenario and the non stop scenario

Case cpr.0 (J/kgK) cpr,f (J/kgK) m,,, (kg) &T(b) PC) A,,T(ns) PC) diff (%)

Al 2100 2100 1.1 86.6 90.7 4.76

A2 2100 2100 2 47.6 63.5 33.3
A3 2100 2100 3 31.7 47.6 50.0
Bl 2100 4200 1.1 43.3 59.5 37.5
B2 2100 4200 2 23.8 38.1 60.0
B3 2100 4200 3 15.8 27.2 71.4
Cl 4200 2100 1.1 86.6 61.4 - 29.0
c2 4200 2100 2 47.6 47.6 0.0
c3 4200 2100 3 31.7 38.1 20.0
mr.o = 1 kg heat of reaction = 200 kJ

The maximum of this function is always at the start- runaway of Synthesis Reaction, MTSR, of the studied
ing point of the addition. It can be calculated by equ- process.
ation (7).

Butch scenario with dosing improvement

1f.
QW
AJ’,Jmax) = JO
(W&)0 + (Wk)f
2 ment is applied in order to obtain a more realistic result
If the heat capacity of the reaction mixture increases
during the addition, the adiabatic temperature increase
in this scenario is always higher than the temperature
increase in the most common batch scenario. If the heat
capacity decreases, the temperature increase in the non
stop scenario can be lower or higher than the one in the
batch scenario depending on the dosed mass. In Table
I the results of theoretical calculations for nine different
cases are compared.
In Figure 2 the relative position of these values are
shown for each case. The batch scenario value is higher
than the non stop scenario value only in case Cl and
they are equal when the mass increase is compensated
by the heat capacity decrease (case C2).
After the adiabatic temperature increase has been
calculated by each method, the highest value is used to
calculate the real Maximum Temperature attainable by
In this scenario and the one that follows, an improve-
(7) ment for the calculation of the value of the adiabatic
temperature increase will be presented. This improve-
in this calculation. In the batch scenario, the heat
required to increase the temperature of the added reac-
tant to the temperature of the reaction mixture has not
been taken into account. Here we assume that the tem-
perature of the added reactant is lower than the reaction
temperature and as a consequence a part of the total heat
evolved by the reaction is consumed in order to increase
the temperature of the added reactant. After applying the
improvement resulting of this assumption, equations (1)
and (2) have to be replaced by equations (8) and (9).
AadTb,dos(max)
= (9)

If&(W
0
- P - Tdos)I
[mdoscpdos(T

Non stop scenario with dosing improvement

The same improvement has been applied in the case of
the non stop scenario. In this case the equations (6) and
(7) have been replaced by equations (10) and (11).

Al A2 A3 Bl 82 83 Cl C2 C3
Case

Figure2 Comparison between the values obtained applying

the batch scenario and the non stop scenario 2
214 Maximum attainable temperature: E. Serra et al.

Table 2 Amount of reactants

Reactant m (kg) tdos mol/mol B

A 1.067 3h 1.71
__end of dosing
B 0.700 initial 1

Table 3 Heat capacity values of the reaction mass

r cp, (J/kgK)

begin 1634 0 1 2 3 4 5
end 3805
fdl h

Figure4 Results of the application of the three scenarios.

MTSR vs fad

reaction. The curves presented in Figure 4 are obtained

Application
In order to show the differences in the values obtained
by each method we present a real process, that is more
complex than the example presented in Figure I. A
molar excess of 71% of reactant A is dosed into the
reactor where reactant B is at lOO”C, the process tem-
perature. The amounts of reactants are presented in
Table 2.
In Table 3 the heat capacity values at reaction tem-
perature, lOO’C, at the beginning and at the end of the
addition are presented. Its variation is assumed linear
with the addition.
In Figure 3 the real heat release of the reaction and
the associate ideal heat release profiles are presented.
The ideal heat release is calculated with a stoichiometric
dosing time of 105 min.
The integration of these curves gives a total heat of
1486 kJ/kg of B, which corresponds to the total heat of
------~
I ._____...___..-
I maximum temperature attainable by runaway of the syn-
150-, dr ides1
.’ dos
I I I.
from equations (l), (5), (6), (8) and (10). The maximum
values for each method and the respective values of
MTSR are presented in Table 4.
Just as it has been exposed, the non stop scenario
value is 71% higher than the value calculated assuming
a batch charge of the added reactant. If the dosing
improvement is taken into account, the obtained values
are 40°C and 69’C below for the batch scenario and for
rzon stop scenario, respectively. This application demon-
strates the big differences between these methods and
the importance of calculating the AadT using each
method. This importance becomes more obvious if the
results are used for the classification of the process
according to the relative values of the five parameters
presented. The values of these parameters for this rezic-
tion and the corresponding level of risk [I] are presented
in Table 5.
It is worth mentioning that changes in the assumed
scenario for the MTSR calculation change the resultant
level of risk of the process.
Conclusions
If the heat capacity of the reaction mixture at the end
of the reaction is higher than it is at the beginning, the
100
thesis reaction has a higher value in a lzon stop scenario
-80 than in the most usual batch scenario.
In consequence, it is very important for semi-batch
-60 8 processes to operate under a very good control of dosing.
.
$
w
-40
Table 4 MTSR values obtained by applying each method

-20 Scenario A,, T (“C) MTSR PC) t/t,

batch 156 256 0

-/ 0 stop 87 187. 0.58
0 1 2 3 4 5 non stop 267 367 0
batch, dos 116 216 0
t/h
non stop, dos 198 298 0
Figure 3 The experimental and the ideal reaction heat release
 Maximum attainable temperature: E. Serra et al. 215

notes documenraires, 144, 371-385 (3’ trimestre 1991). Securire’

l%ble 5 Classification of the process thermique des pro&dt% chimiques: 2. Prevention des &actions
secondaires de decomposition, INRS Cahiers de notes docu-
T, (“C) bp PC) MAXST (“C) MINST (“C) menraires, 145, l-25 (4’ trimestre 1991).

100 109 280 <o Nomenclature

bp: Boiling point of the reaction mixture, “C
Scenario MTSR PC) Level of risk Specific heat of the reaction mixture, J/kgK
cp,:
CPdor: Specific heat of the dosed reactant, J/kgK
batch 256 3 m,: Mass of reaction, kg
stop 187 3 ydOs: Mass of dosed reactant, kg
non stop 367 4 mdor: Dosing rate, kg/s
MAXST: Maximum safe temperature, “C
batch, dos 216 3 MINST: Minimum safe temperature, “C
non stop, dos 298 4 MTSR: Maximum Temperature attainable by runaway of
Synthesis Reaction, “C
Heat release of the reaction, W/kg
Ideal heat release, W/kg
Time of reaction, h
The dosing set should allow halting of the addition if Time of reaction which the reaction mass begins to
adiabatic conditions or another incident are detected. be in adiabatic conditions, h
Dosing time, h
If the scenarios with the dosing improvement are Time of reaction which the stoichiometric amount of
taken into account, more realistic scenarios are evalu- reactant has been dosed, h
ated. This has the benefit of avoiding refusal of good Tc,c,.: Dosed reactant temperature, “C
T,,: Process temperature, ‘C
processes that are near to the safety limit. TMR: Time to maximum rate of decomposition reaction, h
Normalized time of reaction adm
References :,,T: Adiabatic temperature increase, “C
0: Initial. At the beginning of dosing
Ill Stoessel, F., Chemical Engineering Progress, 68-75, Ott, 1993. f: Final. Time which the reaction is considered to be
PI Nomen, R., Sempere, J., Serra, E., II European Forum on Science completed
and Safety, Barcelona, 1994. b: Batch scenario
Dl Gygax, R., ISCRE! 10th. Chemical Enginering Science, 1988, 43, s: Stop scenario
1759-1771. ns: Non stop scenario
141 Gygax, R., translated by Riethmann, J. and Stoessel, F., Securiti b,dos: Batch scenario with dosing improvement
rhermique des prockdb chimiques: 1. Principes fondamentaux et ns,dos: Non stop scenario with dosing improvement
conception d’un pro&de’ thermiquement srir, INRS Cahiers de max: Maximum value