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Batch and Semibatch Reactor Performance For An Exothermic Reaction
Batch and Semibatch Reactor Performance For An Exothermic Reaction
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Abstract
In this work, a study of a batch and semibatch reactor has been carried out based on a very exothermic reaction between
thiosulfate and hydrogen peroxide. The experiments were carried out in a glass-jacketed reactor of 5 l, provided with different
sensors and a data acquisition system. Thermal and kinetic studies were carried out previously using an adiabatic batch reactor.
Then, these results have been used for experiments in semibatch mode of operation with heat transfer. Several experiments have
been carried out at different operating conditions (addition flow, initial temperature, initial concentration of reagents…). In batch
and adiabatic mode of operation, experimental measures of the reaction mass temperature provided concentration profiles of
reagents and products which have been compared to those determined by simulation. In semibatch mode of operation,
temperature profiles have also been simulated and validated with experimental results. An algorithm describing the mathematical
model has been developed and implemented in a software module written in FORTRAN 77 language. With this mathematical
model it has been possible to obtain concentration and heat profiles for the semibatch mode of operation. © 2000 Elsevier Science
S.A. All rights reserved.
1. Introduction concern.
Studies with adiabatic reactors have been reported by
Batch processes play a very important role in the several authors using the thiosulfate–peroxide reaction.
chemical process industry, being their main applications Most of them have studied the influence of different
in the production of specialty chemicals, polymers, or initial reagent concentrations, and started the reaction
bioproducts. These processes are characterized not only at 273 K, in order to obtain the kinetic equation in an
by small scale flexible production and high added value adiabatic batch reactor. For example Root and Schmitz
products, but also by reaction systems that may be [1] and Vetjasa and Schmitz [2] studied the reaction in
quite complex and not entirely known. For this reason, a batch reactor and used the data obtained for the
batch reactors are also very much used in studies of study of steady state multiplicity in a loop reactor and
reaction kinetics and thermal effects modelling. Semi- a stirred tank reactor (CSTR), respectively. Similar
batch mode of operation can be used to have a better work was made by Chang and Schmitz [3]. Guha et al.
control of the reaction, and is particularly important [4] reported also a study of transient behavior of an
for highly exothermic processes where safety is of high adiabatic CSTR.
On the other hand, Ausikaitis and Engel [5] and Lin
and Wu [6] studied the stability and performance of an
adiabatic controlled cycled stirred tank reactor
* Corresponding author. Tel.: +34-934016678; fax: +34- (CCTR). Also, Lo and Cholette [7] studied optimum
934017150. performance of an adiabatic MT reactor.
0255-2701/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 2 5 5 - 2 7 0 1 ( 9 9 ) 0 0 0 1 5 - X
142 M.D. Grau et al. / Chemical Engineering and Processing 39 (2000) 141–148
dcB
In this work, the method used is more similar to the = − 2·k·cA·cB (5)
dt
one presented by Cohen and Spencer [8]. As a previous
work [9], the kinetic equation can be derived from data dcP 1
= − ·k·cA·cB (6)
obtained in a series of runs in which the initial reagent dt 2
concentrations is held constant and the initial tempera-
ture is varied. Where, cP is the concentration of the products Na2S3O6
The objective of this work is to obtain the maximum and Na2SO4.
information about the reaction, by only measuring the The equation of Energy Balance is solely referred to
temperature of the mass reaction. The data of tempera- the reaction mass:
ture versus time obtained is used to determine the dT DHr·k·cA·cB
concentration evolution of reagents and products, rate =− (7)
dt r·Cp
of reaction, heat generated, etc. Then, the profiles ob-
tained experimentally are compared to those deter- It is possible to introduce a correction factor: (1 +o) in
mined by simulation. An algorithm describing the the denominator of Eq. (7) to take into account the
mathematical model (written in FORTRAN 77) has heat absorption effect of the reactor wall and stirrer.
been developed, using the thermodynamic and kinetic Lin and Wu [6] estimated o from the equation:
data obtained in the previous experiments. 2·rW·CPW·DrW
This information will be useful for the semibatch o= (8)
r·CP·rW
mode of operation, because of the exothermicity of the
reaction contemplated. Gygax [10] and Stoessel [11] In this work the ratio between the concentrations of
reported the importance of adiabatic determinations to reagents used is cA/cB = 2/3; therefore, H2O2 (B) is the
the study of potential runaway reactions. Hugo et al. limiting reagent.From Eqs. (5) and (7) it is obtained:
[12] determined the maximum temperature in a CSTR
DHr
and a SBR in case of breakdown of cooling and used dT= ·dc (9)
data obtained by adiabatic operation. 2·r·CP B
By integrating this equation, the following expression is
obtained:
2. The mathematical model
DHr
T− T0 = ·(c − cB0) (10)
For an adiabatic batch reactor the mathematical 2·r·CP B
model is made up by a set of differential equations Taking into account the relationship of cB with conver-
resulting from Mass and Energy Balances referred only sion Eq. (10) becomes:
to the reaction mixture, because there is not heat
transfer. DHr·cB0
T− T0 = − ·x (11)
The stoichiometry of the reaction studied is: 2·r·CP
Na2S2O3 + 2 H2O2 where the difference between initial and final tempera-
tures, when conversion is x= 1, is defined as DTad:
1/2 Na2S3O6 + 1/2 Na2SO4 +2 H2O
DHr·cB0
The kinetic equation is first order with respect to two DTad = − (12)
2·r·CP
reagents: Na2S2O3 (A) and H2O2 (B).
and Eq. (11) can be rewritten as:
r= k·cA·cB (1)
T= T0 + DTad·x (13)
Considering constant density conditions, the equations
Parameter DTad is very useful to determine Maximal
corresponding to the Mass Balance are:
Temperature attainable by runaway of the desired Syn-
Total Mass Balance:
thetic Reaction (MTSR). Also, DTad gives a method to
d(r·V) obtain DHr from Eq. (12).
(2) Eq. (13) allows one to find the conversion at any
dt
instant using only one measure of temperature. Then,
dV concentrations of the reagents and products can be
=0 (3)
dt found:
Component Mass Balance: 1
cA = cA0 − cB0·x· (14)
dcA 2
= − k·cA·cB (4)
dt cB = cB0·(1−x) (15)
M.D. Grau et al. / Chemical Engineering and Processing 39 (2000) 141–148 143
Run Initial temperature Final temperature −DHr(kJ Figs. 2 and 3 show the experimentally recorded tem-
(K) (K) kmol−1) perature versus time curve obtained for experiments (A)
and (B), respectively. With these measures it is possible
1A 288.37 317.76 5.722 E5
to determine all variables related in Eqs. (12)–(18).
2A 293.47 321.57 5.471 E5
3A 298.23 326.37 5.478 E5 As a previous work [9], the thermodynamic and
4A 307.12 335.08 5.443 E5 kinetic data are calculated. First, DHr is calculated from
1B 293.07 322.34 5.698 E5 Eq. (13), taking into account the correction factor of
2B 297.66 327.19 5.749 E5
Eq. (8). Thus, an estimated value of o= 0.0478 is ob-
3B 303.41 333.17 5.794 E5
4B 306.90 336.00 5.665 E5 tained. It is assumed that the density and heat capacity
of reacting fluids are the same as those of water. The
results of the calculation of DHr are indicated in Table
Table 2 1.
Arrhenius values of the bibliography
Most of the experiments (A) give values of DHr lower
Authors k0 (m3 kmol−1 s−1) Ea/R (K) than those of experiments (B). This can be due to the
different method used to carry out the mixing of the
Cohen and Spencer [8] 6.85 E11 9200 two reagents. Chang and Schmitz [3] and Lo and
Lo and Cholette [7] 2.13 E10 8238
Cholette [7] reported the importance of the type of the
Lin and Wu [6] 2.00 E10 8238
reagent employed and the ratio of the reagents’ concen-
tration. This also means the necessity to measure values
Table 3 of kinetic constants for our experiments.
Operation conditions for semibatch reactor
Table 4
Experiments with different addition temperature
Experiment F0×106 (m3 s−1) T0 (K) Fig. 2. Experimental temperature profiles for experiments A.
1 1.75 292.3
3 4.67 293.1
6 7.58 293.5
10 1.75 277.7
11 4.67 283.9
12 7.58 282.4
6. Conclusions
Fig. 13. Experimental and simulated temperature profiles for experi-
ments 1 and 6.
An adiabatic batch reactor has been modelled for a
very exothermic reaction between thiosulfate and hy-
drogen peroxide. Experimental results show a good
agreement with the results obtained by simulation. Sub-
stantial information has been obtained by measuring
only the variation of temperature inside the reactor.
The experimental results obtained in adiabatic opera-
tion have been very useful in work realised in semibatch
mode of operation using the same reaction. Because the
heat transfer is insufficient to remove heat generated by
reaction, in further work it will be interesting to control
the temperature of reaction by adding H2O2 with vari-
able and controlled flow, in order to study safety
aspects.
Fig. 14. Concentration profiles of reactants and products for experi- Acknowledgements
ments 1 and 6.
Financial support received from CIRIT is thankfully
acknowledged (Project QFN95-4702).
Appendix A. Nomenclature
r Rate of reaction kmol m−3 [2] S.A. Vetjasa, R.A. Schmitz, An experimental study of steady
s−1 state multiplicity and stability in an adiabatic stirred reactor,
rw Inside radius of reactor m AIChe J. 16 (3) (1970) 410 – 419.
R constant of gases kJ K−1 [3] M. Chang, R.A. Schmitz, An experimental study of oscillatory
states in a stirred reactor, Chem. Eng. Sci. 30 (1975) 21–34.
kmol−1
[4] B.K. Guha, G. Narsimhan, J.B. Agnew, An experimental study
t Time s of transient behaviour of an adiabatic continuous-flow stirred
T Reactor temperature K tank reactor, Ind. Eng. Chem. Process Des. Dev. 14 (2) (1975)
T0 Initial temperature K 146 – 152.
T0a Temperature of H2O2 added K [5] J. Ausikaitis, A.J. Engel, Steady state multiplicity and stability in
TH Delayed temperature K an adiabatic controlled cycled stirred tank reactor, AIChe J. 20
V Volume of reaction mass m3 (2) (1974) 256 – 262.
[6] K.F. Lin, L.L. Wu, Performance of an adiabatic controlled
x Conversion –
cycled stirred tank reactor, Chem. Eng. Sci. 36 (1981) 435–444.
DHr Heat of reaction kJ kmol−1 [7] S.N. Lo, A. Cholette, Experimental study on the optimum
DrW Thickness of the wall m performance of an adiabatic MT reactor, Can. J. Chem. Eng. 50
DTad Increment of adiabatic temper- K (1972) 71 – 80.
ature [8] W.C. Cohen, J.L. Spencer, Determination of chemical kinetics
o Correction factor – by calorimetry, Chem. Eng. Prog. 58 (12) (1962) 40 – 41.
r Density of reacting mass kg m−3 [9] M.D. Grau, L. Puigjaner, Internal report No. EUPM388, UPC,
1997.
rW Wall density kg m−3
[10] R. Gygax, Chemical reaction engineering for safety, Chem. Eng.
Sci. 43 (8) (1988) 1759 – 1771.
[11] F. Stoessel, Design thermally safe semibatch reactors, Chem.
References Eng. Progress, September (1995) 46 – 53.
[12] P. Hugo, J. Steinbach, F. Stoessel, Calculation of the maximum
[1] R.B. Root, R.A. Schmitz, An experimental study of steady state temperature in stirred tank reactors in case of breakdown of
multiplicity in a loop reactor, AIChe J. 15 (5) (1969) 670 – 679. cooling, Chem. Eng. Sci. 43 (8) (1988) 2147 – 2152.