Chemical Engineering Science 55 (2000) 291}302

On the simulation of stirred tank reactors via computational

#uid dynamics
Alberto Brucato *, Michele Ciofalo
, Franco Grisa" , Roberto Tocco 
Dipartimento di Ingegneria Chimica dei Processi e dei Materiali (DICPM), Universita% degli Studi di Palermo, Viale delle Scienze, 90128 Palermo, Italy

Dipartimento di Ingegneria Nucleare (DIN), Universita% degli Studi di Palermo, Viale delle Scienze, 90128 Palermo, Italy
Received 30 March 1999; accepted 1 April 1999

Abstract

Predictions of #ow "elds in a stirred tank reactor, obtained by computational #uid dynamics, were used for the simulation of
a mixing sensitive process consisting of two parallel reactions competing for a common reagent:
A#BPProd.1 A#CPProd.2.
Experimental data were obtained for A"OH\, B"Cu>> and C"ethyl-chloroacetate. For this reaction scheme the "nal

selectivity of the process, easily measured by a simple colorimetric analysis of the residual Cu>>, was found to depend on agitation
speed and therefore on the mixing history during the batch process. The #ow "eld-based three-dimensional simulations performed
here led to predictions that compared very well with the experimental data, though no adjustable parameters were used. Interestingly,
these encouraging results were obtained by modelling only the `macromixinga phenomenon, while `micromixinga phenomena were
neglected, i.e. the system was always considered as being locally perfectly micro-mixed. The good agreement found between simulation
predictions and experimental data retrospectively con"rms the negligibility of micromixing phenomena in the system investi-
gated.  1999 Elsevier Science Ltd. All rights reserved.

Keywords: Stirred tanks; Computational #uid dynamics; Macromixing; Micromixing; Parallel reactions

1. Introduction other hand, all these parameters may show considerable

Due to their importance in the "eld of process indus-
tries, mixing operations have been for decades the subject
of many investigations. In spite of these research e!orts,
many aspects of mixing processes are still to be properly
understood. As a consequence of this lack of knowledge,
considerable uncertainties, and associated losses of
money (Smith, 1990), are still involved in the set up of
full-scale mixing processes. This lack of design reliability
is partly due to the fact that so far most investigations
have attempted to set up correlations among spatially
averaged (`lumpeda) parameters, such as average tem-
perature and reagents concentration (perfect mixing as-
sumption), average power dissipation per unit volume,
average mass transfer coe$cients, and so on. On the
* Corresponding author. Tel.: #0039-091-6567216; fax: #0039-
091-6567280.
E-mail address: abrucato@dicpm.unipa.it (A. Brucato)
 Present address: SULZER Italia S.p.A., Milano, Italy.
gradients, which are strongly connected with the geo-
metry of the mixing tank and, in general, scale-up di!er-
ently for the various (often interacting) parameters of
interest. All these inhomogeneities are wiped o! by the
lumping process, which is therefore bound to lead to
uncertainties on the "nal result.
In order to avoid the limitations associated with the
lumping process, distributed parameter models, based on
the actual hydrodynamics of mixing tanks, should be
preferred. These require an accurate knowledge of local
properties of the #ow "eld in the mixer, i.e. a huge
amount of information that in practice cannot be ob-
tained from experimentation. The only viable way for
gathering the required information is through numerical
simulation of the relevant #ow "elds.
The simulation of three-dimensional #ow "elds is
a complex, computation-intensive task. However, the
never-ending decrease of computing costs and the conti-
nuing development of commercial codes for computa-
tional #uid dynamics (CFD) have prompted several

0009-2509/00/$ - see front matter  1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 9 9 ) 0 0 3 2 4 - 3
292 A. Brucato et al. / Chemical Engineering Science 55 (2000) 291}302
Nomenclature
Abs absorbance of solutions
A cell face surfaces, m
G G
C concentration, mol m\
c impeller clearance, m
CH reference initial ECA concentration, mol m\
C initial CuSO concentration, mol m\
 
C initial ethyl-chloroacetate concentration, mol m\
!
D impeller diameter, m
D turbulent di!usivity, m s\
2
H liquid height into the vessel, m
k kinetic constant of reaction (4), m mol\ s\

mr element of the `relation matrixa, s\
G
N agitation speed, s\
Q #ow rate, m s\
r reaction rate, mol m\ s\
studies aimed at its application to the case of mixing
tanks (see for example Brucato, Ciofalo, Grisa"
& Micale, 1998 and references therein). It can be stated in
general that the predicted #ow "elds show a reasonable
agreement with the experimental data, but quantitative
discrepancies can usually be observed (Daskopoulos
& Harris, 1996). These depend on the inadequacy of
the spatial resolution as well as of turbulence models, e.g.
on the hypothesis of isotropic turbulence implicitly as-
sumed by the commonly adopted `k}ea model (Ciofalo,
Brucato, Grisa" & Torraca, 1996).
Improvements in the accuracy of results are expected
from the "ner and "ner griddings of the computational
domain allowed by nowadays computers (Lee, Ng
& Yianneskis, 1996) and especially from the application
and tuning of more advanced turbulence models such as
RNG k}e, ASM, RSM and large eddy simulation (LES).
In the meantime, though the currently available #ow "eld
predictions are not entirely accurate yet, it is worth
starting to explore the potential of CFD-based simula-
tions of mixing sensitive processes. Among these, the
simulation of multiphase systems is still an area that
requires further developments of fundamental models
(Kuipers & Swaaij, 1997), while the simulation of homo-
geneous complex reaction schemes is probably the most
viable one at present.
In this last "eld relatively few works have appeared so
far. In the pioneering work by Middleton, Pierce and
Lynch (1986) not only CFD was used for the "rst time to
simulate the three-dimensional #ow "eld in a stirred
vessel, but the results were also used to simulate the
selectivity of a well-known parallel-consecutive reaction
scheme. The comparison of simulation results with ex-
perimental data was highly encouraging. Interestingly,
these results were obtained by taking into consideration
S mass source term, kg m\ s\
t time, s
¹ vessel diameter, m
u velocity components, m s\
; reference velocity (pDN), m s\
 
< cell volume, m
X selectivity of the reactive process towards reaction
(4) de"ned
> mass fraction
Greek symbols
*x distance between centroids of adjacent cells, m
C molecular viscosity, kg m\ s\
e turbulent energy dissipation rate, W kg\
k turbulent viscosity, kg m\ s\
2
o liquid density, kg m\
p turbulent Schmidt number
2
only the `macro-mixinga phenomena in the tank, though
the reaction pair employed practically coincided with
that used in a number of works aimed at characterising
`micro-mixinga phenomena (e.g. Rice & Baud, 1990;
Thorma, Ranade & Bourne, 1991; Baldyga & Bourne,
1992; Baldyga, Bourne & Hearn, 1997).
In the present work, CFD-based simulations of a dif-
ferent mixing sensitive reaction scheme are carried out
and compared with original experimental data. Both
simulations and experiment regarded the concentration
dynamics in a batch stirred reactor in which a pair of
parallel-competitive reactions takes place. This is a mix-
ing-sensitive reaction scheme which can be represented in
the following way:
A#BPProd. 1, (1)
A#CPProd. 2. (2)
If equimolar quantities of A, B and C are introduced in
a batch system, the "nal products distribution depends
on the kinetics of the two reactions and, if these are not
too slow with respect to mixing times, also on the mixing
history of the components.
Details on the experiments carried out are given "rst;
the #ow "eld prediction is then described, and the way in
which the information from such simulations was utilised
for carrying out process simulations is subsequently de-
tailed. Simulations results are "nally compared with the
experimental data obtained.
2. Experimental work
Experimental data were obtained in the 5.5 l vessel
(¹"0.19 m) illustrated in Fig. 1. It is a fully ba%ed tank,
 A. Brucato et al. / Chemical Engineering Science 55 (2000) 291}302 293

Fig. 1. Stirred vessel employed for the experimentation.

stirred by a Rushton turbine impeller (D/¹"0.5) driven

by a 500 W, speed controlled, DC motor.
This vessel was utilised in batch mode to run a mix-
ing-sensitive pair of reactions. The reaction pair chosen is Fig. 2. Validation of the kinetic model for reaction (4).
a modi"cation of that proposed by Baldyga and Bourne
(1990), and consists of the following two parallel-com-
may be stoichiometrically complex due to the stability of
petitive reactions:
over-hydroxylated ionic species (Cotton & Wilkinson,
NaOH#CuSO PCu(OH) #Na SO , (3) 1988). The reaction with Cu>> is not only stoichiometri-
      
cally simpler, but also the strong coloration of cupric ions
NaOH#ClCH COOCH CH PClCH COONa
    in water makes it possible to measure their concentration
#CH CH OH, (4) by simple colorimetry. The wavelength utilised to this
 
purpose was 800 nm; at this wavelength the absorbance
i.e. the precipitation of cupric hydroxide and the alkaline
of cupric ions shows a maximum, while the absorbance of
hydrolysis of ethyl-chloroacetate (ECA), both competing
all other species is zero, so that interference with the
for the NaOH added to the system.
cupric ions detection is avoided.
Both reactions are second order but the "rst one is
Preliminary calibration tests showed that a linear de-
much faster, having a kinetic constant which is about
pendence of absorbance on cupric ions concentration
nine orders of magnitude larger than the second one; this
exists in the concentration range of interest. Other pre-
implies that, to all practical purposes, the "rst reaction
liminary tests were performed in order to check the
can be considered as instantaneous with respect to the
negligibility of cupric over-hydroxylated species in the
second one.
solutions of interest, as well as the reliability of the whole
The value of the kinetic constant of reaction (4), at the
measurement technique. To this end the absorbance of
temperature of 203C, is 0.023 m mol\ s\ (Kirby,
the solutions obtained by subsequent additions of so-
1972). A preliminary run was conducted by carrying out
dium hydroxide to a cupric sulphate solution was mea-
only reaction (4). In this case the pH dynamics of an ECA
sured, after separation of the precipitated cupric
solution to which an equimolar amount of NaOH had
hydroxide. As a di!erence with similar attempts made
been suddenly added was recorded. The run was conduc-
with Fe> ions, these measurements resulted in a linear
ted in a small vigorously agitated beaker so that a perfect
plot of absorbance vs added sodium hydroxide, which
mixing assumption could be made with negligible errors.
agreed very well with that predicted on the base of the
In Fig. 2, the pH dynamics predicted by a second-order
stoichiometry of reaction (4) assuming a zero re#ectance
kinetics with the above value of the kinetic constant is
for all other species. The symmetric test consisting in
compared with that experimentally observed, and a good
subsequent additions of cupric sulphate to a solution of
agreement can be observed. The slight discrepancies ob-
sodium hydroxide gave rise to similar results.
servable at long times are in fact meaningless due to the
A typical experimental run consisted of the following
very small residual reagent concentrations. These results
steps:
validate both the second-order kinetics and the above
stated value for the kinetic constant, which were then (a) the reactor was half-"lled with distilled water;
retained in the following simulations. weighted amounts of copper sulphate and ethyl-chloro-
The reaction scheme adopted here di!ers slightly from acetate were then added and the vessel content was
that proposed by Baldyga and Bourne (1990), who used mixed until both reagents were completely dissolved. The
Fe> ions instead of Cu>>. The same authors recog- amounts of reagents were such that, when the system was
nised, however, that the reaction between Fe> and OH\ brought to the "nal volume, concentrations C "10.5

294 A. Brucato et al. / Chemical Engineering Science 55 (2000) 291}302
and C "21 mol m\ were obtained for CuSO and
! 
ECA, respectively.
(b) the vessel content was then brought to the desired
"nal volume by adding cold and/or warm distilled water,
in order to obtain the desired temperature of 203C. No
thermostatting was needed in practice, as each experi-
mental run was completed in a few tenths of seconds and
the "nal temperature was always found to be within
0.53C of the starting value;
(c) 20 ml of NaOH solution were suddenly introduced
by gently, yet rapidly, pouring the content of a small
beaker directly on the surface of the liquid, close to the
agitator shaft, in an angular position midway between
ba%es. The whole operation was completed in less than
a second; the amount of soda in the solution was to give an
average concentration of 21 mol m\ in the whole vessel;
(d) reactions were allowed to complete and a sample of
the reacted mixture was withdrawn. This was "rst centri-
fuged at 4000 rpm for 20 min in order to remove the cupric
hydroxide precipitate; the absorbance of the solution was
then measured in order to assess the amount of unreacted
cuprous ions. This last quantity actually coincides, apart
from a stoichiometric coe$cient of 2, with the amount of
NaOH reacted with the ethyl-chloroacetate;
(e) process selectivity towards reaction (4) was then
computed as the amount of NaOH reacted via reaction
(4), divided by the total amount of NaOH reacted. This
last quantity could easily be estimated on the basis of the
amount of unreacted Cu>>, as detailed in the following.
It is worth noting that contingent small overfeedings of
NaOH (reagent A) might give rise to signi"cant overes-
timations of the selectivity X, especially in the range of
small X values. In order to reduce the sensitivity of the
technique to such errors, a slight excess (2%) of CuSO
 the involvement, by turbulent dispersion, of further por-
with respect to NaOH was actually used, so that even if
the selectivity towards reaction (4) had been zero, a cer-
tain amount of Cu>> would have been left anyway in the
solution. This amount was checked by means of `blanka
reaction runs, which were performed exactly as the usual
runs, apart from the fact that no ethyl-chloroacetate was
added to the system. Indicating with Abs , Abs and
M @
Abs , respectively, the absorbances of the solution before
D It is clear that the "nal result of the process, namely its
the introduction of NaOH, at the end of the blank
experiment and at the end of a normal experiment, the
selectivity X of the process towards reaction (4) was
simply computed as
Prod. 2 Abs !Abs
X" " D @. (5)
Prod. 1#Prod. 2 Abs !Abs
M @
3. Experimental results
Experimental runs were performed at various agita-
tion speeds ranging from 60 to 240 rpm; higher agitation
speeds were not experimentally investigated because at
such speeds the surface aeration phenomenon becomes
important, and the consequent changes of the system
hydrodynamics cannot presently be properly accounted
for in CFD simulations. The initial concentrations of
NaOH and CuSO were always kept at their reference

values (21 and 10.5 mol/m\, respectively), while the in-
itial ECA concentration was either the reference one
(21 mol m\) or halved or doubled with respect to it. The
experimental data obtained in terms of X are reported in
Table 1 along with the relevant experimental conditions.
Observation of Table 1 shows that the selectivity of the
process towards reaction (4) increases while increasing
the initial ECA concentration, as it could be expected by
considering that in this case reaction (b) is increasingly
favoured. In all cases selectivity is of the order of 10\,
in agreement with literature results (Baldyga & Bourne,
1990; Baldyga, Bourne & Yang Yang, 1993; Bourne,
Gholap & Rewatkar, 1995; Baldyga et al., 1997). These
results can be compared with the values in the range of
10\ that would be predicted if the system was modelled
as being perfectly mixed. In other words, in the present
case the assumption of perfect mixing inside the tank
leads to results which are in error by several orders of
magnitude with respect to reality.
In order to understand this quite surprising result, one
should consider that when the concentrated A reagent
(NaOH) reaches any volume portion of the agitated
vessel, it reacts almost instantly with the relatively small
amount of reactant B (Cu>>) present there. As a conse-
quence reactant B suddenly disappears from that volume,
leaving a high concentration of A in contact with reac-
tant C (ethyl-chloroacetate) and therefore reaction (4) is
allowed to occur. The evolution of the process concerns
tions of the unreacted mixture of B and C formerly
introduced in the vessel, while the reacting plume is
carried across the vessel by convective #ows. During all
this time reagent B engulfed in the plume suddenly disap-
pears by reaction with A, but always leaving signi"cant
concentrations of A which is therefore allowed to further
react with C.
"nal selectivity, will depend on the whole history of the
mixing process and in turn on the characteristics of the
turbulent #ow "eld existing in the vessel. Observation of
Table 1
Experimental values of selectivity (X)
Agitation speed (rpm)
Initial ECA conc. (mol m\) 60 90 180 240
10.5 0.130
21 0.243 0.202 0.142 0.124
42 0.390 0.336 0.226 0.194
 A. Brucato et al. / Chemical Engineering Science 55 (2000) 291}302 295

Table 1 shows that the process is indeed mixing sensitive, model (Launder & Spalding, 1974) with standard values
as the selectivity decreases with the increase of agitation of model coe$cients.
speed. This is the expected trend if one considers that Due to periodicity considerations only one quarter of
increasing agitation speed means increasing mixing the tank was simulated. The grid employed is illustrated
rates and therefore getting closer to the perfect mixing in Fig. 3 and includes 49*30*30 (axial*radial*circum-
hypothesis. ferential) cells, a discretisation su$cient to obtain prac-
The amazingly high values of selectivity towards reac- tically grid-independent results (Brucato et al., 1998). As
tion (4) are therefore to be explained on the basis of the
concentration inhomogeneities existing at any instant
during the evolution of the process. Such concentration
inhomogeneities may exist over several length scales,
from vessel size down to molecular size. The related
unmixedness phenomena take di!erent names: `macro-
mixinga is the term employed when concentration di!er-
ences at the vessel scale are considered (i.e. from
centimetres to tens of centimetres for the vessel here
employed) while the term `micromixinga is usually em-
ployed to characterise concentration variations at the
scale of Kolmogoro! eddies (usually in the range of tens
of microns) down to molecular scale (Baldyga et al.,
1997). The term `mesomixinga has also been introduced
(Baldyga & Bourne, 1992) to characterise concentration
variations at intermediate scales (here millimetres to cen-
timetres). In the present case concentration gradients at
all of these scales might in principle be signi"cant and
therefore a!ect the "nal results. Interestingly, the same
reaction pair was used in the past to validate micromix-
ing models as well as mesomixing model (Baldyga &
Bourne, 1990; Baldyga et al., 1993; Bourne et al., 1995;
Baldyga et al., 1997). Macromixing was not taken into
consideration in these works, probably due to the di$-
culties involved in properly accounting for such e!ects.
However, concentration gradients certainly exist at the
vessel scale during the whole process evolution. For
instance, when X"0.1, 90% of the initially uniformly
distributed B reactant has to come into physical contact
with A, implying that at least 90% of the vessel content
has to mix with the concentrated A-solution before the
reactive process ends. This also clearly involves concen-
tration histories on the whole vessel scale, and not only in
the proximity of the injection point.
In the present work an attempt was made to explicitly
take into account the complete mixing history in the
vessel in order to verify how much of the "nal result obs-
erved is to be related to the macroscale inhomogeneities
and how much is to be attributed to unmixedness at
smaller scales.

4. Flow 5eld simulation

The CFDS-FLOW3D code (release 2.3) was used to

simulate the #ow "eld in the tank. This computer code
makes use of a "nite volume method to solve the time-
averaged Navier}Stokes equations. The turbulent stres-
ses were modelled using the well-known k}e turbulence Fig. 3. Computational grid employed for the simulations.
296 A. Brucato et al. / Chemical Engineering Science 55 (2000) 291}302
regards the simulation of the impeller, it was obtained by
imposing on the cylindrical surface swept by impeller tips
experimental values of velocity, turbulent energy and
dissipation rate. The values utilised to this purpose were
extrapolated from published experimental LDA data
(Wu & Patterson, 1989).
The `hybrid di!erencing schemea (HDS) was em-
ployed for the convective terms and the #ow equations
were coupled using the SIMPLEC algorithm (Van Door-
mal & Raithby, 1984), with under-relaxation factors set
at 0.3 and 0.4 for velocities and turbulence quantities,
respectively. 2000 SIMPLEC iterations were performed
in order to ensure a high degree of convergence. This
required a CPU time of about 6 h on the HP712 work-
station employed.
For each cell, the output of the CFD simulation in-
cludes the values of mean velocity (;), pressure (p), turbu-
lent kinetic energy (k) and dissipation rate (e) at cell
centroids. For the subsequent process simulations, how-
ever, the only relevant quantities are the convective #ow
Fig. 4. Predicted vector plots (N"90 rpm): (a) plane midway between ba%es; (b) plane immediately in front of ba%es.
rates on each of the six faces of a cell, which are inter-
polated from the velocities at cell centroids, and the
turbulent, or eddy, viscosity (k "C ok/e), from which
R I
turbulent di!usivities can be deduced by means of turbu-
lent Schmidt numbers. In fact, convective and di!usive
#uxes for a generic passive scalar (e.g. chemical species)
can be computed from the above quantities.
Typical results of these CFD simulations are shown in
Fig. 4, where velocity vector plots on signi"cant planes
have been reported (the dots indicate the centroids of
cells and are the starting points of each vector). It can be
observed that the general #ow patterns agree quite well
with published experimental information and the posi-
tion of the circulation loci on the plane located midway
between consecutive ba%es (Fig. 4a) is realistic. More-
over, the simulation predicts a displacement of circula-
tion loci towards the impeller (Fig. 4b) as one moves to
vertical planes closer to the ba%e planes; a feature that
has been experimentally observed (Costes & Couderc,
1989). On the other hand, it is worth mentioning that in
 A. Brucato et al. / Chemical Engineering Science 55 (2000) 291}302
general the agreement of simulations with experimental
#ow "elds is not completely quantitative yet, probably
due to the simpli"cations introduced by the turbulence
model (Ciofalo et al., 1996).
The physical properties of the #uid were always as-
sumed to coincide with those of pure water. It was
considered, in fact, that the minor e!ects on the #ow "eld
due to the small density and viscosity changes caused by
the presence of reactants and products (including the
solid precipitate) were negligible in comparison with the
other approximations.
5. Process simulation
In principle, the #uid dynamic information obtained
from CFD computations might allow the modelling of
both macro and micromixing phenomena. In practice,
macromixing phenomena are dealt with more easily as
the information made available by such computations
(#uid velocities and turbulence intensity) is su$cient for
the solution of local mass balances and almost no addi-
tional modelling is required. On the contrary, the simula-
tion of micromixing phenomena requires subgrid models,
which are still a research area (Kuipers & Swaaij, 1997).
In this work only macromixing phenomena are ac-
counted for, while micromixing phenomena have been
neglected. In other words, the agitated system was con-
sidered as being, at any instant, well micromixed and
poorly macromixed. This was considered as a "rst ap-
proach to the problem and was prompted by the pre-
viously mentioned consideration that, if a reacting
system is prone to be a!ected by micromixing phe-
nomena, macroscale inhomogeneities are bound to occur
as well, so that macromixing phenomena will always
have to be simultaneously dealt with. A separate treat-
ment for `mesomixinga modelling is not required with
the present approach, as the #uid dynamic discretisation
can be made "ne enough fully to account for the concen-
tration gradients at mesomixing scales. In the following
the term `macromixinga will be meant as inclusive of
`mesomixinga phenomena.
As far as macromixing is concerned, once the informa-
tion on local values of mean velocity components and
turbulence intensity has been generated, the following
advection-dispersion equation has to be solved for each
of the species participating in the reaction processes:
*o>
G#
) +oU> !(C #D )
> ,"S , (6)
*t G G 2 G G the same species in the adjacent cell identi"ed by the
where U is the velocity vector, while indexed quantities
refer to the generic species `ia: > is the mass fraction, S is
G G
the source term due to the chemical reaction, C and
G G
D are, respectively, the molecular and eddy di!usivities.
2
D is computed as the ratio between the turbulent kin-
2
297
ematic viscosity k /o and the turbulent Schmidt number
2
p , for which a value of 0.8 was adopted for all species
2
(Yakhot, Orszag & Yakhot, 1987). The molecular di!us-
ivity can be neglected in comparison with the eddy di!us-
ivity for highly turbulent #ows, as usually are those
involving stirred low-viscosity liquids.
Facilities to solve a number of such equations are
included in most commercial CFD codes, including
CFDS-FLOW3D. In the present work, however, the
choice was made of solving the set of Eq. (6) by means of
a purposely written post processing code. In this way the
#uid dynamic simulation could be limited to one quarter
of the tank volume, as previously detailed, while, due to
the point injection method used in the experiments and the
consequent loss of periodicity of concentration "elds, Eq.
(6) had to be solved in the whole vessel volume. More-
over, by using a post processing program it was possible
to preserve full control of the computation, an especially
worthy feature for model development purposes.
In order to discretise Eq. (6), one can consider the
vessel volume as split into many lumped cells, which are
interconnected by known convective and turbulent-dif-
fusive #uxes. This information allows the solution of
the time-dependent mass and energy balances in each
cell. In this way, it is virtually possible to simulate any
physicochemical process, provided that all relevant ki-
netics are known and that its evolution does not signi"-
cantly a!ect the #uid-dynamic behaviour of the #uid
phase. The hypothesis implicitly made is, in fact, that the
process evolution does not a!ect the #ow "eld in the tank
(passive scalar assumption).
The way in which Eq. (6) were discretised is now
detailed. Considering a generic cell (i, j, k) in the vessel
volume, its faces can be numbered according to Fig. 5.
A discretised mass balance equation for each chemical
species can therefore be written as
dC 
< " (Q ) C ) (Q '0)#Q ) C ) (Q (0))
dt G G G G G
G
 (C !C)
# AD G #r ) <, (7)
G 2 *x
G G
where the "rst sum on the RHS represents the convective
exchange, the second sum is the turbulent-di!usion term
and the last term is the generation rate due to chemical
reaction; < is the volume of the cell on which the mass
balance is being carried out; C and r are, respectively, the
concentration and the reaction rate of the species under
consideration in the same cell; C is the concentration of
G
subscript i according to Fig. 5; Q is the time-averaged
G
convective #ow through the ith cell face, with a positive
sign for convective #ows entering into the cell and
a negative sign in the opposite case; A is the area of face i;
the logical operations which appear in the "rst term
result into one (1) if the test clause is satis"ed, while the
298 A. Brucato et al. / Chemical Engineering Science 55 (2000) 291}302

mr "A /<[u (u '0)#D /*x ],

    R 
mr "A /<[u (u '0)#D /*x ],
    R 


 
mr "1/< ) !u A (u '0)# u A (u (0)
 G G G G G G
G G
!D A /*x !D A /*x
R   R  
!D A /*x !D A /*x !D A /*x
R   R   R  
!D A /*x
R   

"! mr
G
G
The mr 's terms depend only on #uid dynamics in-
G
formation; therefore they do not change in time during
process simulation, provided that also the #ow "eld does
Fig. 5. Connection scheme for the generic cell: each face bears the index not change. Therefore, they can be evaluated once for all
of the adjacent cell.
at the beginning of the process simulation and stored in
a four-dimension `relation's matrixa mr(i, j, k, l) where
the "rst three indexes identify the cell on which the mass
result is zero (0) in the other case. This expresses the fact balance is being computed while the fourth, ranging from
that, if the convective #ow rate on the i-face is entering 0 to 6, identi"es the six neighbouring cell, with the zero
into the cell (Q '0), then the contribution of this term to index indicating the considered cell itself. Once the rela-
G
the accumulation rate of the species under consideration tion's matrix has been computed and stored, the time
is given by C *Q , where C is the concentration in the cell derivatives of all concentrations can be computed
G G G
adjacent to the i-face. On the other hand, if the convective straightforwardly by means of Eq. (8).
#ow rate is leaving the cell (Q (0) then the above A simple explicit technique, namely the Heun method
G
contribution is negative and given by C*Q ; *x is the (Chapra & Canale, 1989), was used for the numerical
G G
distance between the centroids of the considered cell and solution of the mass balance di!erential (8). This method
of the ith adjacent one; D is the eddy di!usivity at each allows an (over)estimation of the error made at each in-
2
face; in the present case, for all species, a value of 0.8 was tegration step, so that the adoption of an adaptive time
assumed for the turbulent Schmidt number. As the CFD step is possible, a feature that was utilised here.
code employed computes turbulent viscosity at cell cen- In the present case the "rst reaction is extremely fast
troids rather than at cell faces, for each face of the control with respect to the second, so that resolving the actual
volume the relevant value was obtained by linear inter- time dynamics for both reactions would result in a sti!
polation from values at cell centroids; r is a generation set of equations. This problem was overcome simply by
term due to chemical reactions and it is a function of assuming the "rst reaction to be instantaneous with
species concentration in the cell under consideration. respect to the second one, a reasonable assumption in
Such an equation can be written for each chemical view of the large di!erence between the two kinetic con-
component and for each cell of the agitated volume. To stants. In practice, this means that after the convective
compute the concentration dynamics of all components and turbulent contributions to the concentration levels in
in each cell, it is then necessary to solve this set of linear each cell had been computed, concentrations in each cell
ordinary di!erential equations (ODE). were updated by letting the "rst reaction occur up to
In order to speed up the numerical solution of the complete consumption of the limiting reactant before
ODEs set, Eq. (1) may be rewritten as subtracting the sink terms due to the second reaction.
This `instantaneous treatmenta was obviously performed
dC 
" mr ) C #mr ) C#r (8) at each of the two steps involved in the Heun method for
dt G G 
G every time increment.
where: As regards the injection modelling, it was assumed that
the exact amount of NaOH suddenly appeared in the cell
mr "A /<[!u (u (0)#D /*x ],
    R  corresponding to the actual injection point. Though the
mr "A /<[!u (u (0)#D /*x ], real injection was not instantaneous, it took less than
    R 
a second and it was checked that simulating a continuous
mr "A /<[!u (u (0)#D /*x ],
    R  injection over a few seconds did not signi"cantly a!ect
mr "A /<[u (u '0)#D /*x ], the results.
    R 
 A. Brucato et al. / Chemical Engineering Science 55 (2000) 291}302 299

As described above, the process simulations made use

of the #ow "eld (velocities and eddy viscosities) computed
by CFDS-FLOW3D. Each process simulation was stop-
ped when the entire amount of reactant A (NaOH) had
been consumed by the reaction. The reaction time varied
from 2.5 to 12 s, depending on agitation speed and initial
ECA concentration. In all runs the overall mole balance
was successfully checked. The CPU time required for
each run was of the order of 10 h on the HP-712 worksta-
tion utilised.

6. Simulation results and discussion

Several simulations of the reactive process under in-

vestigation were carried out, covering the experimental
range of values of reactant concentrations and agitation Fig. 6. Selectivity towards reaction (4). Experimental data: (䊏)
speeds. C "21; (䉱) C "42 (mol m\) Simulations results: ***
! !
The simulation results obtained are shown as lines in C "21; - - - - - C "42 (mol m).
! !
Fig. 6, where the experimental data have been reported as
symbols for comparison purposes. A satisfactory agree-
ment between simulation results and experimental data
can be observed. Not only the order of magnitude of the
selectivity is well predicted, but even the actual values in
many cases do practically coincide with experimental
data. Also the trends with both agitation speed and ECA
concentration appear to be well predicted.
The agreement tends to worsen at the highest agitation
speeds and ECA concentrations, where selectivities are
slightly overpredicted, which implies some underestima-
tion of mixing intensity. This behaviour cannot be ex-
plained by the fact that micromixing phenomena were
neglected, as their inclusion in any form would have
resulted in a poorer mixing and therefore in a more or
less pronounced increase of predicted selectivities. Nor
can it be explained by the fact that an instantaneous in-
jection was simulated though the real injection extended
over a "nite length of time, since simulations performed Fig. 7. Selectivity towards reaction (4) vs initial ECA concentration.
by spreading the injection over a few seconds (a feature
allowed by the process simulation procedure) did not
result in signi"cantly di!erent "nal selectivity predic-
tions. Probably the observed discrepancies, which are not data were used, so that the simulations performed can be
particularly important in view of the several orders of regarded as being fully predictive.
magnitude already recovered over the perfect mixing It is interesting to compare the above results with
assumption, are somehow due to shortcomings in the previous work (Baldyga & Bourne, 1990) in which prac-
simulated #ow "elds. tically the same reaction scheme and tank geometry was
In Fig. 7 the predicted trend of selectivity vs initial adopted in order to validate micromixing models, on the
ECA concentration for runs conducted at an agitation basis of the assumption that only microscopic concentra-
speed of 90 rpm is compared with the experimentally tion gradients a!ected the observed results. The agree-
observed trend. As can be seen, the predictions obtained ment of model predictions with experimental data was
by computer simulations are again in very good agree- optimised by tuning model parameters, namely the speci-
ment with experimental data. "c energy dissipation in the reaction volume. In sub-
The noticeable agreement between predicted and ex- sequent papers (Baldyga et al., 1993; Bourne et al., 1995;
perimental data is an especially interesting result no Baldyga et al., 1997) it was recognised that in the case of
adjustable parameters were employed for the simula- instantaneous common reagent injections, mesomixing
tions: only published literature kinetic and anemometric may play a signi"cant, though not exclusive, role.
300 A. Brucato et al. / Chemical Engineering Science 55 (2000) 291}302

It is clear that in the simulations performed here the
mesomixing phenomena are probably resolved together
with macromixing phenomena, but no account whatso-
ever is given of micromixing phenomena. The good
agreement obtained between predicted and experimental
results can therefore be regarded as a proof that only
meso- and macro-scale phenomena are actually impor-
tant in the present case and that CFD techniques are an
e!ective tool for properly accounting for such phe-
nomena. Interestingly, practically the same result was
obtained by Middleton et al. (1986) with a well-known
parallel-consecutive reaction scheme, which has been
widely adopted to validate micromixing models (Rice
& Baud, 1990; Thorma et al., 1991; Baldyga & Bourne,
1992; Baldyga et al., 1997).
In order to illustrate the spatial features of concentra-
tion dynamics for the system under investigation, in
Fig. 8 the time evolution of an `iso-surfacea at constant
Cu>> concentration of 0.021 mol m\ has been re-
ported. The concentration level chosen corresponds to
 of the initial, uniformly spread, Cu>> concentration

and therefore the surfaces reported in Fig. 8 can be
regarded as subdividing the vessel volume in a NaOH
rich `reaction zonea (inside the iso-surfaces) where Cu>>
has already been completely depleted and only reaction
2 is taking place, and a Cu>> rich region where no
NaOH can be present and no reaction is taking place. At
any instant the fast reaction 1 is taking place in a narrow
layer just about the iso-surfaces shown.
It can be observed that after 4 s from the start a fairly
large portion of the vessel region above the impeller
plane is involved in the reaction, while the vessel re-
gion below the impeller is practically never interested.
Clearly the process involves macro-scale inhomogeneities

Fig. 8. Concentration dynamics of Cu>> for the case N"90 rpm, C "21 mol m\. The iso-surfaces shown embed the reactor volume where the

Cu>> has been completely depleted and only the slower reaction (4) is taking place.
 A. Brucato et al. / Chemical Engineering Science 55 (2000) 291}302
connected with the whole mixing history of the
reactants.
By looking at Fig. 8, one may wonder whether a simple
model based on the subdivision of the vessel volume in
just two well-mixed zones, one above and the other
below the impeller plane, may be su$cient for the simula-
tion of the present system. With such an approach the full
predictivity of the CFD-based approach would be lost,
due to the need to estimate a proper inter-exchange rate
parameter. It should be noted, however that, though after
4 s the reaction zone is fairly wide, by no means it in-
cludes the whole upper region of the vessel. Also, at this
point almost 95% of the NaOH initially added has
already reacted (it was 55% after 2 s) and from now on
the reaction zone tends to shrink until it completely
disappears shortly after 7 s. If one also considers that the
instantaneous selectivity X tends to decrease as time
elapses (in the present case it is about 0.24 after 0.5 s and
slowly decays towards its "nal value of 0.20) it is clear
that the simpler model based on the segregation between
the upper and lower vessel regions would miss most of
the phenomena actually occurring in the tank.
The present results indicate that the signi"cance of
micromixing phenomena is probably less widespread than
is often assumed, but by no means they rule away the
possibility that micromixing phenomena may be impor-
tant in many practical situations. They only prove that for
the reaction process investigated here, in the case of
instantaneous injection of the common reactant, micro-
mixing does not seem to play any role. Had reaction 2
been signi"cantly faster, the conclusions might well have
been di!erent. Even with the same reaction process, in
the case of su$ciently slow common reactant injections,
micromixing may well start playing a signi"cant role.
In any case, since it is unlikely to deal with systems that
are well macromixed and poorly micromixed, macromix-
ing phenomena should always be properly accounted
for in simulations, and CFD tools appear to be well
suited for such a purpose. Micromixing phenomena
should be dealt with by means of sub-grid models
superimposed on macromixing CFD-based simulations,
as done for instance by Pipino and Fox (1994) for a
tubular jet reactor. This would be needed only for those
cases in which the simple macromixing simulation
failed to yield a satisfactory agreement with experimental
observations.
Notably, the e!ect of superimposing subgrid models
on a CFD-based macromixing simulation was also inves-
tigated by Harris, Roekaerts and Rosendal (1996), for
a more complex reaction scheme and a cylindrical jet-
stirred reactor. Both a probability density function
(PDF) model and an extended eddy break-up (EBU#)
model were tested. The authors found, however, that
results provided by simple macromixing modelling were
satisfactory on their own, and practically una!ected by
the inclusion of subgrid modelling.
301
Finally, the fact that some mixing-sensitive reaction
processes appear to be properly dealt with by CFD-
based simulations despite the still enduring inaccuracies
in the simulated #ow "elds, may be explained by the
consideration that such inaccuracies might have opposite
e!ects in the various reactor regions involved in the
reaction process. In such a case, the predicted "nal selec-
tivity would not be strongly a!ected by local #ow "eld
inaccuracies. It is certainly worth, however, pursuing
further improvements in the accuracy of the #ow "eld
simulations, in order to prevent the applicability range
of CFD-based simulations from being a!ected by such
uncertainties.
7. Conclusions
Fully predictive CFD-based simulations of a parallel-
competitive, mixing-sensitive reaction scheme were car-
ried out. Simulation results were compared with original
experimental data obtained in a standard stirred reactor,
and a good agreement between the two was found, lead-
ing to the conclusion that CFD is a powerful tool for
modelling mixing sensitive processes.
These encouraging results were obtained without giv-
ing any consideration to micromixing phenomena,
though a very similar reaction scheme has been used in
the past to validate micromixing models. This observa-
tion implies that micromixing phenomena were actually
negligible in the investigated system. This is likely to be
the case also for another reaction scheme commonly
employed for micromixing models development and vali-
dation, when instantaneous injections of the concen-
trated reactant are involved.
As macroscale inhomogeneities can now be e!ectively
dealt with by means of CFD tools, they should never be
neglected. For cases where results cannot be explained in
terms of macroscopic inhomogeneities, micromixing
models should be coupled, as sub-grid models, to the
CFD-derived macromixing frame. In this case the para-
meters involved in micromixing modelling could prob-
ably be related to the local values of turbulence
parameters, such as the speci"c energy dissipation rate,
which are provided by the same CFD simulation.
Acknowledgements
The authors wish to thank AEA Technology for pro-
viding CFDS-Flow3D (now CFX4) under a special li-
cence arrangement.
References
Baldyga, J., & Bourne, J. R. (1990). The e!ect of micromixing on parallel
reactions. Chemical Engineering Science, 45, 907}916.
302 A. Brucato et al. / Chemical Engineering Science 55 (2000) 291}302
Baldyga, J., & Bourne, J. R. (1992). Interaction between mixing on
various scales in stirred tank reactors. Chemical Engineering Science,
47, 1839}1848.
Baldyga, J., Bourne, J. R., & Yang Yang (1993). In#uence of feed pipe
diameter on mesomixing in stirred tank reactors. Chemical Engin-
eering Science, 48, 3383}3390.
Baldyga, J., Bourne, J. R., & Hearn, S. J. (1997). Interaction between
chemical reactions and mixing on various scales. Chemical Engin-
eering Science, 52, 457}466.
Bourne, J. R., Gholap, R. V., & Rewatkar, V. B. (1995). The in#uence of
viscosity on the product distribution of parallel reactions. Chemical
Engineering Journal, 58, 15}20.
Brucato, A., Ciofalo, M., Grisa", F., & Micale, G. (1998). Numerical
prediction of #ow "elds in ba%ed stirred vessels: a comparison of
alternative modelling approaches. Chemical Engineering Science, 53,
3653}3684.
Chapra, S. C., & Canale, R. P. (1989). Numerical methods for engineers.
New York: McGraw Hill.
Ciofalo, M., Brucato, A., Grisa", F., & Torraca, N. (1996). Turbulent
#ow in closed and free-surface unba%ed tanks stirred by radial
impeller. Chemical Engineering Science, 51, 3557}3573.
Costes, I., & Couderc, J. P. (1989). Study by laser doppler anemometry
of the turbulent #ow induced by a rushton turbine. Chemical Engin-
eering Science, 43, 2751}2764.
Cotton, F. A., & Wilkinson, G. (1988). Advanced inorganic chemistry (53
Ed.). New York: Wiley.
Daskopoulos, Ph., & Harris, C. K. (1996). Three-dimensional CFD
simulations of turbulent #ow in ba%ed stirred tanks: An assessment
of the current position. I. Chem. E. Symposium Series, 140, 1}13.
Harris, C. K., Roekaerts, D., & Rosendal, F. J. J. (1996). Computational
#uid dynamics for chemical reactor engineering. Chemical Engineer-
ing Science, 51, 1569}1594.
Kirby, A. I. (1972). Hydrolysis and formation of esters of organic acids.
In C. H. Bamford, & C. F. H. Tipper, Comprehensive chemical
kinetics, Vol. 10. Amsterdam: Elsevier.
Kuipers, J. A. M., & Swaaij, W. P. M. (1997). Application of computa-
tional #uid dynamics to chemical reaction engineering. Reviews in
Chemical Engineering, 13, 1}118.
Launder, B. E., & Spalding, D. B. (1974). The numerical computation of
turbulent #ows. Computer Methods in Applied Mechanics and Engin-
eering, 3, 269}289.
Lee, K. C., Ng, K., & Yianneskis, M. (1996). Sliding mesh predic-
tions of the #ows around Rushton impellers. Flud Mixing xfth
International Chemical Engineering Symposium Series, 140,
47}58.
Middleton, J. C., Pierce, F., & Lynch, P. M. (1986). Computation of
#ow "elds and complex reaction yield in turbulent stirred reactors
and comparison with experimental data. Chemical Engineering Re-
search Design, 64, 18}22.
Pipino, M., & Fox, R. O. (1994). Reactive mixing in a tubular jet
reactor: a comparison of PDF simulation with experimental data.
Chemical Engineering Science, 49, 5229}5241.
Rice, R. W., & Baud, R. E. (1990). The role of micromixing in the
scale-up of geometrically similar batch reactors. A.I.Ch.E. Journal,
36(2), 293}298.
Smith, J. M. (1990). Industrial needs for mixing research. Transactions of
the Institution of Chemical Engineers, 68, 3}6.
Thorma, S., Ranade, V. V., & Bourne, J. R. (1991). Interaction between
micro- and macro-mixing during reactions in agitated tanks. Cana-
dian Journal of Chemical Engineering, 69, 1135}1141.
Van Doormal, J. P., & Raithby, G. D. (1984). Enhancements of the
simple method for predicting incompressible #uid #ows. Numerical
Heat Transfer, 7, 147}163.
Wu, H., & Patterson, G. K. (1989). Laser-Doppler measurements of
turbulent-#ow parameters in stirred tanks. Chemical Engineering
Science, 44, 2207}2221.
Yakhot, V., Orszag, S. A., & Yakhot, A. (1987). Heat transfer in
turbulent #uids * I. pipe #ow. International Journal of Heat and
Mass Transfer, 30(1), 15}22.