Ind. Eng. Chem. Res.

2003, 42, 6567-6575 6567

Modeling of Semibatch Agglomerative Gas-Liquid Precipitation of

CaCO3 in a Bubble Column Reactor
Stelios Rigopoulos† and Alan Jones*
Department of Chemical Engineering, University College London, Torrington Place, London WC1E 7JE, U.K.

The outcome of gas-liquid precipitation in industrial reactors, such as bubble columns, is

determined by the interplay between multiphase fluid dynamics; gas-liquid reaction engineering;
and crystallization mechanisms such as nucleation, growth, and agglomeration. In this work, a
modeling approach that takes the above phenomena into account is proposed and applied to
investigate the semibatch precipitation of CaCO3. The main elements of the approach are a
dynamic population balance equation including nucleation, growth, and agglomeration, dis-
cretized with a finite element method; a phenomenological model of interfacial mass transfer
and reaction based on penetration theory; and rigorous prediction of gas holdup via an Eulerian-
Eulerian multiphase CFD code. Experiments on CaCO3 precipitation via reaction of CO2 and
Ca(OH)2 in a 21-L bubble column are conducted and simulated with the aid of the model. The
evolution of the process is adequately reproduced, and qualitative comparisons with the product
CSD are possible, but more fundamental work on precipitation kinetics in the gas-liquid
hydrodynamic environment is required to obtain quantitative agreement.

Introduction bubble column carrying out precipitation of CaCO3,

Gas-liquid precipitation is the formation of a solid
crystalline product via chemical reactions involving a
gas phase and a liquid phase. It is a process of consider-
able industrial importance, as it is involved in the
production of a variety of speciality chemicals.1,2 The
ability to quantify the phenomena that effectively
determine the product crystal size distribution (CSD)
and establish a predictive model based on design and
operating parameters would be of great value for process
design and scale-up purposes, as it would lead to
improved product quality and enable tailoring of the
product properties to new applications.
Gas-liquid reactive precipitation was first studied in
laboratory-scale reactors with a flat gas-liquid inter-
face.3-5 Other laboratory-scale devices that have been
employed are an agitated tank in which the gas was
dispersed in the form of bubbles6,7 and a Couette-Taylor
reactor.8 The latter was employed to study the morphol-
ogy of precipitated CaCO3 by careful control of solution
composition and shear.
A proper analysis of industrial-scale equipment,
however, requires consideration of hydrodynamics, and
accurate prediction of the CSD can be accomplished by
solution of the population balance equation. The coup-
ling of the above approaches requires excessive compu-
tational resources, and it has been realized1 that a
stagewise model should be employed rather than a
differential one. The complexity is further increased by
the fact that such processes are usually operated in
batch or semibatch mode with time-varying supersatu-
ration levels and precipitation rates, so that a time-
dependent model is required and numerical methods
must be employed for its solution.
Earlier work by the present authors9 employed a
stagewise dynamic model for the simulation of a tall
* To whom correspondence should be addressed. E-mail:
a.jones@ucl.ac.uk.
†
Present address: Department of Mechanical Engineering,
Imperial College, Exhibition Road, South Kensington, London
SW7 2BX, U.K.
10.1021/ie020851a CCC: $25.00 © 2003 American Chemical Society
Published on Web 11/05/2003
based on an implementation of penetration theory and
CFD predictions. Mean crystal size was predicted with
the method of moments, resulting in qualitative repro-
duction of the main trends, but several issues such as
the rapid increase in mean size after the pH drop,
possibly attributed to agglomeration, were left unad-
dressed. This was because both the experimental results
and the model predictions reported only mean values
of the CSD. Agglomeration seems to be pronounced
during gas-liquid precipitation, as experiments7 have
shown. It has a profound effect on the CSD and might
determine the physical properties of the end product as
well as its potential for separation; depending on the
application, either its promotion or prevention might be
desirable. The mathematical analysis of agglomeration
is complex, however: it requires solution of the popula-
tion balance, and no definitive kinetic model is available.
In this work, a recently developed finite element
method for solving the time-dependent volume-based
population balance11 is coupled with a reaction engi-
neering model, to simulate the evolution of the CSD
while accounting for agglomeration in the kinetic model.
In addition, new experiments on CaCO3 precipitation
in a bubble column, during which the entire CSD was
retrieved by laser light scattering, are reported. Thus,
deeper insight into the gas-liquid precipitation process
and the underlying phenomena can be obtained, while
it is also shown that a model combining CFD, reaction
engineering, and population balance can provide design
and scale-up data in reasonable CPU time.
Experimental Part
The objective of this section is to describe the equip-
ment and analytical methods employed in the experi-
mental work and to obtain several clues regarding the
precipitation mechanism from a preliminary inspection
of the experimental results. These clues will prove to
be of vital importance for configuring the kinetic model
of CaCO3 precipitation. It must be stressed that the
present work does not constitute an exhaustive study
of CaCO3 precipitation kinetics. Such a study would
6568 Ind. Eng. Chem. Res., Vol. 42, No. 25, 2003
Figure 1. Experimental rig used for gas-liquid precipitation.
require the isolation of individual mechanisms,8,12 which
is not possible in a bubble column, an apparatus whose
simplicity of design gives rise to extraordinary complex-
ity in the physical and chemical phenomena. Instead,
our purpose is to explore whether the complex hydro-
dynamic, reaction engineering, and crystallization phen-
omena taking place in an industrial type of reactor, such
as the bubble column, can be investigated with the aid
of a mathematical model.
Gas-Liquid Precipitation Rig. The experimental
work was conducted using a bubble column reactor,
equipped with an internal concentric draft tube to
enhance circulation and mixing. The outer cylinder was
0.77 m high and had an internal diameter of 0.215 µm;
the corresponding dimensions of the draft tube were
0.45 and 0.135 m, respectively. Gas (a mixture of CO2
and N2) was injected through a sparger ring situated
at the bottom of the inner annulus (Figure 1). In each
experiment, the column was filled with approximately
22 L of Ca(OH)2 solution [AnalaR grade Ca(OH)2-
deionized water]. Before initiation of the experiment,
pure N2 gas was injected for some time to enhance the
dissolution of the Ca(OH)2 by intense circulation and
mixing. Different gas flow rates and initial solution
compositions were explored.
Because the aim was to observe the dynamic behavior
of the process, during the course of each experiment,
regular samples were taken and analyzed immediately
for pH, calcium ion concentration ([Ca2+]), and CSD. The
CSD analysis was carried out with a laser scattering
instrument (Malvern Mastersizer S), equipped with
lenses valid for measuring particles in the range 0.05-
900 µm. To gain more insight into the particle form,
selected samples were dried and further analyzed by
scanning electron microscopy (JEOL JSM-820).
Time Course of Precipitation. Typical plots of the
temporal evolution of pH, calcium ion concentration,
mean crystal size, and CSD are shown in Figures 2, 5,
and 7. The main features can be summarized as follows:
Most of the precipitation occurs during a period of
high pH (11-12), with calcium ion being consumed at
a slightly decaying rate. This period is followed by a
rapid fall in the pH, while the calcium ion concentration
has reached a miminum. Subsequently, the calcium ion
concentration increases again.
After an induction period, the mean crystal size slowly
increases. As soon as the pH drops, a rapid increase in
crystal size occurs, eventually stabilizing around 5-6
µm.
Figure 2. Evolution of mean crystal size during a typical
experiment.
The first CSD measurement (immediately after the
induction period) is dominated by a single bell-shaped
peak around 1 µm. Later, a new peak appears at the
size range 0.1-1 µm. The bimodal distribution remains
until the end.
Product Morphology. Figure 3 a,b shows a large-
scale and a closer view, respectively, of the precipitate
at an early stage of the process (soon after the end of
the induction time), evidently comprising mostly single
crystals. Occasional agglomerates are also present, and
in Figure 3c is presented a close view at one of them.
The initial agglomerates have sharp, clearly defined
edges, and the single crystals that comprise them can
be clearly identified. At a later stage, after the pH drop,
the product is dominated by agglomerates (Figure 3d),
confirming the increase in mean size. Meanwhile, the
edges of the agglomerates become increasingly smoother,
until reaching a stage where only agglomerates exist,
exhibiting an almost amorphous shape (Figure 3e). At
the same time, the solids concentration is apparently
lower.
Interpretation of Results. The absorption of CO2
into alkali solutions is accompanied by the formation
of several ionic species, of which CO32- and HCO3-
predominate in the alkaline region. Figure 4 shows the
equilibrium concentrations as functions of pH, calcu-
lated using the data of Astarita.13 Note that CO32-,
which contributes to the precipitation process, is present
at a significant proportion only at pH > 10. This implies
that, after the occurrence of the pH drop in the process,
CO32- is no longer present, and precipitation has
virtually terminated.
The increase in mean size after the pH drop is in
accordance with previous findings,1,10 which were ex-
plained in the following way: During the high pH stage,
particles experience slow growth, while agglomeration
is being inhibited by the electrical charge on the
particles’ surface. Once the pH has fallen, the mean size
increases rapidly through agglomeration.1 This inter-
pretation, however, leaves an important question un-
answered: How does agglomeration occur after the
depletion of supersaturation, which is necessary to
create solid bridges and unify the loose aggregates?
Furthermore, the experiments of Kotaki and Tsuge7 on
the same system clearly evidenced agglomeration at
high pH; our own experiments also detected agglomer-
ates during early stages (Figure 3c).
The evolution of crystal shape provides vital clues for
the understanding of the process. The loss of the sharp
edges in the agglomerates, coinciding with the reap-
pearance of free calcium ion after the pH drop, suggests

Figure 3. (a) Large-scale view of the precipitate, shortly after the induction time. (b) Closer view of the single product crystals. (c) Close
view of an agglomerate during an early stage of the process. (d) View of the precipitate during a later stage of the process. (e) Closer view
of an agglomerate during a very late stage.
Figure 4. Equilibrium concentrations of the CO32--HCO3--CO2
system
that the crystals are redissolving. Edges exhibit more
rapid dissolution, thus leading to the almost amorphous
material of Figure 3e. The redissolution can be ex-
plained by the shift of the equilibrium from CO32- ion
toward HCO3- ion. At high pH, when CO32- ion is
favored, a balance is maintained between the migration
of ions from the crystal lattice to the surrounding
solution and deposition of ions in the lattice. After the
pH drop, however, the CO32- ion that migrates is
converted to HCO3- ion, and as a result, the balance is
disrupted. The overall dissolution process can be de-
scribed by the following reaction
2+ - -
CaCO3 + H2O T Ca + HCO3 + OH
The rate of dissolution of a crystal is proportional to
its surface area. Smaller crystals with a higher surface
area-to-volume ratio disappear faster, leaving only the
larger agglomerates in the system. This explains the fact
that agglomerates dominate the precipitate after the pH
drop, despite the fact that supersaturation has been
depleted. The increase in the mean crystal size after the
pH drop is therefore only an apparent growth.
Bimodality in the CSD is usually explained by ag-
glomeration or breakage. Although agglomerates were
indeed detected in the precipitate through SEM, the fact
that the second peak appears in the small size range
indicates that agglomeration is not the cause. Disrup-
tion of the weak aggregates is another candidate, but
Ind. Eng. Chem. Res., Vol. 42, No. 25, 2003 6569
it must be ruled out by the fact that the new peak
appears at sizes smaller than the size of the single
crystals that comprise the agglomerates (∼1 µm).
The crystals comprising the new peak must, therefore,
be produced by a new wave of nucleation-growth. This
could be the effect of secondary nucleation, which is
proportional to the existing crystal mass.14,15 Size-in-
dependent growth exhibits a third-order polynomial
increase in crystal mass with respect to time. It is rea-
sonable, then, that, at some point, a sharp increase in
crystal mass will rapidly generate a large amount of
secondary nuclei, thus inducing a new wave of crystal
growth.
To confirm this speculation, an experiment was con-
ducted during which the introduction of CO2 was halted
just before the new peak was expected to appear. N2
continued to be introduced, maintaining the total gas
flow rate constant, to ensure that the turbulent condi-
tions would remain unchanged. After 30 min, the dis-
tribution remained unchanged (i.e., single peak), indi-
cating that disruption or breakage of the existing crys-
tals alone does not account for the new peak. As soon
as CO2 was introduced again, the new peak appeared,
thus demonstrating that it consists of freshly grown
particles and does not occur without the presence of
supersaturation.
Process Simulation
Population Balance. Most of the previous studies
of gas-liquid precipitation have employed a nucleation-
growth population balance model, solved using the
method of moments.5,9 Experiments, however, in both
gas-liquid4 and liquid-liquid16,17 precipitation of Ca-
CO3 have evidenced the presence of agglomeration and
demonstrated its importance in determining the product
CSD. A new method for solving the time-dependent
population balance equation with combined nucleation,
growth, agglomeration, and breakage was recently
developed by the authors11 and will be employed in this
study. It belongs to the class of finite element methods
and emphasizes conservation of moments and stability.
A brief description follows.
The time-dependent population balance equation that
describes the evolution of the CSD in a finite, spatially
6570 Ind. Eng. Chem. Res., Vol. 42, No. 25, 2003
uniform domain, with particle volume as the “internal”
coordinate, and including nucleation, growth, and ag-
glomeration, is formulated as
∂n(v,t) nin(v,t) - n(v,t) ∂ (2-16 s). In most industrial equipment, however, such
) - [G(v) n(v,t)] +
∂t τ ∂v
1 v
∫
B0δ(v - v0) + 0 βa(v - v′,v′) n(v - v′,t) n(v′,t) dv′ -
2
n(v,t) ∫0∞βa(v,v′) n(v′,t) dv′
where n(v,t) and nin(v,t) stand for the population density
at the reactor and at the inlet, respectively; G(v)
represents the volumetric growth rate; and B0, βa, and
v0 stand for the nucleation rate, agglomeration kernel,
and volume of the nuclei, respectively. The following
initial and boundary conditions apply
n(v,0) ) n0(v) (initial distribution)
n(0,t) ) 0 (no crystals of zero size)
The solution is obtained by dividing the domain of the
independent variable (particle volume) into a number
of elements, over which the solution is approximated
with first-order trial functions that are subsequently
collocated at the element boundaries. The use of first-
order functions contributes to the stability of the method
and allows it to capture the nearly discontinuous
solutions that can arise from the combination of nucle-
ation and growth in precipitation. Furthermore, the
method emphasizes conservation of the moments during
the evaluation of the aggregation source integral. The
time-dependent distributed population balance equation
is transformed into a system of ordinary differential
equations describing the temporal evolution of the
population density at the element boundaries, and the
solution is propagated along time.
Reaction Engineering. The concept of penetration
theory13 is adopted here to treat simultaneous mass
transfer and chemical reactions at the interface. Any
reaction system can thus be incorporated without the
need to resort to simplified assumptions with respect
to the reaction regime (e.g., slow, instantaneous). The
implementation is similar to our previous work:9 the
interface and the bulk are considered as two separate
dynamic reactors that operate independent of each other
and interact at discrete time intervals. The diffusion and
reaction of chemical components is described by the
following system of PDEs (note that variables at the
interface and bulk are denoted by superscripts I and B,
respectively)
∂CIi ∂2CIi K
∂t
)D
2
+ ∑ rk(CI1, CI2, ..., CIn)
∂x k)1
with initial and boundary conditions
t ) 0, x > 0 w CIi ) CBi
x ) 0, t > 0 w CIi ) C/i
(volatile species) (6)
dCIi
x ) δ, t > 0 w )0
dx
(nonvolatile species) (7)
Previous studies of the flat-interface reactor4,5 have
accounted for precipitation occurring at the interface,
because the low mass-transfer coefficient in that ap-
paratus results in very long values of the contact time5
as the bubble column, the contact time is several orders
of magnitude lower (0.02 s for 5-mm bubbles moving at
a slip velocity of 0.25 m/s, values typical for such
equipment and assumed in this work), and the extent
(1) of precipitation phenomena at the interface is negligible
compared to the bulk.
If significant spatial variation in the concentration
profiles in the reactor were observed (as in ref 9), a
network of backmixed compartments would be required
to describe the bulk. However, the bubble column used
in the present work was found to be almost fully
backmixed because of its short height and intense
recirculation; moreover, the uncertainty in precipitation
(2) kinetics means that a too-detailed model would be
wasted. However, nonideal mixing should certainly be
(3) considered in future work, possibly in conjunction with
techniques such as CFD or network-of-zones, provided
that satisfactory models of precipitation kinetics become
available. In the present model, the bulk is considered
to be fully mixed and described by the species’ mass
balances and the ODEs for the nodal values of the
population density
dCBi K
dt
) ∑ rk(CB1 ,CB2 ,...,CBn ,n1,n2,...,nm)
k)1
(8)
dnj
) fj(CB1 ,CB2 ,...,CBn ,n1,n2,...,nm) (9)
dt
Here, fj(CBi ,nj) stands for the right-hand side of the
ODEs into which the original population balance is
transformed via the finite element discretization. Initial
conditions are calculated from the mixing of bulk and
interface at the end of the previous contact time. Note
that the mass balances and the ODEs resulting from
the population balance are coupled via the source terms.
The coupling results because (a) precipitation kinetics
are strongly dependent on supersaturation and (b) the
rate of consumption of the precipitating species is the
rate of volumetric crystal growth and must be calculated
from the population balance.
The solution of the interface PDEs is obtained nu-
merically with an implicit iterative scheme, while the
bulk ODEs are propagated with the LSODE set of
subroutines18 implementing an Adams method.
Reaction Kinetics. The reaction of CO2 into alkali
solutions has been extensively studied.13,19 The first step
to consider in a CO2 absorption system is the gas-liquid
(4) equilibrium, which determines the boundary condition
for the volatile species
CO2(g) f CO2(aq) (i)
(5)
This step can be approached by an equilibrium
equation such as Henry’s law. To calculate Henry’s
constant in an ionic system, the effect of ionic strength
must be taken into account19
H
log
Hw
)- ∑i Iihi (10)
 Ind. Eng. Chem. Res., Vol. 42, No. 25, 2003 6571

hi ) h+ + h- + hg (11) Table 1. Parameter Values Used in the Simulations

parameter (units) value
equilibrium constant of reaction i, Ki (m3 mol-1) 6.1 × 104
The values for the contributions of cations (h+), anions equilibrium constant of reaction ii, Kii (m3 mol-1) 5.88
(h-), gas (hg), and compounds (hi) are taken from ref kinetic constant. of reaction i, ki (mol-1 m3 s-1) 5.0
21. The kinetics of CO2 absorption into alkali solutions kinetic constant of reaction ii, kii (mol-1 m3 s-1) 1 × 104
are determined by the conversion of CO2(aq) into solubility product, Ksp (mol2 m-6) 0.0047
growth constant, kg (m/s) 6.2 × 10-11
HCO3-, a reaction that proceeds at a great, but finite
kn1 (eq 20) (s-1) 7.5 × 106
rate. This is followed by an instantaneous ionic reaction kn2 (eq 20) 6
kn3 (eq 20) (kg-1) 1.6 × 1014
kn4 (eq 20) 0.1
CO2(aq) + OH- h HCO3- (ii) kn5 (eq 20) 1
agglomeration constant, ka (m3/s) 1.2a
1.8b
HCO3- + OH- h CO32- (iii) a At 0.6 × 10-4 m3/s gas flow rate. b At 1.1 × 10-4 m3/s gas flow

rate.

The values of the kinetic and equilibrium constants equation, with a modification proposed by Davies23
are from Astarita.13 The kinetic constant of instanta-
neous reaction iii is approximated by a very high value. Ri ) γiCi (14)

( )
The precipitation of CaCO3 can be written concisely as
xI
log(γi) ) -ADHzi2 - 0.3I (15)
2+ 2- 1 + xI
Ca + CO3 h CaCO3(s) (iv)
where ADH is the Debye-Huckel constant and I is the
ionic strength, given in terms of the concentration and
This expression, however, obscures the underlying charge on each ionic species
crystallization mechanisms that determine the rate. The 1
rate of CaCO3(s) production is essentially that of volu-
metric crystal growth, but it is size-dependent even
I) ∑
2 i
Cizi2 (16)

when the linear growth is size-independent (McCabe’s

∆L law). To obtain the rate of change for the whole Precipitation Kinetics. The following expression is
crystal mass, we need to integrate the volumetric usually employed to describe growth rate kinetics
growth function over the whole range of crystal volumes
Gl ) kg(λs - 1)2 (17)

d[CaCO3(s)] FCaCO3
dt
) ∫vv G(v) n(v) dv‚MWCaCO
0
∞
(12)
3 The experiments of several authors17,24 seem to agree
Note how the CSD enters this expression, in the form
of the population density n(v). Thus, the rate of crystal
mass production is inherently coupled with the popula-
tion balance, and to estimate it, we need a complete
kinetic model of precipitation that accounts for all
crystallization mechanisms, namely, nucleation, crystal
growth, and interparticle phenomena such as agglom-
eration and breakage. The kinetics of the precipitation
mechanisms are, in turn, functions of the chemical
species’ concentrations, as they depend on supersatu-
ration.
It is generally agreed that the driving force of super-
saturation is best related to R+βxλs - 1, where R and β
are the kinetic orders of the cation and anion in the ionic
reaction, respectively, and λs is the saturation ratio. In
an ionic solution, this is best expressed in terms of
activities17,22
Here, Gl is the linear growth rate, i.e., the increase in
particle diameter or radius, and kg is a kinetic constant.
on the order of magnitude of the parameter kg; the data
of the former17 were used in this work. See Table 1 for
a summary of the parameter values used.
Nucleation, on the other hand, is much more difficult
to study because of the variety of mechanisms (homo-
geneous, heterogeneous, secondary) that might be re-
sponsible for it. Primary nucleation depends mainly on
supersaturation, and a power law of the following form
is commonly used to describe it
B0 ) kn1(λs - 1)kn2 (18)
Secondary nucleation is induced by the existing
crystals14,15 and is a function of the crystal mass
B0 ) kn1(λs - 1)kn2Mckn3 (19)
Although several studies on calcium carbonate have
appeared,25,26 their results cannot be extrapolated to
equipment of different type and scale, where nucleation
might occur via a different mechanism. Moreover,
relatively few data have been reported on gas-liquid

x
RCa2+RCO32- systems. Most important is the fact that, during a batch
process, different nucleation mechanisms might prevail
xλs - 1 ) Ksp
-1 (13)
during different periods. In our case, the experiments
indicate that, in the beginning, high supersaturation
levels induce primary nucleation, but later, secondary
Activities are calculated according to the Debye-Hückel nucleation gives rise to a new wave of crystal growth.
6572 Ind. Eng. Chem. Res., Vol. 42, No. 25, 2003

The two mechanisms are fundamentally different and

can operate independent of each other. To account for
these facts, our overall nucleation model consists of the
sum of the two models, primary and secondary

B0 ) kn1(λs - 1)kn2 + kns(λs - 1)kn3Mckn4 (20)

Finally, although the prevailing polymorph appears

to be calcite, it must be acknowledged that all three
polymorphs of CaCO3 are likely to appear during the
precipitation process. The derivation of a kinetic model
accounting for their simultaneous presence is an ex-
ceedingly difficult task, however, and will not be at-
tempted here; one is referred to ref 22 for this purpose.
Agglomeration of crystals is a two-step process. The
first stage of agglomeration, i.e., the formation of
flocculates through collisions and interparticle attrac-
tion, is akin to similar phenomena occurring in colloids
and aerosols. Thus, the starting point for the formula-
tion of a mathematical description of agglomeration are
the theories developed in those fields, most importantly
the pioneering work of Smoluchowski.27 The second step
is the growth of crystalline material between the clus-
ters at spots called cementing sites. This step differenti-
ates crystal agglomeration from other clustering pro-
cesses, and few mechanistic models of it have appeared
so far. Certain studies28,29 have approached the problem
by considering crystal growth at a cementing cite
between a pair of spherical particles. Although these
approaches have yielded valuable insights, the formula-
tion of a definitive model of the agglomeration process
as a whole is still faced with severe obstacles:
(1) Particles of various states (flocculates, aggregates
of various ages, firm agglomerates) are likely to be pre-
sent in a crystal agglomerating system. CSD measure-
ments, however, provide no information on these states.
(2) The interparticle phenomena that modify the CSD
are also various. Unsuccessful collisions, aggregate Figure 5. Experimental and simulated evolution of pH and
disruption, and the breakage of firm agglomerates are calcium ion concentration: (a) [Ca(OH)2] ) 3 mol/m3, CO2/N2 )
all possible, depending on the conditions, and it is very 0.000 01:0.0001 m3/s; (b) [Ca(OH)2] ) 4 mol/m3, CO2/N2 ) 0.000 01:
difficult to distingush between these events. 0.0001 m3/s; (c) [Ca(OH)2] ) 4 mol/m3, CO2/N2 ) 0.000 01:0.000 05
(3) Current mechanistic models tend to describe m3/s.
aggregation as a two-particle event; in reality, however,
it might occur through multiparticle clusters with that, when agglomeration is the only interparticle event
bridges of various ages and strengths. in the population balance, the results refer to the net
(4) The size-independent kernel seems to be in good effect of an agglomeration-disruption equilibrium.
agreement with most agglomeration experiments in Stirred tanks exhibit higher shear forces, and therefore,
stirred tanks and is used extensively. This agreement, disruption of the weak, not fully cemented aggregates
however, is likely to be due to mutual cancellation of (especially the larger ones) is likely to occur more often,
competing mechanisms, and we do not know whether yielding an apparent size-independent agglomeration.
it would be maintained in an arbitrary environment. On the other hand, the more gentle agitation in the
As a result, agglomeration kinetics are heavily system- bubble column might be the reason the effect of the size-
dependent and difficult to scale-up. The dependency of dependent kernel becomes apparent.
the agglomeration kernel on hydrodynamics has been MSMPR experiments29 have shown agglomeration to
investigated mainly in stirred tanks,29 whose flow fields be roughly proportional to growth. The underlying cause
are very different from those of bubble columns. For this of both phenomena is supersaturation, and during a
reason, no explicit dependency on hydrodynamics will batch experiment, supersaturation varies. It seems
be employed here; instead, the agglomeration constant appropriate, then, to correlate agglomeration to super-
will be adjusted to fit experiments with different gas saturation directly. Given the second-order dependency
flow rates. of growth on supersaturation, we can infer a similar
Among the most common theoretical agglomeration dependency to the agglomeration model. Our formula-
kernels, we found the fluid shear kernel (orthokinetic tion is thus
aggregation) to provide the best fit of our experiments.
This is in good aggreement with the theory, but in βa(v′,v - v′) ) ka(λs - 1)2[(v′)1/3 + (v - v′)1/3]3 (21)
contrast with most of the experimental data on stirred
tanks, which showed the size-independent kernel to be Apart from the growth kinetics, the remaining pa-
more suitable.29 It must be borne in mind, however, rameters must be adjusted to fit the experiments. This

Figure 6. Simulation of the evolution of supersaturation in a
typical experiment.
is especially difficult in a batch experiment, where
different mechanisms can prevail at different time
Figure 7. Experimental and simulated CSDs, [Ca(OH)2] ) 3 mol/m3, CO2/N2 ) 0.000 01:0.0001 m3/s.
Figure 8. Experimental and simulated CSDs, [Ca(OH)2] ) 4 mol/m3, CO2/N2 ) 0.000 01:0.0001 m3/s.
Ind. Eng. Chem. Res., Vol. 42, No. 25, 2003 6573
periods and each mechanism is a nonlinear function of
supersaturation. In our study, the determination of the
parameters was guided by (a) the mean size of the
crystals immediately after the induction period, which
is determined by the balance between primary nucle-
ation and growth; (b) the evolution of the Ca2+ concen-
tration; and (c) the appearance of the second peak at
the low size range, which indicates the effect of second-
ary nucleation.
Hydrodynamics. The most important hydrodynamic
parameter in gas-liquid precipitation is the gas holdup,
as it determines the rates of the chemical phenomena.
As in our previous work,9 the Eulerian-Eulerian mul-
tiphase CFD model is used to obtain the gas holdup.
This approach is the best choice for modeling large-scale
equipment, as it does not raise extreme computational
demands and yields sufficiently accurate results with
respect to overall (averaged) properties, although it is
less successful in reproducing more fine details such as
6574 Ind. Eng. Chem. Res., Vol. 42, No. 25, 2003
Figure 9. Experimental and simulated CSDs, [Ca(OH)2] ) 4 mol/m3, CO2/N2 ) 0.000 01:0.000 05 m3/s.
the radial phase distribution. Details on its theoretical
derivation can be found in refs 30 and 31, and its
application to vertical dispersed flows is discussed in
ref 32. Drag force was specified according to the ap-
proach of Scwarz and Turner.33 Turbulence in the liquid
phase was implemented with the aid of the k- model.33
The implementation was carried out with the CFX 4.3
code (AEA Technology, Harwell, UK).
Simulation Results. Figure 5 shows a comparison
of the simulated and experimental results for the
evolution of pH and calcium concentration during the
precipitation experiments. Overall, the time course of
the process is well simulated. The measured pH curve
seems to stabilize at a higher pH (7-8) than predicted,
which falls to pH 5-6. This can be attributed to the
kinetic model of the CO2-OH- process that included
only those subreactions that are important in the high
pH regime. At near-neutral pH, other ionic species apart
from the ones considered (CO32-, HCO3-) might be
present. Moreover, the pH meter was calibrated for the
alkaline region.
The Ca2+ plot is indicative of the precipitation phen-
omena. During the induction time, i.e., the time during
which the nuclei are formed and grow to observable size,
consumption of substrate is minimal, and the Ca2+
concentration is constant. Subsequently, a rapid drop
in Ca2+ concentration indicates a high growth rate. This
is due to very high supersaturation levels, generated
by the accumulation of CO32- during the induction
period. Rapid growth implies rapid consumption, and
supersaturation soon falls to low levels, resulting in a
lower growth rate. This rate is almost constant until
the pH drop, indicating a balance between consumption
and generation of supersaturation. The redissolution of
the crystals, resulting in the reappearance of free
calcium ion, is not included in the model. The above
phenomena are reflected in the supersaturation plot,
shown in Figure 6: a rapid increase during the induc-
tion time is followed by a rapid drop. Then, supersatu-
ration is constant, until dropping to zero upon the
depletion of calcium ion.
Figures 7-9 show comparisons of the experimental
CSD measurements and the simulation results. In most
cases, the main trends are reproduced, although agree-
ment is not quantitative. The first CSD measurement
usually exhibits the highest deviation from the modeling
results, partly because of experimental error. This
measurement was usually taken immediately after the
induction time, when the solution was still too dilute
and the obscuration of the Mastersizer S was below the
limit required for a reliable measurement; large foreign
particles would easily shift the CSD toward greater
sizes. This happened in Figures 7 and 8, where the first
measurement showed a much higher proportion of large
particles, which is clearly unrealistic. The cumulative
undersize distribution reveals that the deviation occurs
mostly at the largest sizes, sometimes larger even than
20 µm, but such crystals were seldom observed by the
SEM, which supports the possibility of the CSD being
biased by foreign particles. The intermediate and final
measurements, however, are in much better agreement
with the predictions. Most important, the combination
of secondary nucleation and agglomeration succeeds in
reproducing the bimodality in the CSD.
The lack of quantitative agreement can be attributed
to the uncertainty in the precipitation kinetics, as the
reaction engineering model was validated by the con-
centration predictions. This was to be expected, as the
precipitation mechanisms have not been adequately
studied in the gas-liquid environment. The modeling
of agglomeration seems to pose the most difficult
obstacles, because of the lack of a definitive mechanistic
model of the cementation step. This problem is espe-
cially pronounced in this study for two reasons: (a) in
a batch process, the agglomeration kinetics are time-
varying, depending on supersaturation, and (b) the
hydrodynamic environment that determines the ag-
gregation-disruption equilibrium (or aggregation ef-
ficiency) in gas-liquid flows is fundamentally different
from that in stirred tanks. The agglomeration model
used in this study takes supersaturation into account
and thus achieves reasonable predictions of the extent
and time scale of the phenomena occurring during the
semibatch process. The sustaining or disruption of the
weak aggregates is not mechanistically incorporated,

however, and this might be the reason the exact shape
of the CSD is not accurately reproduced.
Conclusions
In this work, population balance, reaction kinetics,
and hydrodynamic principles were integrated into a
modeling approach for the gas-liquid precipitation
process. By accounting for all of the above consider-
ations, the model aims to provide tools for the analysis
and scale-up of industrial-class equipment. The ap-
proach was subsequently used to simulate the precipita-
tion of CaCO3 by CO2 absorption into lime, and experi-
ments on a laboratory-scale rig were carried out for
comparison. The main findings can be summarized as
follows:
(1) The increase in mean size after the pH drop is due
to the disappearance of the smaller crystals by dissolu-
tion.
(2) Agglomeration starts to take place at relatively
high pH and proceeds to a considerable extent, possibly
because the aggregates are less frequently disrupted
than in stirred tanks. For the same reason, the shear
(orthokinetic) kernel succeeded in reproducing the net
result of the aggregation-disruption processes better
than the size-independent kernel.
(3) Bimodality in the CSD was shown, by means of
both experiment and model, to be the result of a new
wave of nucleation-growth induced by the existing
crystals (secondary nucleation).
The conjunction of penetration theory and CFD
predictions of the gas holdup seems to yield an adequate
description of the reactor performance, as the prediction
of the evolution of the species concentrations shows.
Therefore, the discrepancies in the CSD predictions can
be attributed mainly to the uncertainty in precipitation
kinetics; the main trends, however, could be explained
and reproduced. Systematic studies of the kinetics, as
well as improved mechanistic models of agglomeration
(especially in relation to hydrodynamics) and nonideal
mixing, should be considered in future work to approach
quantitative agreement.
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Received for review October 28, 2002
Revised manuscript received September 16, 2003
Accepted September 17, 2003
IE020851A