Chrmical Engineering Science, Vol. 47, No. 2, pp. 445456, 1992. ooo9-2509p2 s5.00 + 0.

00
Primed in Great Britain. 0 1991 Pergamoa Fvess plc

DYNAMIC SIMULATION OF BIMODAL DROP SIZE

DISTRIBUTIONS IN LOW-COALESCENCE BATCH
DISPERSION SYSTEMS

E. G. CHAT21 and C. KIPARISSIDES

Chemical Engineering Department and Chemical Process Engineering Research Institute, Aristotle
University of Thessaloniki, P.O. Box 1517, 540 06 University City, Greece

(First received 12 December 1990; accepted in revised form 11 March 1991)

Alastrati-Transient drop size distributions in a batch stirred tank are a manifestation of the drop breakage
and coalescence mechanisms. A recently developed experimental configuration using a laser diffraction
technique suitable for on-line monitoring of drop size distributions, showed increased sensitivity in
measuring the small diameter drops. For all experimental conditions tested it was observed that the batch
low-coalescing dispersion system assumed characteristicbimodal distributions within very short agitation
time. The laser diffraction technique revealed the fine changesof the small size peak of the distribution with
sufficiently high resolution. The objective of the present study was to establish a breakage mechanism in
order to predict the dynamic behaviour of the bimodal drop size distributions by using the population
balance formalism. The proposed model considers breakage of the drops into one daughter and several
satellite drops. The volume ratio between the generated drops as well as the number of satellite drops are
considered to be proportional to the parent drop volume. The obtained agreement between the experi-
mental and theoretical bimodal drop size distributions is quite satisfactory for a range of experimental
conditions.

1. INTRODUCHON mental configuration using a laser diffraction tech-

Drop size distributions are an important character-
istic of liquid-liquid dispersions. The physical and
chemical phenomena taking place in an agitated ves-
sel largely depend upon the size of dispersed droplets
and their distribution. In agitated liquid-liquid sys-
tems the dispersion is formed by two dynamic pro-
cesses: drop break-up and coalescence. The former
mainly occurs in regions of high shear stress near the
agitator blades or as a result of turbulent velocity and
pressure variations along the surface of a drop. The
latter is either increased or decreased by the turbulent
flow and can be considered negligible for dilute dis-
persions with sufficiently high concentrations of sur-
face active agents.
The behaviour of dispersions in agitated vessels can
be simulated by solving the population balance equa-
tion that formulates the interaction rates between
droplets in a turbulent flow field (Valentas and
Amundson, 1966). By making the assumptions of
perfect macromixing and statistical homogeneity of
the vessel content, a homogeneous interaction popu-
lation balance model can be written. This is applicable
to vessels with short circulation times or low coales-
cence rates (Park and Blair, 1975).
Measurements of multimodal or bimodal drop size
distributions in agitated dispersions have been
scarcely reported in the literature (Ward and
Knudsen, 1967; Brown and Pitt, 1972; Hong and Lee,
1985; Laso et al., 1987b). This may be attributed to the
limitations of the conventional techniques, such as
photography, used for measuring the drop size dis-
tributions, which do not allow the accurate interpreta-
tion of this type of data. A recently developed experi-
445
nique suitable for on-line measurements, allows deter-
mination of multimodal drop size distributions with
increased sensitivity especially in measuring the small
diameter drops (Chatzi et al., 1991). This technique
revealed the fine changes occurring in the size dis-
tribution of drops smaller than 80 pm. It is, therefore,
the objective of the present paper to develop a droplet
breakage model in order to simulate the evolution of
the experimentally determined bimodal drop size dis-
tributions. This is accomplished by using the homo-
geneous interaction population balance formalism
written for a batch agitated vessel. To our knowledge,
no similar attempt is reported in the open literature,
mainly due to the limited resolution of the experi-
mental measurements for small droplet sizes. The
basic considerations on the origin and prediction of
bimodality have been previously established (Chatzi
et al., 1989) for steady state drop size distributions
obtained by a photographic technique. In the follow-
ing study a modification of the breakage mechanism is
introduced, in order to predict the dynamic behaviour
of both the fine drops and the large-size tail of the
distribution.
2. BATCH EXPERIMENTS AND PARTICLE SIZE ANALYSIS
The two-phase system used for our experimental
studies consisted of styrene (Fluka AG) as the dis-
persed phase and distilled water as the continuous
phase. The volume fraction of styrene was 0.01. The
continuous phase contained 0.1 B/l polyvinyl alcohol
(PVA) as a suspending agent. The PVA had a degree
of polymerization of 500 -and a hydrolysis ratio of
97.5-99.5 mol% (Fluka AG).
446 E. G. CHATZI
The mixing vessel was a capped, round bottomed
glass cylinder with 15 cm internal diameter fitted with
four vertical, equally-spaced stainless steel baffles. The
width of each baffle was equal to one-tenth of the tank
diameter. A stainless steel six-blade turbine impeller
with diameter equal to one-third the tank diameter
was connected to a controlled variable-speed power
supply. The impeller was immersed to a depth equal
to two-thirds of the total height of ‘the liquid-liquid
dispersion, which was always maintained identical to
the vessel diameter. The total volume of the dispersion
was 2 1.
Water from a constant-temperature Nesiab RTE-
210 bath was steadily circulated through the vessel’s
jacket to maintain a desired temperature inside the
tank, which was monitored by an RS-2 remote tem-
perature sensor. The same constant-temperature bath
was used to maintain a steady temperature in a
secondary agitated vessel filled with continuous
phase. The solution in the secondary vessel was used
for filling and cleaning the sampling lines and for
obtaining the background measurement of the con-
tinuous phase. In a typical experiment, the vessel was
first filled with the required amounts of distilled water
and concentrated PVA solution and the impeller
speed was adjusted to the desired setting. The temper-
ature of the mixture was raised to the specified tem-
perature value. Subsequently, the organic phase was
added into the continuous phase.
At prespecified time intervals samples were with-
drawn from the bottom of the vessel and directed
through a continuous sampling line first to the
measuring flow cell, and through a metering dia-
phragm pump, back to the reactor. The recirculation
of each sample lasted for about 3 min during which
two consecutive measurements of drop size distribu-
tion were obtained for comparison. The circulation
was then stopped, the sampling system (tubing and
measuring-cell) was thoroughly cleaned with the con-
tinuous phase, and a new background measurement
was taken before the next sample analysis. Pumping
and circulation was shown to have a negligible effect
on the drop size distribution (Chatzi et al., 1991).
The drop size distribution was d&ermined by a
Malvern laser diffraction particle sizer model 260%
interfaced with an Olivetti M24 microcomputer. The
particle size analyzer was equipped with a continuous
flow cell. A lens with focal length 300 mm and dynam-
ic range 180: 1 was attached to the optical measure-
ment unit. The analyzer was capable of detecting
particles and droplets in the size range of 5.8-564 pm
with an accuracy of + 4% on volume median dia-
meter. The primary output of the instrument was the
relative volume size distribution stored in 32 size
classes uniformly spaced on a logarithmic scale.
Typical results generated by the instrument include
cumulative size distribution, volume fraction within
each size band and a listing of the main parameters of
the distribution including the volume mean, median
and Sauter mean diameter (Malvem Instruments
Ltd., 1987). A computer program has been written for
and C. KIPARISSIDE~
the mathematical transformation of the measured
volume frequency distribution to corresponding vol-
ume density and diameter density distributions. The
discrete distribution can be transformed into a con-
tinuous one by the use of a quasi-cubic Hermite
splines method. Various characteristic moments and
averages of the discrete distribution such as expected
drop diameter, surface and arithmetic means, max-
imum diameter as well as the total number of drops in
the vessel can be calculated from the measured vol-
ume frequency data.
The validity and reproducibility of the laser diffrac-
tion method and the specific sampling and measuring
arrangement used, was tested by Chatzi et al. (1991).
Furthermore, it was found that the location of sample
withdrawal had no significant effect on the measured
drop size distribution. This was expected for the
particular system and the experimental conditions
employed since the degree of inhomogeneity of the
vessel contents was quite low (Chatzi et al., 1989).
The experiments were carried out at atmospheric
pressure and a temperature of 25°C. Two impeller
speeds were investigated, namely, 200 and 300 rpm.
Both speeds were above the minimum impeller speed
for complete liquid-liquid dispersion. The maximum
impeller speed of 300 rpm was just below the level at
which air entrainment occurred.
The amount of PVA used was sufficient for satura-
tion of the total droplet interfacial area generated
under different experimental conditions. The inter-
facial tension was measured with a KRUSS surface
tensiometer Model K10 using the Wilhelmy plate
method. For PVA concentrations less than 10 g/l, the
physical properties of the continuous phase do not
significantly vary from those of pure water. Therefore,
the average density and viscosity of the dispersion
were calculated as weighted averages of the corres-
ponding values of the dispersed and continuous
phases.
3. POPULATION BALANCE MODEL
The dynamic behaviour of a dispersion in an
agitated tank and therefore its drop size distribution
are determined by the breakage and coalescence pro-
cesses of the dispersed drops. If the dynamic character
of breakage and coalescence is formulated, drop size
distribution can be predicted by the method of popu-
lation balances (Valentas and Amundson, 1966;
Valentas et al., 1966; Chatzi and Lee, 1987).
When the coalescence frequency of the dispersed
phase is very low compared to the circulation fre-
quency of the dispersion in the vessel, the homogen-
eous population balance models can adequately de-
scribe the dispersion (Coulaloglou and Tavlarides,
1976). Homogeneous models are based on the as-
sumption of statistical homogeneity of the contents of
the vessel. This means that the time-average position
distributions of drops in any two small volumes in the
vessel are approximately the same. Therefore, homo-
geneous interaction models neglect the local varia-
 Simulation of bimodal drop size distributions in low-coalesamce batch dispersion systems
tions of flow, energy conditions and interaction fre-
quencies.
The validity of the spatial homogeneity assumption
with regard to the size distribution of the dispersion
system used in this study has been already shown
(Chatzi ef al., 1989) by estimating the relative magni-
tudes of the circulation and collision frequencies in the
system. This is consistent with the Iow dispersed-
phase volume fraction as well as the presence of a
protective colloid, that minimize the coalescence rate
as compared to breakage. For the experimental sys-
tem used in this study it was observed that the
coalescence time was much longer from the time
required for drop breakage (Chatzi et al., 1991). This
implies that breakage is the dominant process in
controlling the drop sire and its distribution. There-
fore, the population balance equation can be simpli-
fied by neglecting the coalescence terms to yield the
following equation for a batch stirred vessel:
hn.r
= B(u’,u)U(y’)B(o’)N(t)A(u’
WI
,r)
sD
- ~we,~)g(v).
The left-hand side represents the rate of change of the
number of droplets of volume u, expressed as the
product of the total number of drops in the vessel,
N(t), and the volume density function, A(u,t). The first
term on the right-hand side accounts for the genera-
tion of drops in the size range (u,u + dv) due to
breakage of droplets of volume larger than u. Finally,
the last term of eq. (1) accounts for the disappearance
of drops of sire u by breakage.
The probability density function A(v, t) is by defini-
tion:
A&r) = dX/du
where X is the fraction of drops of a certain size and:
j-;;;dX = lI;A(u,t)du
447
The sizes of the population of drops are described by
the diameter density distribution, A(d,,t), so that
A(d,, t)d(d,,) is the number fraction of drops at time t
having a diameter from d, to docd. that satisfies the
normalization condition:
d“..m,
A(d,,r)d(d,,) = i. (7)
s d !&.,,a
The function g(r) is the fraction of drops having
volume v that disappear through breakage per unit
time (s- I), u(v’) is the number of droplets formed from
breakage of one drop with volume u’, B(u’,uj is the
number fraction of drops having volume u formed by
breakage of a drop of volume u’(cxxI-~), and N(t) is the
total number of drops in the vessel at time t. Note that
all the terms in the population balance eq. (6) have
dimensions CIII-‘s-~. The d,_,,, and d,__ appearing
in the limits of the integral correspond to the min-
imum and maximum droplet sires present in the
mixing vessel. The above considerations are valid for
an isothermal system with no interphase species trans-
fer or chemical reactions occurring and for interaction
frequencies independent of the droplet age.
3.1. Discretization of the population balance
(1) In order to obtain the numerical solution, the
integro-differential population balance equation was
transformed into a system of differential equations by
discretizing the range of drop diameters according to
the method of classes. An excellent formulation of the
method of classes is given by Marchal et al. (1988).
Thus, the size range of the population of drops was
divided into a suite of equally-spaced diameters, D,,(t),
DIM . . * , DN(t) as shown in Fig. 1. D,,(t) is equal to a
preset minimum size of drops, d,$,, and Dx(f) is the
size of the largest drop, d,,, at any time t. These sizes
define iV classes denoted as Ci, where in general the
width of the class Ci is:
(2)
AC,(t) = Di(t) - D,._ I(z) (8)
and the characteristic sire of the drops corresponding
= 1. (3) to the class C,(r) is:

It is often more desirable to express the drop size d,(t) = Di- I(t) +
Di(t) - Di- 10)
(9)
distribution in terms of the drop diameter instead of 2 .
the drop volume. Therefore, we introduce another
probability density function A&, t) defined as:

W,,t) = dXld(d,). (4)

Y(d,J)
+
It follows that
A(d,,t) = A(u,~)/(~/R)(~/~L)-*‘~L)-~‘~. (5) Yi(t)

After suitable mathematical manipulations the popu-

lation balance eq. (1) becomes: Yi+l(t) -----__---

q(t) ._
; EN(t)A(d,,r)] = (2/n)-’ (6/~)“~ $+1(t)

d di(tl dj+l(t)
x p “-= *
B(u’,4 ~(4 gWN(O AK,, 6 d6-b) Dj-f(t) tljw (t)
s d” Di4.l d,(t)
- N(WKA g@). (6) Fig. 1. Discretization of the diameter density function.
448 E.G. CHATZI and C. K~PARISSIDES
Let Y,(t) be the presumed constant value of the
number of drops in the class C,(t) at time t:
W)
where Y(d,, t) is the number of drops having diameter
d, at time t and thus:
Y(d,,t) = N(t)A(d,,t). (11)
The total number of drops in the suspension can be
calculated similar to eq. (10):
(12)
Joott)
The set of N differential equations obtained from
discretization of the population balance (6) can be
solved for YJt) by using the normalization condition
(7). The total number of drops in the suspension can
be obtained from eq. (12) and the number density
function A(d,,t) can be calculated according to eq.
(11).
Finally, the mean drop diameters, d,,, can be calcu-
lated based on the general equation proposed by
Mugele and Evans (1951):
(d&Q-’ =
s DNW
Do($1
44dwt) d(d,)/
where q and p are the characterjstic subscripts and
exponents used to define the mean diameters (q > p, q
= 1, 2, 3 and p = 0, 1, 2).
3.2. Solution of the population balance
The system of first-order ordinary differential equa-
tions resulting from application of the method of
classes was solved numerically for the number of
drops in each size class, Yi(t), by two alternative
methods, a fourth-order Runge-Kutta routine with a
variable time step suitable for stiff equations and
yielding fourth-order accuracy, and alternatively the
Gear predictor-corrector method with a global error
of O(h:), where h, is the time discretization step. The
integrals were approximated by the composite
Simpson’s rule with a global error of O(h4), where h is
the width of the discretization class Ci. For an even
number of equally spaced intervals (“panels”) the
Simpson’s l/3 rule was used, while for an odd number
of panels Simpson’s 3/8 rule was employed over the
last three panels.
Both RungeKutta and Gear methods required the
initial conditions on the number of drops in each
class, Y,(t), as well as a subroutine to compute
d(Yi)/dt as a function of (Y,, Y,, . . . , Y,). No
significant differences were observed between solu-
tions obtained by the two different integration
methods. The Runge-Kutta method, however, re-
quired more computational time per time step. On the
other hand, the only draw-back of the Gear
predictor-corrector method was the high com-
putation time required for integration at the first time
step.
For each time step the calculated values of the
number of drops in the last five size classes, YN-4(t),
. . . ) YN(t), were compared to the maximum value of
the distribution. When the ratio approached a limit
beyond which the distribution tail could be neglected,
for example 10V4, the last size class(es) was omitted
and integration was continued by using a reduced
number of size classes.
3.3 Expression of the breakage rate
Solution of the population balance eq. (6) pre-
supposes knowledge of the breakage frequency, g(v),
the breakage distribution function, /~(v’,v) and the
number of drops formed per breakage, ~(0’). Further-
more, the evolution of the drop size distribution in the
liquid-liquid dispersion is characterized by the trans-
ition probability of drop breakage and the number
and size distribution of the droplets resulting from
breakage of a parent drop (Narsimhan et al., 1980).
However, limited information is available on the
breakage of drops in turbulent liquid-liquid disper-
sions. It has been postulated in the literature that
breakup in turbulent fields may be caused by viscous
shear forces, by turbulent pressure fluctuations
(Hinze, 1955; Shinnar and Church, 1960) or by relative
velocity fluctuations (Mikos et al., 1986, Narsimhan
et al., 1979). Considering breakup by viscous shear,
the droplet is first elongated into two fluid lumps
separated by a thread and breaks into two almost
equal size drops corresponding to the lumps and a
series of smaller drops corresponding to the thread.
Also, it may be elongated into a cylindrical thread
which then breaks into several smaller droplets
(Taylor, 1932, 1934). Only in rare instances does the
deformed liquid droplet break up into two equal
droplets (Sleichter, 1962). In most cases, the liquid
droplets break up into a series of small droplets
(Karam and Bellinger, 1968). This is known as
thorough breakage (Narsimhan et al., 1980). On the
other hand, a droplet suspended in turbulent flow is
exposed to local pressure and relative velocity fluc-
tuations. For nearly equal densities and viscosities of
the two liquid phases, the droplet can be assumed to
oscillate with the surrounding fluid. When the relative
velocity is close to that required to make a drop
marginally unstable, a number of small drops are
sripped out from a larger one (Sleichter, 1962). This
situation of breakage is referred to as erosive breakage
(Narsimhan et al., 1980). Also it is possible that a
transition in the type of deformation and breakage
may take place, depending on the size of the droplet
(Narsimhan et al., 1980).
In the past, various generalized phenomenological
breakage models were applied in order to predict the
steady state drop size distribution as a function of the
basic hydrodynamic and physical properties of the
system. Coulaloglou and Tavlarides (1977) have de-
veloped a model for the the two lumps-neck deforma-
tion and breakage of a drop in a turbulent flow field
 Simulation of bimodal drop size distributions in low-coalescence batch dispersion
and derived two functional forms of the breakage
frequency. Their basic consideration was that the
extent of the drop deformation and the turbulent
kinetic energy transmitted to the drop by the
turbulent eddies determine whether or not the drop
will break or will return to its initial state. The derived
expressions for the breakage distribution function
were shown to be unable to simulate bimodal experi-
mental drop size distributions (Chatzi et al., 1989).
Narsimhan et al. (1979) developed another model
that describes the fragmentation of the droplet if the
turbulent motion provides the minimum increase in
the surface energy for breakup in a locally isotropic
flow field. The basic consideration of this model is
that the droplet breaks as a result of oscillations due
to the relative velocity fluctuations. The relative velo-
city fluctuations around the surface of a droplet ex-
posed to a turbulent field are viewed as due to arrival
of either one or more eddies of different scale (fre-
quency) on the surface of the droplet. The breakage
frequency depends on the average number of eddies
arriving on the surface of the drop per unit time (1)
and on the probability that the arriving eddy will have
energy greater than or equal to the minimum increase
in the surface energy required to break a droplet of
diameter d. The parameter 1 can be regarded as a
constant and referred to as Cv,r in the general ex-
pression for the breakage frequency (Cbatzi et al.,
1989):
g(d) = C,, efrc {C,,,(~/~d)1’Z/[d5’6N*(~~)2’3 1 }.
(14)
This expression was used successfully to predict
steady-state bimodal drop size distributions in an
agitated vessel (Chatzl et al., 1989) and was therefore,
applied in the present study in order to simulate the
dynamic behaviour of the system.
The breakage process cannot be completely de-
scribed, unless we know the distribution of the droplet
sizes resulting from breakage of a larger drop, 8(v’, u),
and the number of drops per breakage, u(u’). If we
consider the breakage distribution function as the
combined result of a large number of independent
random events, it is reasonable to expect that it is
normal or approximately normally distributed
(Coulaloglou and Tavlarides, 1977).
For binary or thorough breakage and for a parent
drop of volume u’, the daughter drops are distributed
about a mean value 6 as:
B(o’,u) = (l/u.(2n)1’Z)exp[ -(u - 92/2a~]_ (15)
If 99.6% of the droplets lie inside B + 30,, then the
standard deviation trVwill be:
IT”= il/3 = lY/[3u(u’)]. (16)
systems 449
For erosive breakage Chatzi et al. (1989) introduced
a breakage distribution function similar in principle
to that proposed by Collins and Knudsen (1970) in
order to predict bimodal drop size distributions pro-
duced by turbulent pipe flow. Tho model was capable
of simulating bimodal drop size distributions ob-
tained at steady state by using a photographic tech-
nique. In general, a parent drop of volume u’ was
considered to break into N,,., equal-volume (ur)
daughter drops and N, equal-volume (11~) satellite
drops with a fixed volume ratio x = ur/vz. The
daughter drops are normally distributed and range
from umin/[Ndo+ WAX)1 to U,ICNd, + W,lx)l-
Depending on their size, the drops produced by
breakage may be either daughter or satellite drops
and therefore, the number of drops with volume u
formed by breakage of a drop of volume II’,
u(u’) J?(u’,a), equals:
if u’/(N,x + N,) < 2, 4 u’/[Naa + (N,/x)f (18)
if u > u’/CNd. + (N,,/x)l . (19)
In the present work, this breakage distribution func-
tion is used for simulating the dynamic behaviour of
the drop size distribution and it is also extended for
the more general case of a number of satellite drops
and a volume ratio of daughter-to-satellite drops
varying with the parent drop size.
4. RESULTS AND DISCUSSION
The unreliability of steady-state experiments for
evaluating the interaction rates, i.e. breakage and
coalescence, has been recognized in the literature
(Laso et al., 1987a). In general, steady-state data can
only yield a simple check of the relative importance of
the breakage and coalescence processes, and a very
rough discrimination between breakage and coales-
cence mechanisms. A more detailed description of the
dynamics of these processes may be obtained by
simulating the transient behaviour of the system.
Figure 2 shows transient drop size distributions
obtained at 200 rpm for stirring times 15, 30,45 and
180.min. The distributions are clearly bimodal, with
the large-size peak of the diameter density distribu-
tion shifting from 130 to 110 pm and the small-size
peak from 55 to 45 pm as the agitation time increases.
In fact, the 55 pm peak gradually decreases in intens-
ity, while a new peak emerges at 45 w. A similar
tendency was also observed in other experiments at
different impeller speeds, temperatures and concentra-
tions of surface active agent (Chatzi et al., 1991). For
all experimental conditions tested the system assumes
its characteristic bimodal shape of the size distribu-
tion in less than 5 min. Further stirring does not
substantially alter the shape of the distribution but
at&&s the fine features of the small-size part of the
distribution.
The fast initial breakdown of the dispersed phase is
termed as the primary phase of breakdown (Bajpai et
 E. G. CHA-IZI ‘md C. ~IPARISSIDES

Euolutlon of drop size dicrtrlbullon (experimental data)

40 60 120 160 200 240

Drop dlsm~ter. pm

40 60 120 160 200 240 260 320

Drop 6lamater. pm

Fig. 2. Experimental transient diameter and volumedensity distributions for a system of 1% styrcne in
water at 25°C and 200 rpm and for agitation times 15. 30.45 and 180 mh.

al., 1975) and is followed by a secondary phase during
which the droplet dispersion phenomena occur at a
much slower rate. During the secondary breakage
process the size distribution changes gradually until a
dynamic equilibrium is achieved. Bimodal distribu-
tions have been scarcely reported in the literature
(Ward and Knudsen, 1967; Brown and Pitt, 1972;
Hong and Lee, 1985; Laso et al., 1987b). This may be
attributed to the limited resolution of the methods
used for measuring the drop size distributions (i.e.
photography). Ward and Knudsen (1967) obtained
drop size distributions characterized by two peaks
from photographs of a flowing dispersion. As circula-
tion proceeded, the position of the peaks remained
relatively constant with respect to diameter but the
relative frequency of the small diameter drops in-
creased. It was found that the median volume of the
low-diameter peak was only from 0.03 to 4% of the
median volume of the high-diameter Peak. As a result,
Ward and Knudsen (1967) suggested that drop break-
age was of an erosive type according to which a
droplet breaks off a much larger drop, leaving it
virtually unchanged. For a’ non-coalescing
liquid-liquid system Brown and Pitt (1972) measured
photographically drop size distributions of a bimodal
form and attributed the bimodality to a breakage
pro&s that invol.ves an orderly removal of small
elements from drops whose sizes are approaching the
maximum stable value. Hong and Lee (1983) observed
bimodal distributions by a microphotographic tech-
nique. The multimodality was more pronounced at
shprt agitation times and the peaks exhibited a shift to
smaller diameters as the agitation time increased.
Laso et al. (1987b) commented on the tendency of the
observer to preferentially count larger drops whilst
neglecting smaller ones. The same investigators em-
ployed a photographic technique and observed
bimodal transient distributions for a slow-coalescing
system.
For a system with negligible coalescence rate, all
drops are generated by the breakage process.
Thorough breakage of the large drops into several
small ones would presumably be a random process
and result in a normal distribution of daughter drops.
Thus the production of a bimodal distribution from a
break-up process must be attributed to erosive break-
age involving removal of a number of small drops
from a larger one. This gives rise to two superimposed
 Simulation of bimodal drop size distributions in low-coalcsoence batch dispersion systems 451

distributions with the modes correspopdi4g to the
daughter or satellite drops, depending on their vol-
ume ratio (Brown and Pitt, 1972, Chatzi et al., 1989).
A first screening of the various phenomenological
breakage models based on their ability to predict
bimodal drop size distributions measured at steady
state (Chatzi et al., 1989) revealed the applicability of
eq. (14) for such systems. This model proposed by
Narsimhan et al. (1979) considers droplet breakage as
a result of oscillations due to relative velocity fluc-
tuations. The best fit to the steady-state distributions
has been obtained for erosive breakage to one
daughter and several satellite drops. Therefore, the
same model is applied in this study for the simulation
of the dynamic experiments.
The simulations were performed by using experi-
mentally measured distributions as the initial condi-
tion for integration of the population balance eq. (6).
The experimentally obtained volume frequency histo-
grams were transformed into the corresponding dia-
meter frequency histograms by using the equation:
where Xi and XVi are the corresponding diameter and
volume frequencies at each experimental size class
C i,srp having a width AC,,,,. Subsequently, the cor-
responding diameter density distribution was calcu-
lated as:
Ai = X,/AC,,.,,. (21)
The calculated discrete diameter density distribution
was interpolated to yield a continuous one by the use
of a one-dimensional quasi-cubic Hermite splines
method. Finally, the continuous diameter density dis-
tribution was evaluated at the characteristic diameter
of each size class used for the discretization of the
population balance equation. This set of values rep-
resents the initial condition used for the simulation, as
illustrated in Fig. 3 for an agitation rate of 200 rpm.
Figure 4 shows a comparison between the experi-
mental and predicted diameter and volume density
distributions after stirring for 45 min. The agreement
is quite satisfactory, except in the region of relatively
large drop sizes. The discrepancy appears to be more
significant in the volume density distribution and can
be attributed to an exaggeration of the dependence of
breakage rate on the breaking drop volume. There-
fore, eq. (14) predicts an almost instantaneous break-
down of the distribution tail.

ia1 condition for slmulatlon (at 15 min)

40 80 120 160 200 240

Drop dlametsr. pm

25

40 80 120 160 200 240 280 320

Drop dlamotmr. pm

Fig. 3. Experimentally
determinedinitialcondition(at agitationtime 15 rain)LIE&for simulationof the
dynamicdrop size distributionaat 25°C and 200 rpm.
452 E. G. CHATZI and C. KIFARISSIDFS

PredIction of D.S.O. at 45 mtn for constant X and NSA

$ 250

S
2 200
t;
5
=n 150
Z
e
g 100
-I

5 -- t

40 a0 120 160. 200 240

Drop diameter. pm

_ 125-

‘,E
$ loo--

5
2
5 75--
4

31
z 50 --
z!
t

$J 25

f I, ,,,

40 80 120 160 200 240 280 320

Drop diameter. pm

Fig. 4. Comparison between experimental and predicted diameter and volume density distributions at
45 min and an agitation rate of 200 rpm, according to the original breakage frequency eq. (14).

A reasonable modification of this model is to con- For breakage into a number of daughter and satellite
sider that the number of satellite drops, N,, stripped drops the minimum increase in the surface energy
out of the parent drop as well as the volume ratio of provided by the kinetic energy of oscillation of the
the daughter to the satellite drops, X, increase with the droplet equals:

PO’
size of the breaking drop. Several alternatives have

1
been tested based on their ability to fit the dynamic Ndexzf3 + N,
_ 1 a51u36u3”1/3

behaviour of the drop size distribution, the most CN,ox + NSnI”3

prevalent one being that of a linear dependence of

Therefore, the parameter Cvm in the expression (14)
both N, and x on the parent drop volume:
for the breakage frequency can no longer be treated as
N, = 1 + Int[S,,u,] (22) a constant but it should be recalculated for each
different breaking drop size according to:
x = 1 + S,VP (23)
where S,, and S, are the corresponding slopes. N,,x=~~ + N, l/2
c vm (24)
Equation (14) for the breakage frequency has been
-
- ‘& (Ndax + NsJZi3 - 11
derived as the product of the average number of
where C$,, is an adjustable constant.
eddies arriving on the surface of a droplet per unit
Fiure 5 shows the dependence of the breakage
time, 2, and the probability that the arriving eddy
rates on the parent drop diameter for constant and for
possesses energy greater than or equal to the min-
variable x and N,. In both cases the calculations were
imum increase in the surface energy required to break
performed by using the parameter values giving the
a drop of volume v (Narsimhan et al., 1979). In the
best fit to the experimental distributions obtained at
original derivation it was considered that the min-
an agitation rate of 200 rpm. Equation (14) for con-
imum increase in the surface energy for fragmentation
stant x and N, tends to overestimate the breakage
corresponded to binary equal breakage:
rate of the large drops, as compared to a more gradual
(2u3 _ ~)~n~~343/3y~3. increase of the breakage frequency with the drop
 Simulation of bimodal drop size distributions in low-coalescence batch dispersion systems 453

0.004 breakage rates calculated for our system at 200 rpm.

- Variable x 6 Nsa
1 Constant x 6 Nsa
q
0.00 0.01
mop Diameter, cm
Fig. 5. Comparison between the breakage rates calculated at
200 rpm for: (a) a variable volume ratio of the daughter and
satellite drops, r, and number of satellite drops, IV,, (b)
constant x and N, and (c) according to the model eq. (25)
proposed by Laso et ol. (1987b).
diameter predicted by using the modification eq. (24).
Laso et al. (1987) calculated empirical equations for
the functional dependence of the breakage and coales-
cence rates on drop volume, from transient behaviour
experiments and by using a simplified population
balance equation. Their data were represented by the
following expression for the breakage frequency:
g(v) = 4.04(10-6)(o,/D~)0~g’(N,&67
x(1 + 4)-1.94z-o.l9
where (NTYe)= is the Weber number of the main flow
[ = p,(N*)2Df/a], Z is the Ohnesorge number
[ = pd/(pcD,~)l’z] and C$is the dispersed phase vol-
ume fraction.
Although the breakage frequency evaluated from
eq. (25) is quite different from that necessary in the
full-scale population balance equation used in this
work, it may be qualitatively compared to the model
derived based on eqs (14) and (24). Figure 5 shows the
Considering the differences in experimental arrange-
f
ment, i.e. impeller to tank diameter ratio, and the fact
that eq. (25) has been evaluated by fitting unimodal
transient drop-size distributions, the agreement be-
tween eq. (25) and the present work is reasonably
good. Furthermore, the modified model introduced in
this work considering x and N, increasing propor-
tionally with the parent drop volume has the unique
ability to simulate the dynamic behaviour of bimodal
0.02 0.03 drop size distributions. Also the present model inher-
ently takes into account possible differences in the
breakage characteristics of different-size drops. Thus,
one satellite drop of size almost identical to the size of
the daughter drop is stripped off the very small-size
parent drops, whereas a larger number of satellite
drops of significantly smaller size is stripped off the
larger drops. The diameters of the daughter and
satellite drops produced by breakage are plotted in
Fig. 6 as a function of the parent drop diameter for
parameter values corresponding to the fitted experi-
mental data. For constant x and N,, both diameters
increase linearly with the diameter of the parent drop.
On the other hand, for variable x and N, one
daughter and one satellite drop of equal size are
produced for parent drop diameters of approximately
up to 50 q. After the smooth transition region of 50
to 100 pm, the daughter drop diameters increase al-
most linearly, bhereas the satellite drop diameters
(25) reach a value independent of the parent drop size.
The fit between the experimentally obtained drop
size distributions and those predicted by the modifikd
breakage frequency equation is significantly improved
as compared to the original model, especially in the
region of large-size drops. The simulated evolution of
the bimodal drop size distributions obtained at
200 rpm is summarized in Fig. 7. As the agitation time
increases, the 55 pm peak gradually decreases in in-
tensity giving rise to a new peak at 45 pm, similar to

0.02 1
0
daughter drops, verlable x & Nsa
1
satellitedrops, variable x & Nsa
.
daughter drops, constant x &*Nse
*
satellitedrops, constant x & Nsa

0.01 -

Parent Drop Diameter, cm

Fig. 6. Dependence of the daughter and satellite drop deters on the parent drop diameter: comparison
of the model assuming a constant volume ratio of the daughter and satellite drops, x, and number of
satellite drops, N,, to the one considering a variable x and N, for an agitation rate of 200 rpm.
454 E. 43. CHA~Z~and C. KIPARI~SIDE~
T Evolution of drop
40 80
Fig. 7. Predicted evolution of the diameter and volume density distributions for an agitation rate of
200 rprn, according to the modified model based on eqs (14) and (24).
the experimental observations (Fig. 2). The model also
predicts quite closely the evolution of the bimodal
drop-size distribution for different agitation rates.
In summary, the modification of the breakage
model introduced in this work successfully describes
the transient behaviour of the measured bimodal drop
size distributions. To our .knowledge, no previous
attempts of this sort are published in the literature.
The model proposed by Laso et (11. (1987b) was
reported to be unsuccessful in incorporating the
bimodality observed in several of their experiments.
Therefore, we believe that the present study is a step
towards understanding and describing the origin and
evolution of bimodality in di-rsed phase systems.
The observed differences between simulated and ex-
perimental data may be attributed to the underlying
assumptions in formulating the interaction model, to
the inherent experimental errors, as well as to a
limited contribution of coalescence to the experi-
mentally observed drop size distributions.
5. CONcL.USlONS
This work is a first attempt to incorporate the
bimodality into the equations describing the droplet
size distribution (simulation data)
120 160 200 240
Drop diameter. gam
Drop diameter. pm
interactions in agitated vessels. It has been possible to
modify the breakage model in order to predict the
dynamic behaviour of bimodal drop size distributions
measured by a laser diffraction technique, in terms of
the controlling process variables, such as physical
properties of the dispersed and continuous phases,
interfacial tension and agitation rate.
The modified model considers breakage of the
parent drops into one daughter and several satellite
drops. The volume ratio between the generated drops
as well as the number of satellite drops are considered
to be proportional to the parent drop volume. The
present model inherently takes into account possible
differences in the breakage characteristics of different-
size drops. Thus, one satellite drop of size almost
identical to the size of the daughter drop is stripped off
the very small-&e parent drops, whereas a larger
number of satellite drops of significantly smaller size is
stripped off the larger drops.
Though various assumptions and simplifications
are implied in the formulation of the breakage pro-
cess, the obtained agreement between observed and
predicted transient drop size distributions is quite
satisfactory.
 Simulation of bimodal drop size distributions in low-coakscence batch dispersion systems 455

Acknowledgment-The authors gratefully acknowledge the continuous and dispersed phase

EEC and the CPERI. for supporting this research under the densities, g/cm3
BRITE Project P-1560. ’ inter-facial tensibn, dyn/cm
standard deviation of daughter
drop distribution
NOTATION
dispensed phase volume fraction
A(4) diameter density distribution,
cm-t
A@,t) volume density distribution, cm-’
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