MohantyS-2000 - Modeling of Liquid-Liquid Extraction Column - Mohanty PDF

MODELING OF LIQUID-LIQUID EXTRACTION
COLUMN: A REVIEW
Swati Mohanty
Regional Research Laboratory (C.S.I.R.),

Bhubaneswar-751013, India
E-mail: swatijnohanty@yahoo.com
ABSTRACT
Mathematical models are reviewed for different types of commonly used

extraction columns, viz. pulsed sieve plate column, rotating disc contactor,
Kuhni column, spray column, Scheibel extractor, packed column,
Oldshue-Rushton contactor and reciprocating plate column. In addition,
numerical techniques, process simulators and some estimation methods for
model parameters have also been included. The review cites over 120
references.
Keywords: mathematical modeling, extraction column, population balance,

diffusion model, solvent extraction
INTRODUCTION
Liquid-liquid extraction is the second most important separation process

after distillation in chemical industries. Its early application was in
oil-refining, but it has now been extended to such varied applications as the
petrochemical industry, Pharmaceuticals, hydrometallurgy, nuclear industry
and environmental protection. Despite years of study, a design procedure
employing sound basic principles has not been developed and until today, the
design of extraction column is based on pilot plant data and design experience
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Vol. 16, No. 3, 2000 Modeling of Liquid-Liquid Extraction Column:
A Review
and hence is far from the optimum. Polydispersity of turbulent drop swarm is
the main obstacle in designing liquid-liquid extractors.
Mathematical models that adequately define the system lead to better
design of these equipments. However, adequate research has not been carried
out in this area, although attempts have been made to develop models based
on certain simplified assumptions. This is mainly due to the complexity of the
system where the dispersed phase constantly loses its identity due to breakage
and coalescence. Insufficient attention has been paid to the experimental
effort required to verify the utility of the models. Much remains to be done
before dispersed phase behaviour is adequately modelled and column
performance can be confidently predicted. Recent books edited by Godfrey
and Slater /!/ and Thorton 121 present detailed analysis of various types of
extraction equipment. Steiner and Hartland /3,4/ have discussed the
advantages and disadvantages of two early models proposed by Sleicher 15,61
for liquid-liquid extraction. One is the backmixing model, which assumes that
the dispersed phase consists of uniform sized drops without breakage and
coalescence. The other is the forward mixing model, which takes into
consideration the different drop size, drop breakage and coalescence, varying
velocities of the drops due to varying size. Some of the stagewise and
differential models and their solution methods have also been reviewed by
Pratt and Baird I and Steiner and Hartland /8/. Use of stochastic simulation
techniques (e.g., Monte Carlo techniques) has been introduced for simulating
liquid-liquid extraction, but these have been primarily applied to stirred tank
contactors and hence have not been included in this review. The purpose of
this paper is to present a general review of various models available for some
most widely used liquid-liquid extractors.
TYPES OF MODELS
Mathematical models for liquid-liquid extraction are categorised into

three basic types.
a) Empirical: These are the simplest of all the models and are obtained by
fitting experimental data with empirical correlations which are functions
of liquid physical properties, column geometry and operating conditions
of the column. The drawback of this type of model is that this cannot be
extrapolated beyond the stipulated range of application. This type of
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Swafi Mohanty Reviews in Chemical Engineering
model has been proposed for predicting the mean drop size and hold-up in
various types of extraction columns. The hold-up, , or the mean drop
diameter, d,n, is given as
or dm =f(z,,z2,.... zj (1)
where Z|, z2, ... z are physical properties, column geometry and
operating conditions,
b) Differential: These models are obtained by formulating differential
conservation equations for the column, both for the dispersed phase and
the continuous phase. Based on the representation of the dispersed phase,
the differential model is further classified into
i) pseudo-homogenous dispersion model (Fig.la), applicable for both
single phase as well as dispersed multiphase system and are based on
the principles of physico-chemical laws. The system is represented as a
continuum with the dispersed phase treated as pseudo-homogeneous.
The general unsteady state mass balance equations for the continuous
and dispersed phase are given as
a.= Vcc oz +EcC -L-koc(Ccc -Ccc/ )

^2 ' (2)
(3)
where is measured in the direction of flow of the dispersed phase 151.

ii) population balance dispersion model, applicable where the continuum
transport equation fails e.g. when a dispersed phase is discontinuous
and constantly undergoes changes and loses its identity due to
coalescence and breakage. Thus a differential drop population balance
for drops of different sizes in the dispersed phase is formulated for the
column (Fig.lb). The general drop population balance equation is
written as
201
A Review
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202
Swati Mohanty Reviews in Chemical Engineering
**\ ' T\ /- / j . " IE ~ / I . D/ j r/j\ /4\
where the birth, B(d), and death, D(d) of drops of size d, relates to
breakage and coalescence in the volume element of height, dZ. A good
review of population balance models applied to chemical processes is
presented by Ramakrishna 191.
c) Stagewise: In this type of model, the column is described as a series of

completely mixed stages and the model equations are developed based on
the principle of mass conservation applied to each stage (Fig.lc). These
are similar in form to equations (2), (3) and (4) 161. The stages may be
real, as in agitated stagewise columns, or cascades with a large number of
hypothetical stages, as in differential extractors.
MATHEMATICAL MODELS
The first models of extraction column that were reported were simple in
nature. Both the phases were assumed to be in differential contact with each
other, with each phase assumed to be a continuum. The dispersed phase was
treated as pseudo-homogeneous and backflow was accounted for by the axial
dispersion coefficient. In the subsequent models, the dispersed phase was
represented by monodispersed or polydispersed drops without undergoing
breakage or coalescence. The complex behaviour of the dispersed phase,
consisting of swarms of droplets with a wide size distribution, varying
velocities relative to the continuous phase, and varying mass transfer rates,
could be represented by the hydrodynamic and mass transfer behaviour of
some representatively-sized single drop, normally the surface-volume or
Sauter mean diameter drop. In the later models, the coalescence was
accounted for by introducing a coalescence height, which indicates the
average distance the drops actually travel before they coalesce and redisperse
to maintain the original drop size distribution. The concentration of the
dispersed phase was assumed to be constant throughout a given cross-section
of the column due to sufficiently intensive coalescence and redispersion.
More recently, population balance models have been developed to predict
drop-size distribution and hold-up profiles along the length of the column
taking into account drop breakage and coalescence. In addition, a number of

203
A Review
empirical correlations for predicting the hold-up in different types of

extractors have also been reported. A unified correlation which can predict
the hold-up in eight different types of extraction columns has been proposed
by Kumar and Hartland /l O/. A summary of different models for various types
of liquid-liquid extractors is presented in Table 1.
Pulsed Sieve Plate Extraction Column (PSE)

This type of liquid-liquid extractor finds application mainly in nuclear
processing industries. Most of the models reported for this type of extractor
are based on population balance of drops. Models by Haverland et al l\ I/,
Dimitrova AI Khani et al I\2I and Zimmermann et al /13/ are based on the
basic population balance model given by equation (4). In the steady state
hydrodynamic model, Haverland et al /I I/ have neglected drop-drop
coalescence and have proposed a normalised Beta-distribution for the drop
size distribution which was found to fit best with the experimental data. A
correlation for break-up probability for drops of different sizes has been
proposed based on experimental data. Although the model predictions for
hold-up and drop size distribution agree quite well for the system
toluene-water and under operating conditions where coalescence is negligible,
it would not be applicable for systems and operating conditions where
coalescence is significant. Dimitrova Al Khani et al. I12I have made certain
assumptions for drop-drop interaction, such as that a mother drop breaks into
three equisized drops and the breakage rate is proportional to the eighth
power of the drop diameter. For coalescence, experimental values for the two
parameters, one for collision efficiency and another for coalescence
probability, have been used but no detailed method of determination of these
two parameters has been reported. For the mass transfer model, a linear
equilibrium relationship and the mass transfer coefficient independent of the
drop diameter have been assumed. The model contains two fitting parameters,
one for the drop transport and the other for the drop breakage which limits the
applicability of the model. Zimmermann et al. /13/ have applied the
population balance model to multi-component extraction. The model involves
too many parameters to be known. The authors have validated the model
against pilot plant data, but the values used for various model parameters
have not been given. Methods of determination of these parameters would
have been useful for applying the model to other sieve plate extractors.

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Mohanty and Vogelpohl /14/ have simplified the differential population

balance model of equation (4) into a stagewise model which considerably
reduces the computational time. The space between two consecutive
sieve-plates is taken to be a single stage. Both breakage and coalescence have
been considered. A beta distribution for the daughter drop size distribution
has been used and the experimental breakage probability has been used.
However, the coalescence parameters have been taken as adjustable. Qian and
Wang 1151 have developed a stagewise model where it is assumed that the
drop size distribution does not change throughout the column. At the end of
each stage, the drops coalesce to equalise the concentration and then
redisperse to maintain the original drop size distribution. For the mass
transfer coefficient of the dispersed phase, the Handlos and Baron /16/
correlation is used, while the Higbie penetration model is used for the
continuous phase. Although the model is quite simple, the predicted
concentration profile agrees well with the experimental data. The stagewise
population balance model by Garg and Pratt /17/ accounts for drop breakage
and coalescence and uses experimentally determined coalescence and
breakage parameters, which is unlike other models where these are used as
adjustable parameters. The breakage and coalescence rate constants have
been expressed as functions of hold-up and drop size. However, the
assumption of binary breakage of drops and coalescence occurring only
between adjacent and same drop sizes does not adequately represent the
actual system. Moreover, the colorimetric method used for determination of
coalescence rates, where drops of two different colours (yellow and green)
coalesce to give rise to a third colour (red), makes it difficult to distinguish
the colours when multiple coalescence takes place. Although the prediction of
drop size distribution at the outlet compared well with experimental data,
comparison of predicted number of coalesced red drops with experimental
data showed that the agreement was good only for the first few plates.
Blass and Zimmermann /18/ have presented a simple stagewise, backflow,
mass transfer model for a pulsed sieve-plate extraction column assuming a
constant holdup. A recirculation regime model developed by Prabhakar et al
1191 compares well with experimental data obtained for mixer-settler and
emulsion regime. Experimental determination of hold-up shows that in the
mixer settler region, the hold-up is affected by the hole diameter whereas in
the emulsion region it is affected mainly by the free area. Also, the drop
formation takes place in the mixer-settler region due to dispersed phase flow
211
Vol. 16. No. 3, 2000 Modeling of Liquid-Liquid Extraction Column:
A Review
through the perforations and drop breakage takes place in the emulsion region
due to pulsing action within the plate stack. Hold-up was found to be high
when the solute transfer was from the continuous to the dispersed phase.
The empirical correlation for predicting the hold-up in a PSE proposed by
Kumar and Hartland /20/, which was compared with other available empirical
correlations, is
| Af -(Af)m
(5)
where
O.33
(Af)m = (6)
The constants k b k2 and k3 that appear above are given in Table 2 for the
case of no solute transfer, solute transfer from continuous to dispersed phase,
and solute transfer from the dispersed to continuous phase. The correlation is
based on the available data for column diameters of 25-213 mm and is
applicable for prediction of hold-up in the mixer settler, transition and
emulsion regions of operation within an average error of 17.8%. The
influence of hole diameter and column diameter was insignificant.
Table 2
Parameter values for no solute transfer, solute transfer from continuous to
dispersed phase and solute transfer from dispersed to continuous phase.
k, k2 k3
no solute 2.10xl0 6 44.53 9.69 10
c-d 2.14x10* 44.53 9.69 xlO' 3
d-c l.lOxlO6 50.56 9.69 xlO' 3

Rotating Disk Contactor (RDC):

This type of extractor is commonly used for deasphalting of petroleum,
for desulfurisation of gasoline, and for recovery of phenol from wastewater. A
new Open Turbine Rotating Disk Contactor (OTRDC) has been developed by
Zhu et al. I2\l that has higher efficiency than the RDC and is also suitable for
liquid-liquid-solid as well as liquid-solid systems. Modeling studies on the
RDC include pseudo-homogenous and population balance models, as well as
those that take into account the interfacial reaction. The complexity of models
accounting for interphase
\
chemical reaction increases since the observed rate
is a function of both chemical kinetics and diffusion.
The differential pseudo-homogenous dispersion model by Chartres and
Korchinsky 1221 includes a mass balance equation for each drop size fraction
for the dispersed phase and a mass balance equation for the continuous phase.
Drop coalescence has been accounted for by introducing a coalescence height
to equalise the solute concentration and to then redisperse maintaining the
original drop size distribution. The drop size distribution has been estimated
using Mugele-Evans functions /98/. The effect of drop size distribution was
found to decrease with a decrease in the coalescence height. The study also
shows that the axial dispersion in the dispersed phase does not influence the
mass transfer significantly and can be neglected. However no verification of
the model equation has been made with experimental data.
Korchinsky and Cruz Pinto /23/ have improved this model by introducing
a settling zone above the agitated section of the column, and by eliminating
the assumption of constant continuous phase concentration for estimating the
mass transfer coefficient by replacing it with rigid drop and turbulent
circulating drop model. The predicted number of transfer units was, on the
average, ca. 10% higher than the experimental values. In order to improve the
agreement, the mass transfer coefficient and the axial dispersion coefficient of
the continuous phase were adjusted. Thus four parameters, two for the
agitated zone and two for the settling zone, can be adjusted. Cruz-Pinto and
Korchinsky 1 have also solved the model equation of a RDC by
incorporating one of the two diffusion models, i.e., either the Newman rigid
drop model 1251 or the Handlos-Baron /16/ turbulent circulating drop model,
but taking into account the variation in the solute concentration of the
continuous phase. This has been done by solving simultaneously the
hydrodynamic and mass transfer equation for swarm of liquid drops. The
213
A Review
model takes into consideration the axial mixing and the time dependent mass
transfer coefficient. The mass balance equation for the continuous phase is
solved simultaneously by the drop diffusion model using a finite difference
method and the results compared with that obtained by exact solution. The
predicted results have been compared with experimental data. The operating
condition of the RDC was so chosen that drop coalescence and drop breakage
were negligible. The discrepancy has been attributed to an inaccurate estimate
of the extent of mixing in the continuous phase and by accounting for the
range of drop mass transfer that depends on the size.
A population balance model developed by Casamatta and Vogelpohl 7267
for a RDC accounts for drop coalescence and drop breakage with an
assumption that the drops break-up into three equal size daughter drops. The
factors accounting for the coalescence and breakage have been taken as
adjustable parameters.
The population balance model by Ghalehchian and Slater 7277 considers
drop breakage but no coalescence. The characteristic velocity predicted from
correlation from literature has been modified to minimise the discrepancy
between the predicted and experimental hold-up. Also the parameter, m, used
to account for the drop swarm, to predict the drop velocity has been taken as
the adjustable parameter. The beta function has been assumed for daughter
drop size distribution. The error in predicting hold-up is between 20% and
Sauter mean diameter between 18%.
A steady-state differential pseudo-homogenous dispersion model
involving extraction with interphase chemical reaction is given by Sarkar et al
/28,29/. The model treats the disperse phase as pseudo-homogeneous. The
surface area for mass transfer is based on the average drop size measurement.
Expressions for extraction rates for very slow reactions, slow reactions, and
fast reactions based on the film penetration, and Dankwerts models have been
given. The predicted extent of reaction has been compared with experimental
data for RDC with a maximum deviation being 20%. However, the model has
certain limitations, one being that it assumes the resistance to mass transfer
lies only in the aqueous phase and experimental values of mass transfer
coefficient without reaction under actual conditions of turbulence are
required. Also the effect of droplet interaction has not been taken into
consideration.
The stagewise model by Azimzadeh-Khatayloo 7307, which is an
improvement over Misek's model /31/ includes the possibility of entrainment

Swat i Mohanty Reviews In Chemical Engineering
of smaller drops by the continuous phase. A mean diameter based on d43 =

Znjdj4/Znjdj3 has been used instead of the Sauter mean diameter for better
estimation of the characteristic velocity. The model incorporates into it the
influence of drop size distribution on mass transfer.
A new approach by Zhang et al. 7327 uses stochastic process theory to
account for forward mixing, backmixing and mass transfer behaviour of the
drops in the model. The drops move in the column in a stochastic manner and
the displacement of the drops is described by the Fokker-Planck equation 7337
m
where q is the transition probability density, t and are time (1>), and both w
and are positions of the drop at time and t, respectively. Also, U is the
average velocity of the drop and Ed is the axial dispersion coefficient of the
dispersed phase. The solution to this equation gives the age distribution of
drops at different heights. From the age distribution of different drops, the
RTD of drops at any height can be determined. The axial dispersion
coefficient is a function of the RDC rotor diameter, the height of a
compartment, the drop axial velocity and the free cross-sectional area. The
concentration of the dispersed phase is then calculated by solving the mass
transfer equation for a single drop and then integrating over all drops at any
height to get the overall concentration of the dispersed phase. Both
coalescence and redispersion have also been neglected. The drop size
distribution was measured experimentally and found to fit well with
Mugele-Evans upper limit log-normal distribution function. Three types of
model, namely, those of Newman 7257, Kronig and Brink /34/, and Handlos
and Baron /16/ have been used for estimating the mass transfer coefficient of
the dispersed phase, depending on the drop Reynold's number. The mass
transfer coefficient for the continuous phase is based on the Calderbank and
Moo Young /35/ correlation. For the axial dispersion coefficient, the
correlation suggested by Zhang et al. 7367 has been used. The mass transfer
resistance in the continuous phase has been assumed to be negligible. A
comparison between the number of transfer units when the solute transfer is
from the continuous phase to the dispersed phase has been found to agree
well with experimental data, but the deviation was appreciable when the
transfer was in the opposite direction, i.e., from the dispersed to the
215
A Review
continuous phase. This may be due to coalescence as coalescence is high

when the solute transfer is from the dispersed phase to the continuous phase.
Zhu et al. I2\l have studied the hydrodynamics, axial mixing and mass
transfer in OTRDC using the combined forward mixing and backflow model
for axial mixing.
In addition to the above discussed models, there are some empirical
correlations that predict the hold-up in an extraction column. Sarkar et al /37/
have correlated the experimentally determined hold-up as a function of rotor
or impeller speed, column height, and dispersed phase velocity using the
toluene-water system. The correlation cannot be taken as a general one, since
the constants in the correlation may not be same for a RDC with a different
configuration and when a different system is used. However, Kumar and
Hartland 738, 39/ have suggested correlations for predicting the mean drop
size and hold-up in a RDC as a function of column geometry, operating
conditions and physical properties.
Kiihni Column:
This type of column has been used for separation of aromatic and aliphatic
hydrocarbons. Modeling studies reported for this type of column are
relatively few in number and include both pseudo-homogenous and
population balance models. A dynamic pseudo-homogenous dispersion model
has been applied for simulating a Kiihni column by Hufnagl et al /40/ and
Hufnagl and Blass /41/ assuming constant flow rate of both the phases and
constant levels in the column. The hold-up and the Sauter mean diameter have
also been assumed to be constant along the length of the column. At the
column inlet and exit, the model includes a mixer and a dead-time term to
describe the separation chamber. Correlations for estimating the Sauter mean
diameter, relative phase velocity, axial dispersion coefficient and mass
transfer coefficient have been taken from literature and in some cases the
correlation constants have been modified to obtain a best fit with
experimental data. Correlations for the distribution coefficient and interfacial
tension have been suggested that are dependent on solute concentration. This
model is a component part of the DIVA simulator /42,43/. Simulated
responses for disturbances in feed concentration and flow rate have been
compared with experimental data. In the case of a disturbance in the feed
concentration, the simulated curve at feed inlet attained steady state faster

than the experimental curve. This may be due to the mixing in the feed line
that has not been accounted for by the model. When an increase in flow rates
of both the phases occurs, there is a sudden overshoot in the concentration
due to the level controller action to maintain constant interface level. The
deviation of the simulated values from the experimental value are due to the
assumption that the flow rate of both the phases are constant, whereas in
actual practice, due to the counteraction to maintain the interface level, there
is significant deviation in hydrodynamics. The model has not taken into
consideration the level controller.
In addition to the pseudo-homogenous dispersion models, several models
based on drop population balance have been reported. The differential
population balance model given in equation (4) was used to perform a steady
state simulation of the Khni column by Haunold et al. /44/. Coalescence has
been neglected whereas breakage has been described by a breakage
probability function (function of impeller speed and Weber number) and a
daughter drop size distribution function. All the parameters have been
determined experimentally. However, comparison between the predicted and
experimental hold-up shows that the agreement is satisfactory only at low
flow rates. Steiner /45/ has presented a population balance model based on
geometrical droplet size classification for estimating the hold-up in Khni
column. The advantages and disadvantages of population balance models
have also been discussed.
The transient stagewise population balance model by Gerstlauer et al. /46/
neglects coalescence and assumes a binary breakage of drops. The model
considers each drop in the dispersed phase to be characterised by the mass of
the solvent and the mass fraction of the solute. The breakage rate is predicted
by the model proposed by Tsouris and Tavlarides /47/ and the daughter drop
distribution is predicted using the method of Coulaloglou and Tavlarides /48/.
Although the model considers polydispersity of the drops, all drops are
assumed to have the same velocity, which is not true in reality. The mass
transfer coefficient has been calculated using the Handlos and Baron /16/ and
Heeitjes et al. /49/ models. The Gerstlauer et al. /46/ model has been used to
simulate the startup behaviour of a Khni column for drop number
distribution, dispersed phase hold-up, and solute mass fraction. No
comparison has been made with experimental data in order to check the
validity of the model. In their later work /50,51/, the same model has been
simplified by assuming that the solute concentration is same in all the drops.
217
A Review
The backflow of the continuous phase has been calculated by the wake
volume of the continuous phase carried away by the dispersed phase. The
simulated start-up and step change behaviour of the column agreed well with
measured solute concentration profile. This model has been incorporated into
the DIVA simulator.
Spray Column:
This is the simplest of all extractors and is used for washing, treating and
neutralisation. The disadvantage of this type of column is its poor
performance due to intensive continuous phase backmixing. Not many models
have been reported for this type of column.
A hydrodynamic model for a spray column operating in the dense packing
region of drops has been developed by Noworyta and Kroti 1521 taking into
account the drop coalescence. The model assumes uniform sized drops across
any cross-section and constant flow rates of both the phases. The analytical
solution of the differential equation has been presented for predicting the
hold-up along the length of the column, which is found to agree well with
systems with low coalescence.
Seibert and Fair 1531 developed mechanistic hydrodynamic and mass
transfer models based on fundamental principles for spray columns. The key
assumptions are that the drops are spherical and drop size can be represented
by the Sauter mean diameter. Models for determining the drop diameter, drop
velocity, drop-drop interaction, hold-up and flooding velocity along with a
model for estimation of the mass transfer coefficient from fundamental
principles with limited number of empirical correlations have been presented.
Comparison between experimental and predicted hold-ups shows that the
agreement is good at low hold-up, but deviates significantly near flooding
regions. The predicted and experimental overall mass transfer coefficients
based on the continuous phase agreed quite well.
Schermuly and Blass /54/ have developed a model for a 3-component
mass transfer in a spray column. The system chosen is
glycerol-acetone-water. The model takes into account the variation of
concentration and mass flow rate along the column and liquid phase
backmixing. The mass transfer coefficients are based on both the theoretical
and experimental results available in literature on mass transfer in saturated
and unsaturated phases. A correction for the eddy diffusivity parameter

calculated using the Handlos Baron formula and the backmixing parameter
has been determined by adjusting these parameters using a best fit criterion
between the calculated and experimental data. Since adjustable parameters
have been used, the model cannot be confidently used for predicting the
column performance adequately.
Kumar and Hartland 7557 have proposed a correlation for predicting the
hold-up for a spray column in the loose and dense packed region of operation
for with and without mass transfer. The correlation is a function of column
geometry, physical properties and known operating parameters.
Scheibe! Extractor
Literature on modeling of Scheibel extractor is relatively sparse and
includes works by Alatiqi et al. 756,577 and Pang and Johnson 7587. Alatiqi et
al. 7567 have developed a stagewise, backflow model for mass transfer in a
Scheibel extractor. Each stage is assumed to consist of a mixing zone and a
settling zone. In the mixing zone, mass transfer takes place while coalescence
takes place in the settling zone. A correlation for hold-up which is a function
of agitation speed and phase ratio has been suggested for predicting the
hold-up at different heights of the column. The distribution coefficient is also
expressed as a function of solute concentration. Physical properties, such as
viscosity and surface tension, have been correlated as functions of solute
concentration. For estimating the continuous phase and drop-side mass
transfer coefficients, the correlations by Gamer and Tayeban 7597, and Rose
and Kintner 7607 have been used, respectively. The three parameters that are
adjusted to minimise the discrepancy between the simulated and experimental
results are the two backmixing parameters (one for the continuous and the
other for the dispersed phase) and the overall mass transfer coefficient. It was
found that the two backmixing coefficients were close to zero and hence were
neglected and the simulation was done with one adjustable parameter. This
shows that extrapolating a single droplet mass transfer correlation to droplet
swarms does not accurately predict the mass transfer coefficient. Steady-state
analysis studies were carried out and they found that the agitation speed and
the phase ratio had considerable influence on the control structure.
In their further studies, Alatiqi et al 7577 have studied two types of
dynamic stage-wise models, one equilibrium and the other non-equilibrium
with backflow, assuming constant mass transfer coefficient, flow rates and

219
Vol. 16, No. 3. 2000 Modeling of Liquid-Liquid Extraction Column:
A Review
hold-up. Response to step disturbances in flow rates, solute concentration,

agitation speed and backmixing coefficients were studied. However, no
verification has been made with experimental data.
Transient response studies have been reported in simulation of
liquid-liquid extraction column. Pang and Johnson /58/ have developed a
stagewise dynamic model for a modified Scheibel extractor and have studied
the frequency response to a pulse input at the feed concentration in the range
zero to 1.2 radian/minute. The model equations have been transformed to the
frequency domain to obtain the frequency response instead of the time
domain transient response for any disturbance in the feed concentration. The
stages were assumed to be non-identical (i.e., the overall mass transfer
coefficient was assumed to vary from stage to stage) and under
non-equilibrium conditions. The mass transfer coefficient, the time delay and
the number of mixing stages at both ends of the column, as well as the
fraction of the feed and the solvent entrained at two ends of the column, were
taken as fitting parameters and were obtained by obtaining a best fit with
experimental and predicted frequency response (amplitude ratio and phase
shift). When the predicted frequency response was transformed to the time
domain and compared with experimental transient response, the agreement
was good.
Packed Column:
Packed columns are preferred to spray columns since they increase the
drop coalescence and breakage and decrease axial mixing, which results in
improved performance. Inspite of their popularity, not many modeling
studies have been reported in the literature. The mechanistic hydrodynamic
and mass transfer model for spray columns developed by Seibert and Fair 1531
has also been extended to packed columns and has been applied to various
types of packings. However, the axial mixing of the continuous and dispersed
phases has been neglected and a tortuosity factor has been introduced in the
drop velocity equation. The discrepancy between the predicted hold-up and
overall mass transfer coefficient was higher than that for spray columns.
Steiner et . /61/ have presented simplified differential as well as stagewise
models for predicting the hydrodynamic and mass transfer performance of an
extraction column filled with regular packings. For the differential model, the
coalescence and breakage time, the drop velocity, and the mass transfer

coefficient have been assumed constant and a linear equilibrium relationship

has been assumed. The drops are assumed to be monodispersed with
negligible axial dispersion. Analytical solutions for the drop volume and
concentration profiles for the continuous and dispersed phases have been
presented. The drop breakage-coalescence parameter and the inlet drop size
were taken as adjustable and were obtained by minimizing the difference
between the measured and predicted drop size profile. For the stagewise
backflow model, the breakage and coalescence times, drop velocity and the
mass transfer coeffioient are estimated as functions of drop diameter. The
mean mass transfer coefficient was estimated using the Newman's function
1251 and the age distribution of drops as given by the penetration theory of
Dankwerts I62I. The diffusivity factor, R, which is the ratio of eddy to
molecular diffusivity, was taken as adjustable in the estimation of mass
transfer coefficient from Newman's function by minimising the difference
between the predicted and experimental concentration profiles. The authors
have shown that there is significant change in the mass transfer coefficient
along the height of the column, hence the assumption of constant mass
transfer coefficient in the differential model is not justified. The model
developed by Garg and Pratt /17/ for sieve plate extraction columns has been
extended to packed columns by Hamilton and Pratt 7637 and the coalescence
and breakage rate constants were obtained by the same -method of
colorimetry. The predicted column height has been presented for three
different cases, i.e., (1) when no breakage and coalescence takes place; (2)
when measured coalescence and breakage rates are used; and (3) when
infinite coalescence and monosized dispersion are assumed. However, no
comparisons have been made with experimental data. In determining the
coalescence and breakage constants, experimental data on the fraction of red
drops in different drop size intervals have been used. The experimental data
have been smoothed and correlations have been proposed for breakage and
coalescence rate constants as functions of drop diameter and hold-up. The
predicted rate constants vary significantly from experimental rate constants,
which shows that this method of determining the coalescence and breakage
rates may not be very accurate.
In addition to the above models, Salem et al. 7647 have proposed a model
based on non-equilibrium stages. An overall and component balance is made
for the column. The flow rate of the extract stream in each stage is estimated
by Edmister group relationship 7657
221
A Review
(8)
which is then used to calculate the raffinate flow rates in each stage. The
composition of the raffinate and the extract phases are then calculated and
compared with the experimental compositions. If the discrepancy is not
within the convergence limit, then a new number of stages is assumed and the
calculations repeated until convergence is achieved. The ratio of the
calculated extract phase solute concentration to raffinate phase solute
composition gives m'. The m' is therefore the non-equilibrium distribution
ratio of the solute in the two phases. The ratio of m' to the experimental
equilibrium distribution ratio, K, gives the extraction efficiency. Only limited
work has been carried out and no general conclusions have been made as to
how the extraction efficiency could be affected with change in operating
conditions. Arimont et al. I66I have tried to develop a model based on the
complete life-cycle of a single drop, i.e., formation, cleaving, coalescing or
departure from the column. The model equation is applied to each newly
formed drops. The model has been tested for the system n-butyl-
acetate/water/acetone and has been found to agree well with experimental
data.
Oldshue-Rushton Contactor (ORC), Disks and Rings Pulsed

Column:
The ORC's have been used in petrochemical, metallurgical,
pharmaceutical and fertilizer industries. Only limited studies on this type of
extractor have been reported in the literature. Lee et al. 1611 and Lee and Kim
7687 have proposed a stagewise drop population model for this type of
extraction column where the five parameters accounting for drop breakage
and coalescence have been taken as adjustable. These parameters were seen
to vary with varying operating conditions. Experiments on drop breakage in
different types of extractors have been reported in literature. To improve the
model, it would be desirable to obtain the breakup parameters experimentally.
A transient, stagewise, population balance model accounting for backflow and
forward flow has been developed by Tsouris et al. I69I. The drop breakage
model is based on the eddy-drop collision frequency and breakage frequency,

while the drop coalescence model is based on collision frequency and

coalescence frequency. The convective terms have been accounted for by the
forward and backward exit frequency of drops from one stage to another.
Good agreement between the experimental and predicted hold-up and Sauter
mean diameter has been reported. A single adjustable parameter has been
used in the model for forward and backward exit frequency by fitting
experimental data with the population balance model solution. The model has
also been used for simulating model based predictive control. The
pseudo-homogenous dispersion model developed by Sarkar et al. /28, 29/ for
RDC as described earlier has been validated for ORC also. Korchinsky and
Azimzadeh-Khatayloo /70/ have proposed a stagewise model and used it for
predicting the concentration profile along an ORC. The continuous phase was
assumed to be completely mixed and coalescence was neglected in each
stage. The axial mixing was accounted for by assuming a backflow between
the stages. However no comparisons were made with experimental
concentration profile.
The population balance model given by equation (4) has also been used
for simulating the hydrodynamics and mass transfer in a Disks and Rings
pulsed column by Dimitrova AI Khani et al. \. Assumptions made are
similar to that by Casamatta and Vogelpohl 1261, i.e., the drops break into
three equisized daughter drops and the breakage rate is proportional to the 8th
power of the drop diameter. The model involves three adjustable parameters
(the mass transfer coefficient, the breakage intensity and the coefficient for
calculating the characteristic drop velocity), which are obtained by fitting the
predicted and experimental hold-up and concentration profile. The
distribution coefficient is assumed to be constant and equal to 3.636 for the
system water-acetic acid-isopropyl ether.
Reciprocating Plate Column (RFC):

These types of extractors are used in pharmaceutical, petrochemical,
metallurgical and chemical industries. The specific types of RFC include
Karr, Prochazka and Tojo/Miyanami. Hafez et al. nil have presented a
design model for a Karr reciprocating plate extraction column. The model
calculates the diameter of the column at which flooding occurs and if the
degree of extraction is known then the height of the column. A hydrodynamic
and mass transfer model for a Karr RFC has been developed by Camurdan et

223
A Review
. /73 For estimating the hold-up, the following model is proposed:
(1-)2 (9)
where L = -=-;
where Kk =30 for rigid drop and 15 for circulating drops. The model
predicted the hold-up with reasonable accuracy for agitation rates greater than
3 cm/s. The model does not take into account transfer of solute from the
dispersed to the continuous phase which enhances the coalescence rate and
hence the model is not suitable for mass transfer from dispersed to continuous
phase. For the mass transfer, a stagewise model has been proposed with axial
dispersion in both the phases. A linear equilibrium relationship has been
assumed and the aqueous phase mass transfer resistance has been neglected.
The axial dispersion coefficient for both the phases were estimated using the
correlation given by Hafez /74/. The overall mass transfer coefficient was
taken as the adjustable parameter to obtain a best fit between the experimental
and predicted aqueous phase outlet solute concentration. The system chosen
was water-acetic acid-kerosene. This shows that the correlation used for
estimating the mass transfer coefficient is not suitable for the system chosen.
Sovov et al. 5/ have proposed a model for prediction of mean drop size
in any stage for a vibrating plate extractor (VPE) or Prochazka RFC. In this
model, an exponential rate of change of mean drop size has been assumed
(12)
where the constant, Kp depends on the plate type and dm is the limiting drop
size. The total hold-up in any stage is the sum of the hold-up in the densely
packed layer zone and the hold-up in the loosely packed zone. A semi-

empirical correlation has been proposed for predicting the hold-up in the
densely packed zone
V.d (13)
rv , A
where kv is a fitting parameter.

For the loosely packed zone, the hold-up, ; is obtained from the solution
of the nonlinear equation
Hence the total hold-up in any stage is the sum of the above two hold-up,
The model parameters K p and m were evaluated by minimizing the

deviation between the experimental and calculated hold-up profiles. For
predicting the thickness of the densely packed layer at the plate, an extra
parameter is to be determined whereas for the sieve plate, an extra parameter
is required to account for the instability near flooding.
GENERAL
In addition to the above models for various types of columns, there are a
few that are more general in nature and can be extended to different types of
columns.
A drop population model for agitated columns has been proposed by
Steiner et . 6/ assuming a back flow model for the continuous phase and
two different types of models, i.e., forward mixing and mixing in both
directions, for the dispersed phase. In the forward mixing model, the drop
size distribution is assumed to remain constant and coalescence and
225
A Review
redispersion are accounted for by assuming that all the drops coalesce and
redisperse thereby maintaining the original drop size distribution. The number
of such mixing stages introduced into the column is left as a free parameter
and is obtained from the measured concentration profiles. A logarithmic-
normal distribution of drop size is assumed. In addition, it is assumed that
coalescence takes place between two equal sized drops and a drop breaks into
two equal sized drops. The rate constants for the breakage and coalescence
have been taken as the adjustable parameters and were fitted to get good
agreement with experimental data obtained in a pilot-plant agitated column.
Caminos et al. have developed a steady-state stagewise model for
extraction columns assuming each stage to be in equilibrium using phase
equilibria obtained by the UN1FAC group contribution method /78/. A total
and component balance has been made for each stage. The model can be
applied to both stage extractors as well as sieve plates and has been applied to
industrial extractors. A solution method that requires less computation time
has been suggested. Sereno et al. /79f have assumed a constant hold-up along
the length of the column and have obtained a dynamic mass balance equation
for describing the concentration in both phases of the system. Instead of using
a rigorous thermodynamic model for describing the distribution ratios of the
ternary system, local non-linear models have been used that are valid over
moderate range of composition, which saves considerable computer time. The
distribution ratio, which is first evaluated by using a rigorous method such as
UNIFAC, is then fitted by polynomial approximation in the following form
In K-t = LljJc^f +L2y?ef +L3, i = 1,2,3
where LI, L2 and L3 are adjustable empirical local model parameters, and xref
and yref are mole fractions of the reference component in the raffmate and
extract phases, respectively. The dominant component is chosen as the
reference component. Introducing time derivative of the distribution ratios in
the general mass balance equation leads to a differential mass balance of
component i in the equilibrium unit. The differential equation is solved by
GEMS (General Equation Modelling System) /80/. The equation for a single
equilibrium unit has also been modified to account for a multistage model.
Each stage is treated as an equilibrium stage and no backmixing between the
stages has been assumed. The model-predicted concentration profiles of the

raffmate and extract phases in multistage extraction columns has been

compared with those predicted by other workers for extraction of cyclohexane
from -heptane using furfural as the solvent, and extraction of acetone from
water using 1,1,2-trichloroethane as the solvent. The model predictions were
in exact agreement with that of other workers.
PROCESS SIMULATORS
Simulators with built-in models applicable to various process industries

are also available. Black /81/ gives a brief description of a process simulator
/82/ and its application to various petroleum and petrochemical industries for
simulating distillation columns, reactors, heat exchangers, pumps, mixers,
liquid-liquid extractors, etc. However, only stagewise simulation of
liquid-liquid extractors is possible with this simulator. Marquardt et al. /42/
have presented the tools available for dynamic simulation of chemical plants
with special reference to the DIVA simulator /43/, which was developed by
the authors. The DIVA simulator has the dynamic model developed by
Hufnagl et al. /40/ as a component.
NUMERICAL TECHNIQUES
Model equations range from simple to more complicated form. In some

cases, the equations can be solved analytically, while in others, sophisticated
numerical techniques may be needed to solve the equations. Methods for
solving these equations over the years have been suggested by several
authors. Roche /83/ suggested a solution method for solving
multi-component, multistage liquid-liquid extraction column in early work.
Wang and Wang /84/ later reviewed the solution methods available for
simulation of separation process models. The three basic methods, namely,
equation decoupling, relaxation, and simultaneous solution methods,
although discussed with reference to distillation column, are also applicable
to any type of multistage, countercurrent separation process involving mass
transfer between two fluid phases. A general calculation method for
simulation of a stagewise, steady-state, multi-solute, countercurrent
extraction with axial dispersion has been suggested by Ricker et al. 7857. In
227
A Review
this method, the convergence of the solution of the model equations is very
fast without making use of any special convergence-promotion techniques.
Chatzi and Lee 7867 have suggested a numerical solution for the
homogeneous model developed for a batch agitated liquid-liquid extraction
process taking into account the drop breakage and coalescence. An algorithm
for solving stiff differential equations using a semi-implicit Runge-Kutta
method and its application to liquid-liquid extraction has been proposed by
Michelsen/87, 887.
Kronberger et al. 7897 have suggested a new solution method for solving
the system of differential population balance equations. The system of each
Integra Differential Equation (IDE) (mass balance and volume balance
equations) is discretised with respect to the drop diameter by applying the
Galerkins projection technique to give n Partial Differential Equations
(PDE's) where n is the number of drop size intervals considered. The coupled
PDE's are then space-time discretised by using finite-volume technique. The
spatial derivatives in the dispersive flux are approximated by central
differences and integration in time is performed by the Euler method. This
method has been implemented for simulation of an extraction column that is
calculated using the flux-extrapolation method with a time increment of 0.1 s.
Stable discretisation of the convective term has been incorporated. Ribeiro et
al. 7907 suggest an algorithm for solving the population balance equation
(pbe) that adequately predicts the drop distribution function for a perfectly
mixed continuous or batch vessel with spatially homogeneous, stirred
turbulent dispersion. A first-order, explicit finite-difference method has been
used to solve the pbe. For the chosen systems, toluene-water, and methyl-
isobutylketone-water, a logarithmic grid was used for discretization of the
pbe's. This algorithm has also been extended to simulate a trivariate (drop
volume, age and solute concentration distribution) with unsteady state
behaviour of the dispersed phase by Ribeiro et al. 7917 and was found to be
fast enough to be applied to control of extraction columns. Regueiras et al.
1921 have proposed a new simple algorithm for drop population balance that
further reduces the computation time and is therefore suitable for process
control. Instead of calculating the solute concentration distribution for each
drop class at every time interval, it calculates the mean solute concentration
and standard deviation for the solute concentration. However lack of
experimental verification limits confidence in this algorithm.

MODEL PARAMETERS
Various extraction model parameters, such as drop size, drop size

distribution, slip velocity, mass transfer coefficient, and axial dispersion
coefficient play an important role in the modeling of extraction columns.
These parameters are either determined experimentally or estimated using
available correlations. Korchinsky and Young /93/ have discussed the
computational techniques that can be used for estimation of key model
parameters, such as axial dispersion coefficient, mass transfer coefficient,
drop velocity and constriction factor required for a forward mixing model of
a RDC. The constriction factor and the drop velocity in the agitated and
settling zone are estimated from the hold-up and drop size distribution data,
whereas the axial dispersion coefficient is estimated from the concentration
profile data. Initially, the mass transfer coefficient (kc) and the axial
dispersion coefficient (Ec) are estimated using available correlations. The kc
and Ec for the settling zone are varied to optimize the parameters for the
agitated zone. The authors claim that the determination of the Ec from the
concentration profile is a better method than using tracer techniques. They
found that the mass transfer coefficient increased with increasing drop size, a
trend that was correctly predicted by the Handlos-Baron model. In the tracer
technique, Ec is determined in the absence of mass transfer. The mass transfer
experiments are carried using the same Ec as determined without mass
transfer. The tracer technique is less reliable since the pseudo-homogenous
dispersion model does not accurately describe the dispersed phase, so the
solute concentration profile has been used to determine Ec. The book edited
by Godfrey and Slater IM give a critical review of various correlations
available for estimation of these parameters for different types of extraction
columns. A review of various hydrodynamic parameters, such as hold-up,
drop size and slip velocity, is presented by Koganti and Srinivasulu /94/.
Below, only a few estimation methods that have been most commonly used
are discussed.
Drop Size
The dispersed phase, which consists of drops of varying sizes, is
characterised by a mean drop diameter. The Sauter mean diameter (d32),
defined as d32 = ,^/,?, is the volume-surface mean diameter. For mass
229
A Review
transfer studies, where the mass transfer rate depends on the surface area of
the drop and the amount of solute transferred into the drop volume, d32 seems
to be most suitable and has been used by most of the authors. However, d43,
defined as d43 = ZnidjVn,dj3 has been used for estimation of slip velocity.
Misek /31/, discusses the error involved in characterising the dispersion by
Sauter mean drop diameter and has justified the use of d43.
Purely empirical correlations based on column geometry and operating
conditions have been developed for predicting the mean drop sizes in various
type of extraction columns. Kumar and Hartland /38/ have critically reviewed
the available correlations and have proposed a correlation for predicting the
drop size in a RDC. Prediction of the drop size in a spray column from a
multi-nozzle distribution has been suggested by Dalingaros et al. 1951. For
pulsed perforated plate columns, the correlation proposed by Kumar and
Hartland /95/ and Sovov 5 are more reliable. Kumar and Hartland /97/
have presented a unified correlation for predicting the drop size in eight
different types of extraction column.
Drop Size Distribution

Several authors have tried to fit drop size distribution with different types
of statistical distributions of which the most commonly used ones are given
below.
The arithmetic normal distribution function has been used by Qian /15/ to
describe the drop size distribution for a pulsed plate extraction column. The
function is given as
8(d) = \ eXp\-(d-d43)2/2a2] (17)
( "\43
</43 = 0.0123 - fA/;~70 (18)
\Pc)
(19)
where is the standard deviation,

The basic equation of Mugele and Evans /98/ to describe the drop

distribution has been used to describe the drop size distribution in a rotating
disc contactor.
(20)
"
where v is the volume fraction of drops having diameter less than d, a is a

dimensionless constant, is the size distribution parameter and dmax is the
maximum droplet diameter.
The log-normal distribution and Gamma distribution have also been used
frequently for theoretically predicting the drop size distribution based on
operating conditions.
Break-Up Parameters
Cruz Pinto and Korchinsky 1991 have also studied the drop breakage in a
RDC using a population balance technique. The operating conditions were
chosen so that coalescence was minimised. They have made use of a
breakage frequency function and breakage distribution function assuming
binary breakage. Three parameters have been optimised by minimising the
difference between the predicted and experimental values. However, since
these parameters are not generalised, the usefulness of this model will be
restricted only to the system and column configuration chosen by them.
Haunold et al. /44/ have studied the break-up parameters for a Kiihni column.
A correlation for obtaining dm,x as a function of Weber number (We = p2 N2
DR* / ), and impeller length has been suggested. The breakage probability
increases with mother drop diameter with a maximum of 100%. The system
used is water-butanol and water-succinic acid-butanol. Addition of solute
causes an increase of the number of daughter drops.
Mao el al. /100/ have studied drop breakage for different types of
structured packings. They found that the drops broke at the edges and not
within the structures. A correlation for calculating the critical diameter above
which all drops break has been suggested. However, they have assumed that
the drops break into two equal-sized drops. The correlation was obtained by
making an energy balance before and after the breakage. The energy types
taken into account are kinetic energy, potential energy, surface energy, and
energy dissipation during deformation and breakage. The velocity of the
daughter drops after breakage is taken to be zero.
231
A Review
Fang et al. /101/ have suggested correlations for estimating the breakage
probability, p, in a Kuhni column that is not in turbulent flow. One particular
form is
(21)
1-p
where, WeSLM = ^ (/V1'5 -N )pRd / ' (22)
WeSLM is the modified Schlichting laminar Weber number. The

correlation agrees well up to p=0.5 above which the divergence is large.
Slater /102/ has reviewed drop breakage in various types of extraction
columns.
Slip Velocity
For countercurrent flow and constant velocities in two phase flow, the slip
velocity is defined as
* = Vd + V (1-) (23)
where VS|jp is related to the characteristic velocity (V0) by the equation
V*p = VJl-)" (24)
The simplest form of this relationship assumes m=l. However, studies

have shown that m is a function of drop size and Reynolds number. Godfrey
and Slater /103/ give a good review of various other slip velocity
relationships. Characteristic drop velocity is defined as the drop velocity
when the continuous phase velocity is zero and the dispersed phase hold-up
tends to zero. Correlations and methods for determining the characteristic
drop velocity for various type of extraction columns are available /103-105/.
Axial Mixing
The axial mixing of the continuous phase is mainly due to channelling,

circulatory flow of the continuous phase and the continuous phase being
carried away by the rising drops in the form of wakes which then circulate

back to the column. The axial mixing of the dispersed phase is due to the
difference in drop sizes that results in difference in drop velocities. Several
correlations have been reported in literature for predicting the axial mixing
coefficients of the continuous and dispersed phases for different types of
extraction columns, but the percentage error in some cases is very high, lying
between 25-70%/!/.
. For continuous phase:

Kumar and Hartland /l 067 have presented a correlation for prediction of
the axial dispersion coefficients for RDC by making use of steady state tracer
injection and dynamic tracer injection technique. For the Khni column,
Breysse et al. /107/ have proposed a correlation for both single and two phase
flow. The correlation by Kumar and Hartland /108/ and Prvcic et al. /109/ is
applicable to pulsed sieve-plate columns. A physical model has been
proposed by Stevens and Baird /1107 for single-phase axial mixing in a
single-stage Karr column. Two regimes, i.e., poorly mixed and well-mixed
regimes, have been considered to predict the overall axial dispersion
coefficient. The hydrodynamic model predicts the distance for which the
mixing is poor and the distance for which the mixing is good. Two
parameters must be estimated. The model is proposed based on flow rate,
frequency, amplitude, plate spacing, hole size, and fractional free area. These
authors give a good summary of work carried out by other workers on the
estimation of the axial dispersion in PSE and RFC. A correlation has been
proposed by Karr et al. 71117 for axial mixing in a Karr column.
Steiner et al. 71127 have suggested a method for experimental
determination of the axial dispersion coefficient for the continuous phase and
have fitted the data with an empirical correlation. For the dispersed phase, the
data seemed to be scattered with the correlation proposed.
Godfrey et al. 71137 have reviewed the work carried out by various
authors on single-phase axial mixing in pulsed sieve plate extraction columns
and have proposed a correlation for stationary phase axial mixing with the
objective of getting better co-efficient required in calculating the mass
transfer performance. The phenomenon of axial mixing is generally described
by the usual effective diffusional model. They have used the idea and
technique developed by May II147, Misek 71157 and Miyauchi and Oya 71167
for determining the stationary phase axial mixing coefficient.
233
A Review
For dispersed phase:

Correlations available for predicting the dispersed phase axial mixing
coefficient are fewer in number and are unreliable as the error involved is
quite significant. Most of these correlations apply to specific situations.
Kumar and Hartland /106/ have proposed a correlation for axial mixing
coefficients in RDC and have also reviewed other available correlations. For
the pulsed sieve-plate extraction column, the correlation by Miyauchi and
Oya /5/ is more commonly used.
Mass Transfer Coefficient

Mass transfer coefficient measurements are based on two theories:
a) Whitman's two-film theory and b) Higbie's penetration theory.
For the continuous phase, the correlation proposed by Steiner /l 17/ is
recommended. The equation given by Lochiel and Calderbank IIW, derived
from the diffusion continuity equation is recommended for intermediate and
high Reynolds numbers (Re = p d V / ).
For single drop mass transfer coefficient of the dispersed phase, the
Newman's model 1251 for rigid drop and Kronig and Brink's model /34/ for
circulating drops have been used. For mass transfer in drop swarms, the
model by Yaron and Gal-Or /119/ is recommended. Korchinsky and
Cruz-Pinto /120/ have suggested a method for applying the rigid drop and
Handlos-Baron drop models for evaluating the mass transfer co-efficient
when the continuous phase concentration is not constant and the drop sizes
are not uniform. Bahmanyar et al. /121/ have examined the rate of mass
transfer from a single drop in RDC's, pulsed sieve-plate columns, and packed
columns and have compared these with those estimated by Handlos and
Baron model to incorporate necessary corrections.
CONCLUSIONS
From the various types of models reviewed, it can be concluded that these
fall into two groups: (1) the diffusion model with turbulent back diffusion of
solute superimposed on plug flow of both the phases, and (2) the backflow
model with well-mixed non-ideal stages between which backflow occurs.
The major difficulty lies in proper representation of the dispersed phase. The

pseudo-homogenous model assumes the dispersed phase to be pseudo-

homogenous whereas the population balance model treats it as a discrete
element. The drop population balance model takes into consideration the
previous history of each drop as it moves along the column, i.e., its breakage
and coalescence, to give birth to new drops of different sizes. The population
balance models have been found to represent the real system more closely
than the pseudo-homogenous model. As far as the population balance model
is concerned, the major difficulties lie in obtaining the break-up and
coalescence parameters. Several researchers have assumed that the drops
break into 2 or 3 equisized daughter drops. In recent years, however, studies
have been carried out to determine the drop size distribution for various drop
sizes and fitting them to appropriate statistical functions. The constant
parameters depend on the system and operating conditions chosen. These
parameters for some systems are available in literature, but a lot of
experimental data remain to be generated for determining the parameters.
Except for a few, the coalescence parameters in most models have been
estimated by obtaining best fit with experimental drop size distribution data.
Even those who have used experimental values have made assumptions that
are not realistic, such as coalescence only between adjacent and same drop
sizes. However, none of the methods available to date is fully satisfactory and
more research in the area of determination of coalescence parameters for drop
swarms would be helpful in obtaining a better model. Application of
advanced modelling techniques, such as, Computational Fluid Dynamics
(CFD), may lead to a better model, but may be extremely complex since the
dispersed phase continuously changes in size and composition.
ACKNOWLEDGEMENT
The author gratefully acknowledges the financial assistance of the

Alexander von Humboldt Foundation, Bonn; Prof. Alfons Vogelpohl, Institut
fr Thermische Verfahrenstechnik, TU Clausthal, Germany, for his help and
cooperation; and the Director, Regional Research Laboratory (C.S.I.R.),
Bhubaneswar, for permission to publish this paper.

235
A Review
NOMENCLATURE
A = length of pulsation stroke, m

a = asymmetrical distribution parameter
B(d) = rate of birth of drops of diameter d,m"'.s"'
C = concentration, kg.m"3
C* = equilibrium concentration, kg.m"3
d = droplet diameter, m
D(d) = rate of death of drops of diameter d, nf'.s"1
DK = turbine diameter, m
d32 = Sauter mean diameter, m
d43 = drop volume fraction mean diameter, m
E = axial dispersion coefficient, m2.s"'
/ = pulsefrequency,s"'
g(d) = drop volume fraction distribution, m"1
h = centre to centre plate spacing, m
H = height of the column, m
= stage number
k = mass transfer coefficient, m.s"1
ki, k2, k3 = constants in Eqn. (5)
km = overall mass transfer coefficient based on
continuous phase, m.s*1
kv = parameter in Eqn.(13), m"1
K = distribution ratio
Kh Kp = constants in Eqn. (11) and (12) respectively
L = extract flow rate, kg.hr"1
LI, L2,L3 = empirical parameters for local nodes in Eqn.(15)
m = exponent
m ratio of the solute composition in the raffmate to
that in the extract phase
W = turbine speed, s"1
^ = number of stages
= break-up probability
P(d) = volume fraction of drops of diameter d, m"1
q = transition probability density
r = dimensionless function of drop diameter
/ = time, s
u = drop velocity, m.s"1

SwatiMohanty Reviews in Chemical Engineering
U average velocity of the drop, m.s"1

y superficial phase velocity, m.s"1
v volume fraction of the drops having diameter
less than d
characteristic velocity, m.s"1
slip velocity, m.s'1
v, terminal velocity, m.s"1
y- as defined in Eqn. (9)
w position of the drop at time , m
WestM modified Schlichting laminar Weber number
mole fraction of component in the raffinate
y mole fraction of component in the extract
, Z2,... Z parameters in Eqn. (1)
z position of drop at time t, m
Greek letters
a fractional free area of perforated plate
uniformity distribution parameter
Y surface tension, N.m"'
viscosity, Pa.s
density, kg.m"3
standard deviation of drop size distribution, m
hold-up of dispersed phase
time, s
Subscript
c continuous phase
er critical
d dispersed phase
f final
max maximum
n stage number
initial
t total
v densely packed region
237
A Review
REFERENCES
1. Godfrey, J.C. and M.J. Slater (eds), "Liquid-Liquid Extraction

Equipment", John Wiley & Sons, Chichester, England (1994).
2. Thorton, J.D. (ed.), "Science and Practice of Liquid-Liquid
Extraction", Vol.1 & 2, Oxford University Press, Imprint: Clarendon
Press, Oxford (1992).
3. Steiner, L. and S. Hartland, "Modeling of Liquid-Liquid Extraction
Columns", in Proc. Austrian-Ital.-Yugosl. Chem. Eng. Conf. 3rd, 1982,
Tech. Univ. Graz, Graz, Austria, (1982) pp. 397-405.
4. Steiner, L. and S. Hartland, "Neues zur Mathematischen Modellierung
von Flssig/Flssig Extraktionskolonen", Chem. Ing. Tech.. 55,
194-201 (1983).
5. Sleicher, C.A., Jr., "Axial Mixing and Extraction Efficiency", AIChE
J. 5,145-149(1959).
6. Sleicher, C.A., Jr., "Entrainment and Extraction Efficiency of
Mixer-Settler", AIChE J. 6, 529-530 (1960).
7. Pratt, H.R.C. and M.H.I. Baird, "Axial Dispersion", in "Handbook of
Solvent Extraction", T.C. Lo, M.H.I. Baird and C.Hanson, eds., John
Wiley and Sons, Inc., New York (1983), 199-247.
8. Steiner, L. and S. Hartland, "Unsteady State Extraction", in
"Handbook of Solvent Extraction", T.C. Lo, M.H.I. Baird and
C.Hanson, Eds., John Wiley and Sons, Inc., (1983b), pp. 249-264.
9. Ramakrishna, D., "The Status of Population Balances", Rev. Chem.
Eng. 3,49-95 (1985).
10. Kumar, A. and S. Hartland, "Unified Correlations for the Prediction of
Dispersed-phase Hold-up in Liquid-Liquid Extraction Columns", Ind.
Eng. Chem. Res. 34, 3925-3940 (1995).
11. Haverland, H., A. Vogelophl, C. Gourdon and G. Casamatta,
"Simulation of Fluid Dynamics in a Pulsed Sieve-Plate Column"
Chem. Eng. Technol. 10, 151-157 (1987).
12. Dimitrova Al Khani, S., C. Gourdon, and G. Casamatta, "Dynamic
and Steady State Simulation of Hydrodynamics and Mass Transfer in
Liquid-Liquid Extraction Column", Chem. Eng. Sei. 44, 1295-1305
(1989).
13. Zimmermann, ., C. Gourdon, X. Joulia, A. Gorak and G. Casamatta,
"Simulation of a Multicomponent Extraction Process by a

Nonequilibrium Stage Model Incorporating a Drop Population

Model", Comp. Chem. Eng., 16 n suppl., S403-S410 (1992).
14. Mohanty, S. and A. Vogelpohl, "A Simplified Hydrodynamic Model
for a Pulsed Sieve Plate Extraction Column", Chem. Eng. Process. 36,
385-395(1997).
15. Qian, Y. and J. Wang, "Modelling of Mass Transfer in Extraction
Columns with Drop Forward Mixing and Coalescence-Redispersion",
Can. J. Chem. Eng. 70, 88-96 (1992).
16. Handlos, A.E. and T. Baron, "Mass and Heat Transfer from Drops in
Liquid-Liquid Extraction", AIChE J. 3, 127-136 (1957).
17. Garg, M.O. and H.R.C. Pratt, "Measurement and Modelling of
Droplet Coalescence and Breakage in a PuIsed-PIate Extraction
Column", AIChE J. 30,432-441(1984).
18. Blass, E. and H. Zimmerman, "Mathematische Simulation und
Experimentelle Bestimmung des Instationren Verhaltens einer
Flssigkeitspulsierten Siebbodenkolonne zur
FIssig-flssig-Extraction", Verfahrenstechnik 16, 682-690 (1982).
19. Prabhakar, A., G. Sriniketan and Y.B.G. Varma, "Dispersed Phase
Hold-up and Drop Size Distribution in Pulsed Plate Column", Can. J.
Chem. Eng. 66,232-240(1988).
20. Kumar, A. and S. Hartland, "Prediction of Dispersed Phase Hold-up in
Pulsed Perforated Plate Extraction Columns" Chem. Eng. Process. 23,
41-59 (1988).
21. Zhu, J., S. Zhang, X. Zhow, X. Chen, Y. Su and A. Vogelpohl,
"Hydrodynamics, Axial Mixing and.Mass Transfer in Open Turbine
Rotating Disk Contactor (OTRDC)", Chem. Eng. Technol. 14,
167-177(1991).
22. Chartres, R.H. and W.J. Korchinsky, "Modelling of Liquid-Liquid
Extraction Columns. Predicting the Influence of Drop Size
Distribution", Trans. Instn. Chem. Engrs. 53,247-254 (1975).
23. Korchinsky, W.J. and J.J.C. Cruz-Pinto, "Modelling of Counter
Current Flow Liquid-Liquid Extraction Columns" in Proc. of ISEC,
Liege, Belgium, 1980, Assoc. Ing. Univ. Liege, Liege, Belgium
(1980) paper 80-176,10pp.
24. Cruz Pinto, J.J.C. and W.J. Korchinsky, "Exact Solution of the
Newman, and of the Handlos-Baron, Model Equations for
Countercurrent Flow Extractor" Comp. Chem. Eng., 7, 19-25 (1983).

239
A Review
25. Newman, A.B., "The Drying of Porous Solids: Diffusion

Calculations", Trans. AIChE, 27,310-333(1931).
26. Casamatta, G. and A. Vogelpohl, 'Modelling of Fluid Dynamics and
Mass Transfer in Extraction Columns", Ger. Chem. Eng. 8, 96-103
(1985).
27. Ghalehchian, J.S. and M.J. Slater, "Numerical Simulation of
Hydrodynamics of Rotating Disc Contactors With Effect of Drop
Breakage", in Proc. ISEC'96, Vol.2, D.C. Shallcross, R. Paimin and
L.M. Prvcic, eds., Melbourne, Australia, March 1996, University of
Melbourne, Melbourne, Australia (1996),pp.l209-1214.
28. Sarkar, S., C.J. Mumford and C.R. Phillips, "Liquid-Liquid Extraction
with Interphase Chemical Reaction in Agitated Columns. 1.
Mathematical Models", Ind. Eng. Process Des. Dev. 19, 665-671
(1980).
29. Sarkar, S., C.J. Mumford and C.R. Phillips, "Liquid-Liquid Extraction
with Interphase Chemical Reaction in Agitated Columns. 2.
Hydrodynamics and Mass Transfer in Rotating Disk and Oldshue
Rushton Contactors", Ind. Eng. Process Des. Dev. 19, 672-679
(1980).
30. Azimzadeh-Khatayloo, S., "Drop Size Distribution in Stagewise
Liquid-Liquid Contactors", PhD. Thesis, The Victoria University of
Manchester, Manchester, UK, July, 1975.
31. Misek, T., "Behaviour of a Polydisperse Phase in Column-type
Apparatus. I. Hydrodynamics, Entrainment and Partial Flooding",
Coll. Czech. Chem. Comm. 32,4018-4031 (1967).
32. Zhang, S.H., S.C. Yu, Y.C. Zhou and Y.F. Su, "A Model for
Liquid-Liquid Extraction Column Performance - The Influence of
Drop Size Distribution on Extraction Efficiency", Can. J. Chem. Eng.
63,212-226(1985).
33. Risken, H., "Fokker-Planck Equation: Methods of Solution and
Applications", 2nd ed., Springer-Verlag, New York, NY (1996).
34. Kronig, R. and J.C. Brink, "The Theory of Extraction from Falling
Droplets", Appl. Scient. Res. A2,142-154 (1960).
35. Calderbank, P.H. and M.B. Moo Young, "The Continuous Phase Heat
and Mass Transfer Properties of Dispersion", Chem. Eng. Sei. 16,
39-54(1961).

36. Zhang, S.H., X.D. Ni and Y.F. Su, "Hydrodynamics, Axial Mixing
and Mass Transfer in Rotating Disk Contactors", Can. J. Chem. Eng.
59,573-583,1981.
37. Sarkar, S, C.R. Phillips and C.J. Mumford, "Characterization of
Hydrodynamic Parameters in Rotary Disk and Oldshue-Rushton
Column. Hydrodynamic Modeling, Drop Size, Hold-up and
Flooding", Can. J. Chem. Eng. 63, 701-709 (1985).
38. Kumar, A. and S. Hartland, "Prediction of Drop Size in Rotating Disc
Extractors", Can. J Chem. Eng. 64,915-924 (1986).
39. Kumar, A. and S. Hartland "Prediction of Dispersed Phase Hold-up in
Rotating Disk Extractors" Chem. Eng. Commun. 56, 87-106 (1987).
40. HufnagI, H., M. Mclntyre and E. Blass, "Dynamic Behaviour and
Simulation of a Liquid-Liquid Extraction Column", Chem. Eng
Technol. 14,301-306(1991).
41. HufnagI, H. and E. Blass, "Dynamisches Verhalten, Simulation und
Regelung einer Flssig/Flssig-Extractionskolonne", Chem.Ing.
Tech.. 64,742-743 (1992).
42. Marquardt, W., M. Wurst, P. Holl and E.D. Gilles, "Tools for
Dynamic Process Simulation and Their Application", in DECHEMA
Monogr. 115(Mod. Comput. Tech. Their Impact Chem. Eng.), VCH,
Weinheim, 99-126 (l 989).
43. Krner, A., P. Holl, W. Marquardt and E.D. Gilles, "Diva- an Open
Architecture for Dynamic Simulation", Comp. Chem. Eng. 14,
1289-1295 (1990).
44. Haunold, C., M. Cabassud, C. Gourdon and G. Casamatta, "Drop
Behaviour in a KQhni Column for a Low Interfacial Tension System"
Can. J. Chem. Eng. 68,407-414 (1990).
45. Steiner, L. "Drop Population Balance. Tool or Flop!", Chem.Ing.Tech.
68,141-146(1996).
46. Gerstlauer, ., A. Mitrovic, E.D.Gilles and G. Zamponi, "A Detailed
Population Model for the Dynamics of Agitated Liquid-Liquid
Dispersions", in Proc. ISEC'96, Vol.2, D.C. Shallcross, R. Paimin and
L.M. Prvcic, eds., Melbourne, Australia, March 1996, University of
Melbourne, Melbourne, Australia (1996), pp. 1091-1096.
47. Tsouris, C. and L.L. Tavlarides, "Breakage and Coalescence Models
for Drops in Turbulent Dispersions", AIChE J. 40,395-406 (1994).
241
A Review
48. Coulaloglou, C.A. and L.L. Tavlarides, "Description of Interaction

Processes in Agitated Liquid-Liquid Dispersions", Chem. Eng. Sei.
32,1289-1297(1977).
49. Heertjes, P.M., W.A. Holve and H. Talsma, "Mass Transfer Between
Isobutanol and Water in a Spray Column", Chem. Eng. Sei. 3,
122-142 (1954).
50. Zamponi, G., J. Stichlmair, A. Gerstlauer and E.D. Gilles, "The
Transient Behaviour of a Liquid/Liquid Agitated Extraction Column:
Experiment and Simulation" in Proc. 1SEC'96 Vol.2, D.C. Shallcross,
R. Paimin and L.M. Prvcic, Eds., Melbourne, Australia, March 1996,
University of Melbourne, Melbourne, Auatralia (1996a), pp.
1049-1054.
51. Zamponi, G., J. Stichlmair, A. Gerstlauer and E.D. Gilles, "Simulation
of the Transient Behaviour of a Stirred Liquid-Liquid Extraction
Column", Comp. Chem. Eng., 20 (Suppl. B., European Symp. on
Comp. Aided Process Eng.-6, 1996), S963-S968 (1996).
52. Noworyta, A. and M. Krotki "Hydrodynamics of the Dense-Packed
Dispersion Band in the Spray Column", Chem. & Biochem. Eng. Q. 1,
69-75 (1987).
53. Seibert, A.F. and J.R. Fair, "Hydrodynamics and Mass Transfer in
Spray and Packed Liquid-Liquid Extraction Column" Ind. Eng. Chem.
Res. 27,470-481(1988).
54. Schermuly W. and E. Blass, "Three Component Mass Transfer in
Liquid-Liquid Extraction with the System Glycerol-Acetone-Water.
Part 2. Calculation and Experimental Investigation of 3-Component
Mass Transfer in a Counter Current Extraction Column", Chem. Eng.
Technol. 14,253-263 (1991).
55. Kumar, A. and S. Hartland, "Independent Prediction of Slip Velocity
and Hold-up in Liquid-Liquid Extraction Columns" Can. J. Chem.
Eng. 67,17-25 (1989).
56. Alatiqi, I., G. Aly, F. Mjalli and C.J. Mumford, "Mathematical
Modeling and Steady-State Analysis of a Scheibel Extraction
Column", Can. J. Chem. Eng. 73, 523-533 (1995).
57. Alatiqi, I., G. Aly and F. Mjalli, "Dynamic Simulation of Stagewise
Extraction Contactors", in Proc. ISEC'96, Vol.2, D.C. Shallcross, R.
Paimin and L.M. Prvcic, eds., Melbourne, Australia, March 1996,
University of Melbourne, Melbourne, Australia (1996), pp.
1061-1066.

58. Pang, K.H. and A.I. Johnson, "Mathematical Modelling of a Modified

Scheibe! Liquid-Liquid Extraction Column in the Frequency
Domain", Can.. J. Chem. Eng. 49, 837-843 (1971).
59. Garner, F. H. and M. Tayeban, "The Importance of Wakes in Mass
Transfer from Both Continuous and Dispersed Phase Systems. I.",
Anales real Soc. espaft. f is. y quim., 56B, 479-490 (1960).
60. Rose, P.M. and R.C. Kintner, "Mass Transfer from Large Oscillating
Drops", Aichi J. 12, 530-534 (1966).
61. Steiner, L., H. Bertschmann and S. Hartland "A Model for Simulation
of Hydrodynamics and Mass Transfer in Extraction Columns Filled
with a Regular Packing" Chem. Eng. Research. Des. 73, Part A,
542-550 (1995).
62. Dankwerts, P.V., "Significance of Liquid Film Coefficient in Gas
Absorption" Ind. Eng. Chem. 43,1460-1467 (1951).
63. Hamilton, J. A., and H.R.C. Pratt, "Droplet Coalescence and Breakage
Rates in a Packed Liquid Extraction Column", AIChE J., 30(3),
442-450(1984).
64. Salem, Abu Bakr S.H., Mohammad S.H. Al-Fandery and Abdul Al
Haq M. Abdul Al Latif, "Modeling of a Packed Column Contactor",
Ind. Eng. Chem. Res. 34,2084-2093 (1995).
65. Treybal, R.E., "Mass Transfer Operation", McGraw-Hill Book
Company, 3rd ed., 9th printing (1986), pp. 326.
66. Arimont, K., M. Soike and M. Henschke, "Simulation of Pulsed
Packed Extraction Column", Chem. Ing. Tech. 68,276-279 (1996).
67. Lee, Y. K., D.P. Ju and C. Kim, "Drop Size Distribution and Hold-up
in a Rotating Impeller Extraction Column" Korean J. Chem Eng. 8,
80-87 (1991).
68. Lee, Y.K. and C. Kim, "A Study on the Drop Size Distribution and the
Hold-up in a Rotating Impeller Extraction Column", in Proc. of ISEC,
T. Sekine, Ed., Kyoto, Japan, July 1990, Elsevier, Amsterdam (1992)
pp. 1253-1257.
69. Tsouris, C., V.I. Kirou and L.L. Tavlarides, " Drop Size Distribution
and Hold-up Profiles in a Multistage Extraction Column", AIChE J.
40,407-418(1994).
70. Korchinsky, W.J. and S. Azimzadeh- Khatayloo, "An Improved
Stagewise Model of Countercurrent Flow Liquid-Liquid Contactors",
Chem. Eng. Sei. 31, 871-875 (1976).
243
A Review
71. Dimitrova AI Khani, S., C. Gourdon and G. Casamatta, "Simulation of

Hydrodynamics and Mass Transfer of a Disk and Rings Pulsed
Column" Ind. Eng. Chem. Res. 27,329-333 (1988).
72. Hafez, M.M., M.H.I. Baird and I. Nirdosh, "A Model for
Reciprocating Plate Extraction Column", in Proc. of ISEC, Liege,
Belgium, 1980, Assoc. Ing. Univ. Liege, Liege, Belgium (1980), pap.
no. 80-41.
73. Camurdan, M.C., M.H.I. Baird and P.A. Taylor, 'Steady State
Hydrodynamics and Mass Transfer Characteristics of a Kan-
Extraction Column', Can. J. Chem. Eng. 67, 554-559 (1989).
74. Hafez, M.M., M.H.I., Baird and I. Nirdosh, 'Flooding and axial
Dispersion in Reciprocating Plate Extraction Columns", Can. J. Chem.
Eng., 57, 150-158 (1979).
75. Sovov, H. "Countercurrent Pulsed and Reciprocating Plate
Extractors. Prediction of Sauter Mean Drop Diameter", Collect.
Czech. Chem. Comm. 55,409-425 (1990).
76. Steiner, L., M. Laso and S. Hartland, "Models for Performance of
Extraction Columns Based on Actual Drop Behaviour", in Inst. Chem.
Eng. Symp. Ser. 1984,88(Extr. '84), pp. 91-110.
77. Caminos, A.A., R. Gani and E.A. Brignole, "A Liquid-Liquid
Extractor Model Based on UNIFAC", Comput. Chem. Eng. 8,
127-136 (1984).
78. Fredenslund, A., R.L. Jones and J.M. Prausnitz, "Group Contribution
Estimation of Activity Co-efficients in Non-ideal Mixtures", AIChE
J., 21(6), 1086-1099(1975).
79. Sereno, A.M., T.F. Anderson and A.G. Medina, "Dynamic Simulation
of Liquid-Liquid Operations Using Simple Non-Linear Models",
Comp. Chem. Eng. 11, 177-185 (1987).
80. Babcock, P.D., L.F. Stutzman, and T.G. Koup, "General Equation
Modelling Systems (GEMs): A Mathematical Simulation Language",
Simulation 36(2), 41-53 (1981).
81. Black, C., "Simulation Applied to Special Industrial Problems",
Chem. Eng. Prog. 78 (12), 53-60 ( 1982).
82. Brannock, N.F., V.S. Verneuil and Y.L. Wang, "PROCESS
Simulation Program- a Comprehensive Flowsheeting Tool", Comp.
Chem. Eng. 3, 329-352 (1979).

83. Roche,E.C., "Rigorous Solution of Multicomponent Multistage

Liquid-Liquid Extraction Problems", Brit. Chem. Eng. 14, 1393-1397
(1969).
84. Wang, J. C. and Y.L. Wang, "A Review on the Modeling and
Simulation of Multistage Separation Processes", Found. Comput.
Aided Chem. Process Des., Proc. Int. Conf. 1980. R.S.H. Mah and
W.D. Seider, eds., Eng. Found. New York, N.Y. (1981), 2,121-170.
85. Ricker, N. L., F. Nakashio and C.J. King, " an Efficient General
Method for Computation of Countercurrent Separation Processes with
Axial Dispersion", AIChE J. 27,277- 284 (1981).
86. Chatzi, E. and J.M. Lee, "Analysis of Interactions for Liquid-Liquid
Dispersion in Agitated Vessel", Ind. Eng.-Chem. Res. 26,
2263-2267(1987).
87. Michelsen, M.L., "An Efficient General Purpose Method for the
Integration of Stiff Ordinary Differential Equation", AIChE J. 22,
594-603 (1976).
88. Michelsen, M.L., "Application of Semi-implicit Runge-Kutta Method
for Integration of Ordinary and Partial Differential Equation", Chem.
Eng.J. 14, 107-112(1977).
89. Kronberger, T., A. Ortner, W. Zulehner and H.J. Bart, "Numerical
Simulation of Extraction Columns Using a Drop Population Model",
Comp. Chem. Eng, 19(Suppl. European Symposium on Computer
Aided Process Eng -5, S639-644 (1995).
90. Ribeiro, L.M., P.F.R. Regueiras and M.M.L. Guimaraes, C.M.N.
Madureira, J.J.C. Cruz-Pinto, "The Dynamic Behaviour of
Liquid-liquid Agitated Dispersions. -I. The Hydrodynamics," Comp.
Chem. Eng. 19,333-343 (1995).
91. Ribeiro, L.M., P.F.R. Regueiras, M.M.L. Guimaraes, C.M.N.
Madureira and J.J.C. Cruz-Pinto, "The Dynamic Behaviour of
Liquid-liquid Agitated Dispersions. 11- Coupled Hydrodynamics and
Mass Transfer," Comp. Chem. Eng. 21,543-558 (1997).
92. Regueiras, P.F.R., L.M. Ribeiro, M.M.L. Guimaraes, C.M.N.
Maduereira and J.J.C. Cruz-Pinto, "Precise and Fast Computer
Simulations of the Dynamic Mass Transfer Behaviour of
Liquid-Liquid Agitated Contactors", in Proc. ISEC'96, Vol.2, D.C.
Shallcross, R. Paimin and L.M. Prvcic, eds., Melbourne, Australia,
March 1996, University of Melbourne, Melbourne, Australia (1996),
pp. 1031-1036.
245
A Review
93. Korchinsky, W.J. and C. H. Young, "Computational Techniques for

Liquid-Liquid Extraction Column Model Parameters Estimation,
Using the Forward Mixing Model", J. Chem. Technol. Biotechnol,
Chem. Technol. 35A, 347-357 (1985).
94. Koganti, S.B. and K. Sreenivasulu, "Hydrodynamic Aspects of
Liquid-Liquid Extraction Equipment", J. Energy, Heat Mass transfer
18,249-266, (1996).
95. Dalingaros, W., A. Kumar and S. Hartland, "Effect of Physical
Properties and Dispersed Phase Velocity on the Size of Drops
Produced at a Multinozzle Distributor", Chem. Eng. Process. 20,
95-102 (1986).
96. Kumar, A. and S. Hartland, "Prediction of Drop Size in Pulsed
Perforated-Plate Extraction Column" Chem. Eng. Commun.
44,163-182(1986).
97. Kumar, A. and S. Hartland, "Unified Correlations for Prediction of
Drop Size in Liquid-Liquid Extraction Columns", Ind. Eng. Chem.
Res. 35,2682-2695 (1996).
98. Mugele, R.A. and H.D. Evans, "Drop Size Distribution in Sprays",
Ind. Eng. Chem. 43,1317-1324 (1951).
99. Cruz-Pinto, J.J.C. and W.J. Korchinsky, "Drop Breakage in Counter
Current Flow Liquid-Liquid Extraction Columns", Chem. Eng. Sei.
36,689-694(1981).
100. Mao, Z.Q., J.C. Godfrey and M.J. Slater, "Single Liquid Drop
Velocities and Breakage Mechanism in Sections of Structured
Packings" Chem. Eng. Technol. 18,33-40 (1995).
101. Fang, J., J.C. Godfrey, Z.Q Mao, M.J. Slater and C. Gourdon, "Single
Liquid Drop Breakage Probabilities and Characteristic Velocities in
Khni Columns", Chem. Eng. Technol. 18,41-48 (1995).
102. Slater, M.J., "Liquid Drop Breakage in Liquid-Liquid Extraction
Columns", American Inst. of Chem. Eng. Symp. Ser., 140 ( Fluid
Mixing 5) 295-306 (1996).
103. Godfrey, J.C. and M.J. Slater, "Slip Velocity Relationship for
Liquid-Liquid Extraction Columns", Chem. Eng. Res Des. 69(A2)
130-141(1991).
104. Laddha, G.S., T.E. Degaleesan and R. Konnappan, "Hydrodynamics
and Mass Transport in Rotary Disk Contactors", Can. J. Chem. Eng.
56,137-150(1978).

105. Hussain, A.A., T. B. Liang and M.J. Slater, "Characteristic Velocity

of Drops in a Liquid-Liquid Extraction Pulsed Sieve Plate Column"
Chem. Eng. Res. Des. 66,541-554 (1988).
106. Kumar, A. and S. Hartland, "Prediction of Axial Mixing Coefficients
in Rotating Disc Extraction Columns", Can. J. of Chem. Eng. 70,
77-87(1992).
107. Breysse, J., U. Bhlmann and J.C. Godfrey, "Axial Mixing
Characteristics of industrial and Pilot Scale Kiihni Column", AIChE
Symp. Ser. 80(238), 94-101 (1984).
108. Kumar, A. and S. Hartland, "Prediction of Continuous Phase Axial
Mixing Coefficients in Pulsed Perforated-Plate Extraction Column",
Ind. Eng. Chem. Res. 28,1507-1513 (1989).
109. Prvcic, L.M., H.R.C. Pratt and G.W. Stevens, "Axial Dispersion in
Pulsed-, Perforated-Plate Extraction Column", AIChE J. 35,
1845-1855 (1989).
110. Stevens, G.W. and M.H.I. Baird, "A Model for Axial Mixing in
Reciprocating Plate Columns", Chem. Eng. Sei. 45,457-465 (1990).
111. Karr, A.E., S. Ramanujam, T.C. Lo and M.H.I. Baird, "Axial Mixing
and Scaleup of Reciprocating Plate Columns", Can. J. Chem. Eng. 65,
373-380(1987).
112. Steiner, L., A. Kumar and S. Hartland, "Determination and
Correlation of Axial Mixing Parameters in Agitated Liquid-Liquid
Extraction Column" Can. J. Chem. Eng. 66,241-247 (1988).
113. Godfrey, J.C., Houlton, D.A., Marley, S.T., Marrocchelli, A., Slater,
M.J., Chem. Eng. Res. Des., 66,130, 1988.
114. May, W.G., "Fluidised-bed Reactor Studies", Chem. Eng. Prog.
55(12), 49-56 (1959).
115. Misek, T., "Backmixing in Full-scale ARD (Agitated Rotating Disk)
and RDC (Rotating Disk Contactor) Extractors", Coll. Czech Chem.
Comm. 40,1686-1693 (1975).
116. Miyauchi, T. and H. Oya, "Longitudinal Dispersion in Pulsed
Perforated Plate Columns", AIChE J. 11,395-402 (1965).
117. Steiner, L., "Mass Transfer Rates from Single Drops and Swarms",
Chem. Eng. Sei. 41,1979-1986 (1986).
118. Lochiel, A.C. and P.H. Calderbank, "Mass Transfer in the Continuous
Phase Around Axisymmetric Bodies of Revolution" Chem. Eng. Sei.
19,471-484(1964).
247
A Review
119. Yaron, I. and B. Gal-Or, "Convective Mass or Heat Transfer from

Size Distributed Drops, Bubbles or Solid Particles", Int. J. Heat and
Mass Transfer 14,727-737 (1971).
120. Korchinsky, W.J. and J.J.C. Cruz Pinto, "Mass Transfer Coefficients-
Calculation for Rigid and Oscillating Drops in Extraction Columns",
Chem. Eng. Sei. 34, 551-561 (1979).
121. Bahmanyar, H., D. K. Chang-Kakoti, L. Garro, T.-B. Liang and M.J.
Slater, "Mass Transfer from Single Drops in Rotating Disc, Pulsed
Sieve Plate and Packed Liquid-Liquid Extraction Column", Chem.
Eng. Res. Des. 68, part A, 74-83 (1990).
122. Badrinarayan, B. and M. Chidambaram, "Simulation of Liquid-Liquid
Extractors", Chem. Eng. Comm. 95, 121-129 (1990).
123. Hoting, B., "Modeling of Fluid Dynamics and Mass Transfer in
Extraction Columns with Structured Packings on the base of Single
Droplet Experiments", Chem. Ing. Tech. 69,487-472 (1997).


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MODELING OF LIQUID-LIQUID EXTRACTION

Regional Research Laboratory (C.S.I.R.),

Mathematical models are reviewed for different types of commonly used

Keywords: mathematical modeling, extraction column, population balance,

Liquid-liquid extraction is the second most important separation process

Mathematical models for liquid-liquid extraction are categorised into

200 Brought to you by | SUNY Buffalo Libraries

a.= Vcc oz +EcC -L-koc(Ccc -Ccc/ )

where is measured in the direction of flow of the dispersed phase 151.

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**\ ' T\ /- / j . " IE ~ / I . D/ j r/j\ /4\

c) Stagewise: In this type of model, the column is described as a series of

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empirical correlations for predicting the hold-up in different types of

Pulsed Sieve Plate Extraction Column (PSE)

204 Brought to you by | SUNY Buffalo Libraries

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large number ofsystems

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Mohanty and Vogelpohl /14/ have simplified the differential population

212 Brought to you by | SUNY Buffalo Libraries

Rotating Disk Contactor (RDC):

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of smaller drops by the continuous phase. A mean diameter based on d43 =

continuous phase. This may be due to coalescence as coalescence is high

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hold-up. Response to step disturbances in flow rates, solute concentration,

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coefficient have been assumed constant and a linear equilibrium relationship

Oldshue-Rushton Contactor (ORC), Disks and Rings Pulsed

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while the drop coalescence model is based on collision frequency and

Reciprocating Plate Column (RFC):

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. /73 For estimating the hold-up, the following model is proposed:

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where kv is a fitting parameter.

The model parameters K p and m were evaluated by minimizing the

In K-t = LljJc^f +L2y?ef +L3, i = 1,2,3

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raffmate and extract phases in multistage extraction columns has been

Simulators with built-in models applicable to various process industries

Model equations range from simple to more complicated form. In some

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Various extraction model parameters, such as drop size, drop size

Drop Size Distribution

8(d) = \ eXp\-(d-d43)2/2a2] (17)

where is the standard deviation,

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where v is the volume fraction of drops having diameter less than d, a is a

where, WeSLM = ^ (/V1'5 -N )pRd / ' (22)

WeSLM is the modified Schlichting laminar Weber number. The