MohantyS-2000 - Modeling of Liquid-Liquid Extraction Column - Mohanqwety

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
200
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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
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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
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Vol. 16, No. 3, 2000
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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
Vol. 16, No. 3, 2000
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
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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
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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.
no solute c-d d-c
k, 2.10xl0 6 2.14x10* l.lOxlO6
k2 44.53 44.53 50.56
k3 9.69 10 9.69 xlO' 3 9.69 xlO' 3
212
Swati Mohanty
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
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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
214
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
Vol. 16, No. 3, 2000
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
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Swati Mohanty
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.
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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
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Swati Mohanty
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
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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
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Swati Mohanty
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
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(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-butylacetate/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,
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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
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. /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-
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Swati Mohanty
empirical correlation has been proposed for predicting the hold-up in the densely packed zone
2
rv ,
V. d
A
(13)
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
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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 logarithmicnormal 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
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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
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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 methylisobutylketone-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.
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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
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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 = 0.0123 - \Pc)
"\43
fA/;~70
(18)
(19)
where is the standard deviation, The basic equation of Mugele and Evans /98/ to describe the drop
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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.
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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
1-p
(21)
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-)
where VS|jp is related to the characteristic velocity (V0) by the equation V*p = VJl-)"
(23)
(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
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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.
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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
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pseudo-homogenous model assumes the dispersed phase to be pseudohomogenous 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.
Vol. 16, No. 3, 2000

NOMENCLATURE
A a B(d) C C* d D(d) DK d32 d43 E / g(d) h H k ki, k2, k3 km kv K Kh Kp L LI, L2,L3 m m W ^ P(d) q r / u
= = = = = = = = = = = = = = = = = = = = = = = = =
= = = = = = = =
length of pulsation stroke, m asymmetrical distribution parameter rate of birth of drops of diameter d,m"'.s"' concentration, kg.m"3 equilibrium concentration, kg.m"3 droplet diameter, m rate of death of drops of diameter d, nf'.s"1 turbine diameter, m Sauter mean diameter, m drop volume fraction mean diameter, m axial dispersion coefficient, m2.s"' pulsefrequency,s"' drop volume fraction distribution, m"1 centre to centre plate spacing, m height of the column, m stage number mass transfer coefficient, m.s"1 constants in Eqn. (5) overall mass transfer coefficient based on continuous phase, m.s*1 parameter in Eqn.(13), m"1 distribution ratio constants in Eqn. (11) and (12) respectively extract flow rate, kg.hr"1 empirical parameters for local nodes in Eqn.(15) exponent ratio of the solute composition in the raffmate to that in the extract phase turbine speed, s"1 number of stages break-up probability volume fraction of drops of diameter d, m"1 transition probability density dimensionless function of drop diameter time, s drop velocity, m.s"1
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SwatiMohanty
y
v
v, yw WestM
y
, Z2,... Z
z
Greek letters
average velocity of the drop, m.s"1 superficial phase velocity, m.s"1 volume fraction of the drops having diameter less than d characteristic velocity, m.s"1 slip velocity, m.s'1 terminal velocity, m.s"1 as defined in Eqn. (9) position of the drop at time , m modified Schlichting laminar Weber number mole fraction of component in the raffinate mole fraction of component in the extract parameters in Eqn. (1) position of drop at time t, m
a Y
fractional free area of perforated plate uniformity distribution parameter 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 er d
continuous phase
critical
dispersed phase final maximum stage number initial total densely packed region
f
max
n t
v
Vol. 16, No. 3, 2000
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MODELING OF LIQUID-LIQUID EXTRACTION COLUMN: A REVIEW

Vol. 16, No. 3, 2000

Modeling of Liquid-Liquid Extraction Column: A Review

Reviews in Chemical Engineering

+Ec cc/ ) C -L-koc(Cc c -C

Vol. 16, No. 3, 2000

Modeling of Liquid-Liquid Extraction Column: A Review

Reviews in Chemical Engineering

Vol. 16, No. 3, 2000

Modeling of Liquid-Liquid Extraction Column: A Review

Pulsed Sieve Plate Extraction Column (PSE)

Reviews in Chemical Engineering

Vol. 16, No. 3, 2000

Modeling of Liquid-Liquid Extraction Column: A Review

Reviews in Chemical Engineering

large number ofsystems

ii) bcnzcnc-acctic acid -

Vol. 16, No. 3, 2000

Modeling of Liquid-Liquid Extraction Column: A Review

Reviews in Chemical Engineering

Vol. 16, No. 3, 2000

Modeling of Liquid-Liquid Extraction Column: A Review

Reviews in Chemical Engineering

Vol. 16. No. 3, 2000

Modeling of Liquid-Liquid Extraction Column: A Review

no solute c-d d-c

k, 2.10xl0 6 2.14x10* l.lOxlO6

k2 44.53 44.53 50.56

k3 9.69 10 9.69 xlO' 3 9.69 xlO' 3

Reviews in Chemical Engineering

Rotating Disk Contactor (RDC):

Vol. 16, No. 3, 2000

Modeling of Liquid-Liquid Extraction Column: A Review

Reviews In Chemical Engineering

Vol. 16, No. 3, 2000

Modeling of Liquid-Liquid Extraction Column: A Review

Reviews in Chemical Engineering

Vol. 16, No. 3, 2000

Modeling of Liquid-Liquid Extraction Column: A Review

Reviews in Chemical Engineering

Vol. 16, No. 3. 2000

Modeling of Liquid-Liquid Extraction Column: A Review

Reviews in Chemical Engineering

Vol. 16, No. 3, 2000

Modeling of Liquid-Liquid Extraction Column: A Review

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

Reviews in Chemical Engineering

Reciprocating Plate Column (RFC):

Vol. 16, No. 3, 2000

Modeling of Liquid-Liquid Extraction Column: A Review

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

Reviews in Chemical Engineering

Vol. 16, No. 3, 2000

Modeling of Liquid-Liquid Extraction Column: A Review

Reviews in Chemical Engineering

Vol. 16, No. 3, 2000

Modeling of Liquid-Liquid Extraction Column: A Review

Reviews in Chemical Engineering

Vol. 16, No. 3, 2000

Modeling of Liquid-Liquid Extraction Column: A Review

</43 = 0.0123 - \Pc)

Reviews in Chemical Engineering

Vol. 16, No. 3, 2000