chemical engineering research and design 9 2 ( 2 0 1 4 ) 43–53

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Chemical Engineering Research and Design

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Effective diffusivity in a structured packed column:

Experimental and Sherwood number correlating study

Zoha Azizi a,∗ , Mohsen Rezaeimanesh a , Hossein Abolghasemi b,c , Hossein Bahmanyar b
a Department of Chemical Engineering, Mahshahr Branch, Islamic Azad University, Mahshahr, Iran
b Oil and Gas Center of Excellence, School of Chemical Engineering, College of Engineering, University of Tehran,
P.O. Box 11365-4563, Tehran, Iran
c Center for Separation Processes Modeling and Nano-Computations, School of Chemical Engineering, College of Engineering,

University of Tehran, P.O. Box 11365-4563, Tehran, Iran

a b s t r a c t

Mass transfer coefficients along a structured packed column were experimentally determined to obtain a new cor-
relation for dispersed phase Sherwood number based on molecular diffusivity. Then in a comparative investigation,
the correlation was re-established based on effective diffusivity. The applied chemical systems were toluene/acetic
acid/water (T/A/W) and butyl acetate/acetic acid/water (B/A/W). The effects of droplet size and packing height on
experimental Sherwood number were also discussed. It was shown that local Sherwood number could be increased
up to 188% with increasing the droplet size from 6 to 9 mm in fixed dispersed phase flow rate. It was also observed
that when height of packing increased from 10 to 40 cm, local Sherwood number decreased by almost 48% for con-
stant dispersed phase flow rate. The results have shown that the proposed correlation based on effective diffusivity
can estimate the experimental drop Sherwood number with high accuracy (error of less than 5%). Moreover, cur-
rent research shows that replacing molecular with effective diffusivity in some theoretical models can correct their
estimation.
© 2013 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords: Drop Sherwood number; Effective diffusivity; Liquid–liquid extraction; Droplet size; Structured packed
column

1. Introduction a number of structured packings have been developed for

Liquid–liquid extraction is an important chemical engineering
operation used in many industrial processes such as refining
of crude petroleum and extraction of metals. Different kinds
of liquid–liquid contactors are being used in industry, which
are classified according to the mixing type of two phases.
Packed liquid–liquid extraction columns are widely employed
in industrial practice. The flow of liquids in the column is
driven by the difference in densities of the two liquid phases.
Liquid may be made either continuous or dispersed by the use
of suitable distributors. The presence of packing in the col-
umn increases the local velocities, retards recirculation and
back-mixing and improves the distribution and hold-up of
the dispersed phase (Ghaffari Tooran et al., 2009). Recently,
distillation and are being considered for use in liquid–liquid
extraction.
A great deal of experimental effort has been expended prin-
cipally for the purpose of evaluating column performance for
design and scale-up. On the other hand, the design of an
extraction column for a given separation method needs reli-
able correlations for the prediction of overall mass transfer
coefficients, which is generally calculated through correla-
tions involving the Sherwood number. Since the scale-up of
extractors still depends on large quantities of pilot experi-
ments, measuring mass transfer coefficients by single drop
experiments is a promising method which is more economi-
cal and less time-consuming (Zappe et al., 2000; Wei and Fei,
2004).

∗
Corresponding author. Tel.: +98 652 235 7873; fax: +98 652 233 8586.
E-mail address: azizi.zoha@gmail.com (Z. Azizi).
Received 9 October 2012; Received in revised form 17 June 2013; Accepted 11 July 2013
0263-8762/$ – see front matter © 2013 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cherd.2013.07.008
44 chemical engineering research and design 9 2 ( 2 0 1 4 ) 43–53

Nomenclature
 c (c −d )gd232
 N needle
Ar Archimedes number = S solute
2c
Bi constant of Eqs. (2) and (3)
c solute concentration in dispersed phase
The mass transfer rate is strongly affected by droplet size
(kg/m3 )
and hydrodynamics of the two phases. Sometimes neglecting
c0 initial concentration of solute in dispersed
the effects of internal circulations of drops can cause a
phase (kg/m3 )
considerable error in calculating the mass transfer inside the
c* equilibrium concentration of solute in dis-
droplet (Ayyaswamy et al., 1990). Considering all parameters
persed phase (kg/m3 )
involved in prediction of mass transfer coefficient it is possible
d drop diameter (m)
to obtain mass transfer coefficient experimentally and then
d32 Sauter mean drop diameter (m)
an enhancement factor can be defined to correct diffusivity;
dcol column diameter (m)
replacing the molecular diffusivity with effective diffusivity
Deff effective diffusivity (m2 /s)
obtained from that enhancement factor can modify the mass
DM molecular diffusivity (m2 /s)
transfer coefficient. A similar job has been done on packed
dN needle size of nozzle (mm)
column in which a new correlation for effective diffusivity
E local efficiency  
(c −d )gd232 through enhancement factor was introduced (Rahbar et al.,
Eö Eötvös number =  2011). In the present study after a brief discussion on the
 
U2 behavior of mass transfer coefficient and Sherwood number
slip
Fr Froude number = gd32 along an experimental structured packed column, a new cor-
h height of sampling from the top of the nozzle relation for Sherwood number has been developed in which
(m) the effects of operational variables have been considered into
k number of components a group of dimensionless numbers. Then it was discussed
Kd dispersed phase mass transfer coefficient (m/s) that this correlation and other theoretical models can highly
n number of drops be improved by applying effective diffusivity instead of
N number of tests (observation points) molecular diffusivity whenever there are internal circulations
M molecular weight as well as other unknown parameters that can affect the
 (kg/kmol) 
(c −d )g4c mass transfer coefficient.
Mo Morton number =
c2  3
Q volumetric flow rate of dispersed phase (m3 /s) 1.1. Previous works
  for masstransfer
enhancement factor
c Uslip d32
Re Reynolds number = c Several correlations have been presented in past studies for
  calculation of dispersed phase mass transfer coefficient. The
Kd d32
Sh Sherwood number = DM most famous models still being considered for use to predict
t contact time (s) the mass transfer coefficient are Newman (1931) (based on
T temperature (K) molecular diffusion for unsteady state mass transfer inside
Uslip slip velocity of a single drop (m/s) a stagnant spherical drop), Kronig and Brink (1950) (based on
V molar volume at normal boiling temperature laminar diffusion with circulation induced by relative motion
(cm2 /mol)   of drop and continuous phase and neglecting the continu-
c U2 d32
We Weber number = slip ous phase resistance) and Handlos and Baron (1957) (based

on eddy diffusion between internal toroidal stream lines and
neglecting the continuous phase resistance).
Greek symbols The equations from these models are,
 interfacial tension (N/m) Newman (1931):
 ratio of dispersed
 phase viscosity to continuous
phase viscosity = dc
   

d 6 1 −4DM 2 i2 t
i constant of Eqs. (2) and (3) Kd = − ln exp Re < 10 (1)
6t 2 i2 d2
 viscosity (Pa s) i
 Pi number (=3.1415. . .)
ϕ association factor (= 2.6 for water, 1.9 for Kronig-Brink (1950):
methanol, 1.5 for ethanol, and 1 for unassoci- 

ated solvents)
d 3 2
 −64 D t 
i M
Kd = − ln Bi exp 10 < Re < 200
 density (kg/m3 ) 6t 8 d2
i
(2)
Subscripts
c continuous phase
Handlos-Baron (1957):
Deff effective diffusivity
d dispersed phase   

d −i Ut t
eff effective Kd = − ln 2 B2i exp Re > 200 (3)
i counter 6t 128(1 + )d2
i
m mixture
where the constant values of i and Bi were reported by Elzinga
and Banchero (1959),  = d /c and Re = c Uslip d/c .
 chemical engineering research and design 9 2 ( 2 0 1 4 ) 43–53 45

Other investigators have replaced the molecular diffusivity 2. Experimental study

with effective diffusivity, Deff , which is defined to be the prod-
uct of an enhancement factor, , to molecular diffusivity, DM , 2.1. Set up description
in order to show the effect of internal circulation (Amanabadi
et al., 2009). Inspired by this fact, Calderbank and Korchinski Experimental set-up contains a structured packed column in
(1956) have modified the equation of Kronig and Brink (1950) bench scale. The schematic figure of this set up is shown in
replacing DM with DM , Fig. 1(a).
   1/2

This column is made of a Pyrex glass tube. At the lower end

d −42 DM t of the column, there is a discharge valve and a glass entrance
Kd = − ln 1 − 1 − exp (4) nozzle which can be used to connect to different nozzles for
6t d2
dispersed phase inlet. The continuous phase (batch) is fed
from top and dispersed phase whose flow rate is controlled by
in which dimensionless enhancement factor, , is 2.25.
a rothameter enters through the bottom of column. To draw
In Johnson–Hamielec equation this enhancement factor is
the samples of the drops in different heights separate valves
a function of terminal velocity, molecular diffusivity, viscos-
have been provided. Structured packing as shown in Fig. 1(b)
ity ratio and drop diameter (Johnson and Hamielec, 1960).
and (c) has been used for which characteristic parameters are
Skelland and Wellek (1964) presented an empirical equation
described in Table 1.
in which Kronig and Brink’s model have been taken into
Before each run, the column was filled with continuous
account for binary liquid–liquid extraction systems with negli-
phase up to the sampling valve, i.e. at the heights of 10, 25
gible resistance in continuous phase. Steiner (1986) developed
and 40 cm. Opening its valve, dispersed phase was let to leave
a new correlation using Johnson–Hamielec equation based on
the nozzle in a single drop flow condition. Here the single
his own experimental data. Kumar and Hartland (1999) intro-
drops moved along the packing and were drawn to the open
duced a new correlation for prediction of dispersed phase
valve at each height. They scarcely moved beside the wall and
mass transfer coefficient of circulating drops based on the con-
the wall effect can be negligible. The column was operated
tinuous phase Reynolds number and dispersed phase Schmidt
isothermally at 20 ◦ C.
number. In a recent study (Rahbar et al., 2011), an empirical
correlation for prediction of enhancement factor is developed
2.2. Chemical systems
as follows:

The chemical system consisted of distilled water saturated

 = 0.0272(1 + h−1 ) Re1.258
in which the Reynolds number is calculated in each experi-
ment considering the physical properties
 of thecontinuous
c Uslip d32
phase and slip velocity of drops = c
advantage over similar equations in literature is involve-
ment of packing height which is really an important factor in
design.
In a work done by Ubal et al. (2010), numerical simula-
tions of mass transfer were performed for a circulating single
drop with applications in liquid–liquid extraction. However,
it is fair to say that even the mass transfer process on the
scale of a single drop is not fully understood. However, many
correlations are published for prediction of Sherwood num-
ber. Although many of them have a good theoretical basis,
they do not practically have accurate results. For instance,
since stagnant drop models do not consider any circulation
(5)
with toluene or butyl-acetate as continuous phase, while dis-
persed phase involved toluene or butyl acetate saturated with
water and the solute was specific amount of acetic acid.
The mass transfer direction is from dispersed to continuous
. Its main phase. The physical properties of the systems are tabulated
in Table 2. According to this table, these two systems have
almost similar physical properties but are different in interfa-
cial tension, which is lower in system 2. The phases’ densities
are determined by use of a scale in order of 0.0001 g based
on 1000 cc, and the viscosities are evaluated by a laboratory
LAUDA viscometer which has resolution of 0.001 mPa s. Inter-
facial tensions are based on the literature (Murphy et al., 1957;
Jufu et al., 1986). The modified Wilke-Chang correlation (Eq. (6))
was used to calculate the molecular diffusivity (Poling et al.,
2001):
(ϕM)
1/2
T
k

in drop and practically there are some movements in droplets DSm = 7.4 × 10−5 ϕM = xi ϕi Mi (6)
m VS0.6
hence the predicted Sherwood numbers of these models are i=1
considerably lower than experimental ones. Even though cir- i=
/ S
culating drop models give better results than stagnant drop
models as they consider internal circulation of drops (Rahbar
2.3. Calculation of experimental dispersed phase mass
and Bahmanyar, 2012), we can obtain the mass transfer coef-
transfer coefficient
ficient with much better precision by considering the effect of
packing height together with internal circulation in Sherwood
From mass balance for a single drop, we get (Slater and
number.
Godfrey, 1994):
There are also some other works on this topic but most
of them could not be applied for comparison with present
d
study since they have been presented for a specific column Kd = − ln(1 − E) (7)
6t
or a specific condition. For example Jie et al. (2005) studied
on high viscosity solvents or in a study on this topic Koncsag
where
and Barbulescu (2008) presented a correlation in which
there were parameters which were specific for their own c0 − c
E= (8)
experiment. c0 − c∗
46 chemical engineering research and design 9 2 ( 2 0 1 4 ) 43–53

Fig. 1 – (a) Schematic diagram of the apparatus, (b) a piece of Penta-Pack TM PS-500M1 structured packing, and (c)
characteristics of packing.

Table 1 – Characteristic parameters for the structured packed columns used.

Characteristic parameters [Unit] Value/Property

Column diameter, dcol [m] 0.10

Column height [m] 1.25
Type of packing [–] Penta-Pack TM PS-500M1
Number of packing sections used in the column [–] 2
Length of one packed element [m] 0.20
Diameter of one packed element [m] 0.091
Inclination of corrugated sheets [–] 45o
Void fraction within “packed channels” [–] 0.94
Specific surface for the flow [m2 /m3 ] 500
Height of the structured packed section [m] 0.40
Diameter of nozzles [mm] 0.4, 0.8, 1.75, and 2.0
Number of nozzles in each run [–] 1
 chemical engineering research and design 9 2 ( 2 0 1 4 ) 43–53 47

Table 2 – Physical properties of systems at 20 ◦ C.

Physical property System 1 (T/A/W) System 2 (B/A/W)
3
c (kg/m ) 1009.7 1010.2
d (kg/m3 ) 882.7 895.9
c (mPa s) 1.016 1.013
d (mPa s) 0.611 0.684
 (mN/m) 27.5–30.1 12.4–13.2
DM (m2 /s) 2.92 × 10−9 2.66 × 10−9

in which c0 , c, and c* are solute concentration in primary
drop (before contact), concentration in specific position and
the equilibrium concentration, respectively. In each experi-
ment for different heights of the column by measuring acetic
acid concentration, mean drop diameter (d32 ), and the contact
time between two phases (t), the mass transfer coefficients
(Kd ) were calculated by Eq. (7). The Sauter mean drop diame-
ters, d32 , were determined by photographing the drops using a
high-resolution Powershot G9 type camera with a background
reference size located inside the column, followed by analysis
with Photoshop software. At least 200 drops were analyzed for
each determination. Then from Eq. (9) the Sauter mean drop
diameter can be calculated (Slater, 1994).
 3
nd
d32 =  i i2 (9)
ni di
The acetic acid content of the dispersed phase was deter-
mined by a titration technique using normal NaOH and
phenolphthalein as the indicator. The rising time of a drop,
t, was determined by use of a stop watch and measuring time
of a single drop from the moment it left the nozzle until being
collected from the valve. Thus, with regard to mass transfer
coefficient one can obtain the experimental Sherwood number
using Eq. (10):
Kd d32 d2
Sh = = − 32 ln(1 − E) (10)
DM 6tDM
Two different volumetric flow rate of dispersed phase
(Q1 = 21.8 ml/min and Q2 = 15.6 ml/min) have been used, which
were kept fixed by a rotameter during two series of the tests
in order to have the desired range of spherical droplet size.
Moreover, four different needle sizes of nozzles (dN = 0.4, 0.8,
1.75 and 2.0 mm) are used to study the effect of droplet size
on mass transfer. Table 3 illustrates how the tests have been
implemented for full factorial experimental design; with two
different flow rates, Q, three different heights of sampling, h,
and four different needle sizes of nozzles, dN , the number of
observation points would be 2 × 3 × 4 = 24 for each chemical
system. To verify the repeatability, 135 tests have totally been
implemented on both chemical systems.
3. Results and discussion
The experimental values of dispersed phase mass transfer
coefficients versus the height of packing in different nozzles
are presented in Tables 4 and 5 for systems T/A/W and B/A/W,
respectively.
According to these tables, the dispersed phase mass trans-
fer coefficient decreases with increase of the packing height,
i.e., when height of packing increases from 10 to 40 cm, mass
transfer coefficient decreases by almost 46% for the dispersed
phase flow rate of 21.8 ml/min, and by almost 45% for the
dispersed phase flow rate of 15.6 ml/min. We know that by
drop movement along the column, the mass transfer occurs
and the acetic acid concentration inside the drop decreases,

Table 3 – The characteristics of tests (observation points) for full factorial experimental design for each chemical system.
Observation point number Q (ml/min) h (m) dN (mm)

1 15.6 0.10 0.40

2 15.6 0.10 0.80
3 15.6 0.10 1.75
4 15.6 0.10 2.00
5 21.8 0.10 0.40
6 21.8 0.10 0.80
7 21.8 0.10 1.75
8 21.8 0.10 2.00
9 15.6 0.25 0.40
10 15.6 0.25 0.80
11 15.6 0.25 1.75
12 15.6 0.25 2.00
13 21.8 0.25 0.40
14 21.8 0.25 0.80
15 21.8 0.25 1.75
16 21.8 0.25 2.00
17 15.6 0.40 0.40
18 15.6 0.40 0.80
19 15.6 0.40 1.75
20 15.6 0.40 2.00
21 21.8 0.40 0.40
22 21.8 0.40 0.80
23 21.8 0.40 1.75
24 21.8 0.40 2.00
48 chemical engineering research and design 9 2 ( 2 0 1 4 ) 43–53

Table 4 – Mass transfer coefficient (Kd ) versus height of packing for four different nozzle sizes and fixed volumetric flow
rate of dispersed phase (Q), system (T/A/W).
h (mm) (packing height) Nozzle diameter (mm)

0.4 0.8 1.75 2.0

(a) Kd (cm/s) in Q = 15.6 ml/min.

100 0.0155 0.0197 0.0237 0.0275
250 0.0088 0.0138 0.0162 0.0209
400 0.0086 0.0104 0.0129 0.0147
(b) Kd (cm/s) in Q = 21.8 ml/min.
100 0.0192 0.0203 0.0251 0.0304
250 0.0099 0.0142 0.0199 0.0224
400 0.0089 0.0115 0.0145 0.0163

Table 5 – Mass transfer coefficient (Kd ) versus height of packing for four different nozzle sizes and fixed volumetric flow
rate of dispersed phase (Q), system (B/A/W).
h (mm) (packing height) Nozzle diameter (mm)

0.4 0.8 1.75 2.0

(a) Kd (cm/s) in Q = 15.6 ml/min

100 0.0170 0.0180 0.0190 0.0233
250 0.0123 0.0127 0.0148 0.0149
400 0.0083 0.0104 0.0107 0.0109
(b) Kd (cm/s) in Q = 21.8 ml/min
100 0.0246 0.0250 0.0290 0.0298
250 0.0161 0.0165 0.0180 0.0213
400 0.0113 0.0132 0.0139 0.0151

thus the driving force of mass transfer decreases as height
of packing increases. This reason is not generally true unless
we can assume that the continuous phase resistance is neg-
ligible; but since we have a single drop flow of dispersed
phase, the continuous phase remains almost pure and the
assumption is valid. Consequently, the local efficiency and
mass transfer coefficient decrease. Additionally, when using
larger needle sizes of nozzles while the dispersed phase flow
rate is constant, larger drops are produced inside of which
internal circulation becomes significant (Skelland, 1985). This
phenomenon resulted in increase of mass transfer such that
mass transfer coefficient increases by 89% for flow rate of
21.8 ml/min, and by 105% for the flow rate of 15.6 ml/min. It
should be noted that either breakage or coalescences along the
packed bed are negligible as proved by photograph analysis.
Furthermore, for the flow rates we used we had desired range
of droplet sizes with spherical shapes throughout the range of
dispersed phase flow rate. The droplet size range during the
tests was 6–9 mm.
In Figs. 2 and 3 the experimental results of Sherwood num-
ber along the packed column in different nozzles with fixed
volumetric flow rates are shown. While height of packing
increases from 10 to 40 cm, local Sherwood number decreases
by almost 47% for dispersed phase flow rate of 21.8 ml/min,
and by almost 49% for flow rate of 15.6 ml/min. It is apparent
from Eq. (10) that there is a direct relation between the experi-
mental Sherwood number and mass transfer coefficient. Thus,
the decreasing trend of mass transfer coefficient leads to
reduction in Sherwood number. It is also shown that when
using larger needle sizes of nozzles, local Sherwood number
could be increased up to 188% for the flow rate of 21.8 ml/min,
and up to 182% for the flow rate of 15.6 ml/min.

Nozzle diameter=0.4 mm Nozzle diameter= 0.8 mm Nozzle diameter=0.4 mm Nozzle diameter= 0.8 mm
Nozzle diameter= 1.75 mm Nozzle diameter= 2 mm
Nozzle diameter= 1.75 mm Nozzle diameter= 2 mm
900 800
800 700
700
600
600
500
Sh

Sh

500
400
400
300 300
200 200
(a) (b)
100 100
0.1 0.2 0.3 0.4 0.1 0.2 0.3 0.4
h [m] h [m]

Fig. 2 – The local Sherwood number versus height of packing with four different nozzles and in fixed volumetric flow rate
((a) 15.6 ml/min and (b) 21.8 ml/min), for system (T/A/W).
 chemical engineering research and design 9 2 ( 2 0 1 4 ) 43–53
Nozzle diameter=0.4 mm Nozzle diameter=0.8mm
Nozzle diameter=1.75 mm Nozzle diameter=2mm
500
400
300
Sh
200
100
(a)
0
0.1 0.2 0.3 0.4
h [m]
Fig. 3 – The local Sherwood number versus height of packing with four different nozzles and in fixed volumetric flow rate
((a) 15.6 ml/min and (b) 21.8 ml/min), for system (B/A/W).
4. Data correlation
4.1. Correlating the Sherwood number based on DM
The aim is to find a correlation for local Sherwood num-
ber. The Sherwood number is directly proportional to mass
transfer coefficient and generally restate the amount of
mass transfer in a dimensionless form. We have tried to
define the effective parameters on mass transfer coefficient
as dimensionless numbers. If we consider mass transfer
coefficient as a function of drop diameter (d32 ), viscosity
(), density (), interfacial tension (), packing geometry (h
and dcol ) and slip velocity (Uslip ), then we have 7 variables
with 3 reference dimensions of Mass, Length, and Time,
thus according to Buckingham Pi theorem we can group
them as (7 − 3 = 4) dimensionless numbers. There are vari-
ous dimensionless numbers which holds these variables and
can be grouped to have a predictive correlation for Sher-
wood number. Among dimensionless numbers of Reynolds
(Re = c Uslip d32 /c ), Weber (We = c Uslip
2 d /), Eötvös (Eö = ( −
32 c cients are a symptotically normally distributed (QMS, 2002).
d )gd232 /), Morton (Mo = (c − d )g4c /c2  3 ), Archimedes (Ar =
c (c − d )gd232 /2c ), Froude (Fr = Uslip
2 /gd ), etc., we tried to find
32
the most effective and independent ones. Considering their
equations, it is apparent that the Archimedes number (Ar) is
related to Reynolds number. The interaction between gravi-
tational and viscous forces can also be defined by Eötvös (Eö)
number. The Morton number (Mo) is a dimensionless num-
ber used together with the Eötvös number to characterize the
shape of bubbles or drops moving in a surrounding fluid or
continuous phase. The Morton number can also be expressed
by using a combination of the Weber number, Froude number
and Reynolds number (Mo = We3 Fr−1 Re−4 ). With this condi-
49
Nozzle diameter=0.4mm Nozzle diameter=0.8mm
Nozzle diameter=1.75mm Nozzle diameter=2mm
1000
900
800
700
600
500
Sh
400
300
200
100 (b)
0.1 0.2 0.3 0.4
h [m]
predicted by model and experimental values. According to
the strength of EViews computing program in such area, it
is being used for establishment of different combinations of
the dimensionless numbers above. The parameter R2 mea-
sures the success of the regression in predicting the values
of the dependent variable within the sample. In standard set-
tings, may be interpreted as the fraction of the variance of the
dependent variable explained by the independent variables.
The statistic will equal one if the regression fits perfectly, and
zero if it fits no better than the simple mean of the dependent
variable. Another criterion, Prob, is defined in the program,
which tells about the presence probability of each variable in
the defined correlation. The value of Prob is also between 0 and
1, but conversely, the closer to zero indicates that the variable
is more effective, i.e. if the variable’s Prob were zero, it defi-
nitely should be present in the correlation. Thus this criterion
measures the probability of drawing a t-statistic as extreme
as the one actually observed, under the assumption that the
errors are normally distributed, or that the estimated coeffi-
In the computing program, first a general correlation as
Eq. (11) was given with the values of dimensionless numbers
calculated from our 24 observation points for each chemical
system defined in Table 3. The resulted values for the parame-
ters of A, B, C, D and E is shown in Table 6. It can be concluded
from this table that the use of this combination does not seem
to be much appropriate since the Probs are close to 1. It was
also observed that the data reproduced by Eq. (11) is way off
compared to experimental Sherwood number with average
absolute diversion (AARD) of 91.43%. It is noted that the AARD
for the N data is calculated as follows:
 
1  experiment − model 
N
tion, a general expression of grouped dimensionless numbers
to predict the drop phase Sherwood number is as follows:
%AARD =
N
 experiment
 h E
Sh = A ReB WeC EöD
dcol
Having divided by the inside diameter of the column, the
height of packing has also become dimensionless in the above
expression. In this research in the process of correlating, the
method of least square has been applied which is one of
the most appropriate methods and has an extensive appli-
cation in modeling area. It is based on minimizing the sum
of the squares of residuals -the difference between values
 × 100 (12)
i=1
(11) Additionally, residual plot based on Eq. (11) for system 2
as a sample is shown in Fig. 4, which also displays the calcu-
lated versus experimental Sherwood number in comparison.
According to this figure we can conclude that Eq. (11) may not
be useful due to increase of residuals with Sherwood number.
In fact Buckingham’s theorem only provides a way of gen-
erating sets of dimensionless parameters, and will not choose
the most ‘physically meaningful’. Hence, other combinations
of the mentioned dimensionless numbers have been tried in
50 chemical engineering research and design 9 2 ( 2 0 1 4 ) 43–53

Table 6 – The average results of coefficients in the general model for both systems.
Sh = A ReB WeC EőD (h/dcol )E

Coefficient Prob.

A 397.4004 1.0000
B −0.055907 1.0000
C 0.060767 1.0000
D 1.125563 0.9997
E −0.478452 0.0000

R-squared 0.989945
Adjusted R-squared 0.988117
S.E. of regression 25.67054

2500 Exprimental Sh Model Sh Residuals

2000
Sherwood Number

1500

1000

500

0
0 5 10 15 20 25
Observaon Point Number

Fig. 4 – Comparison of experimental results with calculated values from general model (Eq. (11)) and residuals based on DM
for system 2 (B/A/W).

the program and with the given Probs, %AARD, R2 value, and
also considering the resulted residuals finally the correlation
below (Eq. (13)) has been selected.
 h −0.539
Sh = 250.847 Re0.06 Eö0.786
dcol
2 wholly diffusive. For the circulating drop, material is trans-
R = 0.99 AARD = 6.14%
The Probs given by the program were all zero. Consider-
ing the values of R2 it is found that the proposed correlation
has good agreement with experimental data of each chemi-
cal system. As understood from the physical property table
(Table 2), the proposed correlations can be used for systems
of similar physical properties with possible difference in their
interfacial tension. Weber and Eötvös numbers both depend
on physical properties of phases including interfacial tension,
and Hartland, 1999). These circulation patterns convert the
mass transfer process from a purely diffusive one, to an
advective-diffusive process (Juncu, 2001), leading to a con-
siderable complication in the spatio-temporal distribution of
solute. As discussed by Ubal et al. (2010), the circulating drop
equilibrates faster than the rigid drop which is by definition
(13)
ported rapidly along streamlines, and only needs to diffuse
between the surface and an internal stagnation point of the
streamline pattern. This gives a lesser diffusion distance than
the rigid drop, where material diffuses between the surface
and the center, and hence a more rapid equilibration time.
Sys#1 (T/A/W) Sys#2 (B/A/W)
1200.00
Calculated Sherwood Number

1000.00
hence have the same trend, may be interpreted as a conflict,
with the experimental dataset. In fact, passing from Eq. (11) 800.00 +10%
to Eq. (13) to have better R2 and also AARD might be hidden in
the removal of this conflict. -10%
600.00
As shown in Fig. 5, the error produced by the proposed cor-
relation is not considerable and can guaranty the accuracy of 400.00
results for both systems. Corresponding residual plot of Fig. 6
indicates that most of the residuals are randomly scattered 200.00
around zero.
0.00
4.2. Correlating of Sherwood number based on Deff 0 200 400 600 800 1000 1200
Experimental Sherwood Number
Drops dispersed in liquid-liquid extraction systems are gen-
erally not rigid entities. Circulation patterns can affect them Fig. 5 – Comparison of experimental results with calculated
internally and also externally (Kronig and Brink, 1950; Kumar values (Eq. (13)) based on DM .
 chemical engineering research and design 9 2 ( 2 0 1 4 ) 43–53 51

Sys#1 (T/A/W) Sys#2 (B/A/W)

100.00

80.00

60.00

40.00

Residuals 20.00

0.00
0 5 10 15 20 25
-20.00

-40.00

-60.00

-80.00
Observaon Point Number

Fig. 6 – Residual plot for the calculated Sherwood number from Eq. (13).

In the present section, we desire to replace molecular dif- Sys#1 (T/A/W) Sys#2 (B/A/W)
10
fusivity (DM ) with effective diffusivity (Deff ) in the available
correlations to study the effect of other unknown parameters, 9

Calculated Sherwood Number

such as internal circulations interfering in determination of 8
mass transfer coefficient and also of Sherwood number. We 7
are trying to obtain an equivalent correlation for Sherwood 6 +5%
number considering effective diffusivity. Thus the values of -5%
5
experimental Sherwood number should be re-obtained from 4
Eq. (14):
3
2
Kd d32 d232
ShDeff = =− ln (1 − E) (14) 1
Deff 6tDM
0
0 2 4 6 8 10
in which ShDeff is the Sherwood number based on Deff and the
Experimental Sherwood Number
values of  are those calculated in our own recent work for
both systems (Rahbar et al., 2011). According to our literature Fig. 7 – Comparison of experimental results with calculated
survey this replacement is a new proposition in defining Sher- values (Eq. (15)) based on Deff .
wood number. By the modified results of Sherwood number,
a new correlation is resulted from computing program with
(Eq. (15)) and the experimental Sherwood number (Eq. (14))
almost equal coefficients for both systems as follows,
shown in Fig. 7, the modified correlation can well predict the
 h −0.091 Sherwood number with average absolute relative diversion
Sh = 7.264 Re0.046 Eö0.017 of 1.79%, which reveals better agreement with experimen-
dcol
tal results than the previous correlation (Eq. (13)). In other
2
R = 0.92 AARD = 1.79% (15) words, effective diffusivity can improve the proposed corre-
lation. Here, the mass transfer is not controlled by molecular
With above equation the Probs were again almost zero. diffusivity, but by effective diffusivity. Corresponding residu-
According to the comparison made between predicted values als are plotted in Fig. 8. With a comparative look it is found

Sys#1 (T/A/W) Sys#2 (B/A/W)

1

0.8

0.6

0.4
Residuals

0.2

0
0 5 10 15 20 25
-0.2

-0.4

-0.6

-0.8
Observaon Point Number

Fig. 8 – Residual plot for the calculated Sherwood number from Eq. (15).
52 chemical engineering research and design 9 2 ( 2 0 1 4 ) 43–53
Table 7 – The %AARD results of two theoretical Sherwood number based on DM and Deff comparatively.
Type of system ShNewman
Based on DM
T/A/W 89.0
%AARD
B/A/W 88.8
that the random residuals are more concentrated around zero
in Fig. 8 than in Fig. 6.
It is important to note that from Fig. 7, the range of Sher-
wood numbers has been compacted because of using effective
diffusivity. The new range is what we expect from single drop
experiment.
Moreover, two models of Newman and Calderbank-
Korchinski have been selected, in both of which the effective
diffusivity has been used. Actually, among the many theoreti-
cal models available in literature these two have been chosen
to be compared with our proposed models since they are
found to be more general – e.g. Newman model has a strong
mathematical basis – and more similar with respect to our
experimental condition, while others could not be applied for
comparison with present study since they have been devel-
oped for a specific column or a specific condition. Table 7
shows the %AARD of predicted values for both models using
DM and Deff comparatively.
It is obvious from Table 7 that the prediction made by
these models is far way off. Newman studied the unsteady
state mass transfer inside the droplets and assumed that
droplets are so small that internal circulation of them is negli-
gible. Thus the presented equations by Newman are useful for
very small and rigid droplets. Calderbank-Korchinski model
is an approximation form of the Kronig-Brink’s model which
itself considers the small droplet sizes with laminar internal
circulation. Packing cause internal circulation and increases
the mass transfer coefficient (Azizi et al., 2010; Rahbar and
Bahmanyar, 2012), additionally the droplet size range in this
experiment was 6–9 mm, and according to what we know
from literature (Skelland, 1985), when droplet size is more
than 2 mm the internal circulations play a significant role in
changing the mechanism of mass transfer. That’s why these
correlations are not fitted with our experimental data, while
the effective diffusivity can highly improve their predicted val-
ues.
5. Conclusions
Several tests have been carried out in the packed column to
obtain mass transfer coefficient and also Sherwood number,
accompanied by a Sherwood number correlation and attempt-
ing to modify it through effective diffusivity replacement.
The ultimate results indicate that when height of packing
increases, mass transfer coefficient and Sherwood number
decrease. With the increase of needle size of nozzles, larger
drops with internal circulations are produced which can raise
both of the mass transfer and Sherwood number. Results of the
proposed models have proved a good compatibility with exper-
imental data, and when using effective diffusivity instead of
molecular diffusivity their prediction improves significantly.
Defining effective diffusivity for theoretical models can also
highly improve the predicted values. It is possible to extend
the applicability of the well-known Newman, Calderbank-
Korchinski, and also our proposed equation to real drops,
independent of their internal behavior. This approach can
ShCalderbank-Korchinsky
Based on Deff Based on DM Based on Deff
0.040 82.7 6.35
0.045 89.0 6.67
be used to obtain more precise design of structured packed
columns.
Acknowledgements
This work as a research project entitled “Investigation of
Mass Transfer Coefficient in Liquid-Liquid extraction Packed
Columns” was supported by a grant from the Islamic Azad
University of Mahshahr Branch.
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