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hydrometallurgy
ELSEVIER Hydrometallurgy42 (1996) 281-29 !

Separation of liquid-liquid dispersions in a

deep-layer gravity settler: Part II. Mathematical
modeling of the settler
M.C. Ruiz *, R. Padilla
Department of Metallurgical Engineering, University of Concepci6n, Edmundo Larenas 270, Casilla 53-C,
Concepcibn, Chile
Received 2 May 1995; accepted 28 September 1995

Abstract

A mathematical model for the steady-state operation of a deep-layer gravity settler has been
developed by using a population balance approach. This model takes into account the size
distribution of drops within the dispersion band and uses rate expressions for the description of
drop-drop and drop-interface coalescence phenomena. The model was validated with experimen-
tal data obtained in a laboratory mixer-settler unit, for a system consisting of 10% Acorga M5640
in Escaid 103-0.25 M Na2SO4 aqueous solution. The model successfully predicts the thickness
of the dispersion band and the growth of the dispersed phase drops occurring by drop-drop
coalescence within the dispersion band.

1. Introduction

The separation of liquid-liquid dispersions in gravity settlers is a complex process

where sedimentation and coalescence of drops are involved. At present, there is a need
for simple theoretical models for a reliable prediction of industrial settling processes.
Therefore, a mathematical model of a gravity settler based on fundamental principles
would be a powerful tool for analysis and design of this equipment, which is used
extensively in the mining industry.

* Corresponding author. E-mail: mruiz@euler.met.udec.cl

0304-386X/96/$15.00 Copyright © 1996 Elsevier Science B.V. All rights reserved.

SSDI 0304-386X(95)00096-8
282 M.C. Ruiz, R. Padilla / Hydrometallurgy 42 (1996) 281-291

In the past three decades, a large amount of research has been conducted on the
coalescence of dispersions using different liquid-liquid systems. This work has been
reviewed by Glasser et al. [1] and more recently by Blal~ et al. [2]. The main effort of
mathematical modeling was directed toward vertical settlers, while little work has been
reported on the modeling of horizontal settlers. On the latter, a few attempts have been
made to model the separation of phases in a gravity settler with a wedge-shaped
dispersion band. Here, the pertinent work on horizontal settler modeling is briefly
discussed.
Jeffreys and Davies [3] reported a differential model for the case of wedge-shaped
dispersion bands. The model was developed by setting up balances for the volume of
dispersed phase and for the number of drops within the dispersion wedge. The size of
the drops at any position in the wedge was characterized by a mean drop diameter, ~b.
These investigators considered the drop-drop and drop-interface coalescence times as a
function of ~b~5. This model predicted wedge length, mean drop size, and depth along
the dispersion wedge. Later, Hartland and Jeelani [4] presented a similar model for a
horizontal settler which allowed for the dispersion band to have a finite thickness at the
end wall of the settler. A mean drop diameter was also used to characterize the size of
the drops within the dispersion band. This model used a polynomial function to describe
the variation of the dispersion height with the distance from the settler inlet. The fact
that the parameters of this polynomial needed to be determined from experimental data
limited the predictive capacity of the model.
A different approach based on a population balance was used by Ruiz [5] to model a
settler with a wedge-shaped dispersion band. In this model the dimensions of the
dispersion wedge were given by a balance between the rate of entrance of the dispersion
and the rate at which the droplets coalesced at the active interface. This model took into
account the size distribution of the drops within the dispersion band and involved rate
expressions for drop-interface and drop-drop coalescence. The model predicted accu-
rately the drop size distribution along the length of the dispersion band and the thickness
and length of the band as well.
Barnea and Mizrahi [6] studied the separation of phases in a deep-layer gravity settler
and proposed a semi-empirical model. According to them, most of the volume of the
dispersion band was occupied by the smallest size fraction of the feed droplets and had a
structure similar to a liquid-liquid fluidized bed, with a volume concentration of
dispersed phase close to that of the feed. By considering the hindered settling of the
smaller drops in the band, together with the rate of growth of the drops by coalescence,
they were able to reproduce the empirical result of Ryon et al. [7] that the dispersion
band thickness was proportional to the specific flow rate of dispersion raised to a power.
A minimum value of 2.5 for the exponent of the power function was predicted for the
case of creeping flow in the band and when the drop-drop coalescence rate was
controlled by the collision rate.
The aim of the present work was to carry out an experimental study of the separation
of phases in a horizontal gravity settler and to develop a mathematical model of the
settler. In the first part of this series, the experimental study was reported, based on
those observations, in the present paper a mathematical model for the continuous
separation of phases in a deep-layer gravity settler is described.
 M.C. Ruiz, R. Padilla / Hydrometallurgy 42 (1996) 2 8 1 - 2 9 1 283

2. F o r m u l a t i o n o f t h e m o d e l

For the steady-state operation of a horizontal gravity settler, with the incoming
dispersion distributed uniformly at the passive interface (as has been found to occur by
experimental evidence, reported in part I of this series), a mathematical model was
formulated based on a balance for the number of drops in an elemental volume of the
dispersion band. This situation is depicted schematically in Fig. 1. The following
assumptions were considered:
Drop-drop coalescence is a binary event, and the drop size distribution at any
position in the band is well represented by a continuous (in drop volume) distribution.
The vertical velocity of the drops, the drop size, and the dispersed phase hold-up within
the dispersion band in the settler change only in the Z (vertical) direction. Any changes
in the X or Y direction are neglected. Under these conditions, it is only necessary to
model a unit settler area and the results can be extended to settlers of any size.
Let us now consider a stationary elemental volume of unit area (L × W) and
thickness ~z within the dispersion band, located at a height z above the passive
interface and at an arbitrary distance from the settler inlet. Fig. 1 shows this elemental
volume for the case where the lighter phase is the dispersed phase. Characterizing the
size of the drops in the band by their volume, v, a balance for the number of drops over
the stationary volume element can be written as:

[No. of drops of size v to v + dv entering the element per unit time]

- [No. of drops of size v to v + dv leaving the element per unit time]

- [No. of drops of size v to v + dv disappearing by drop-drop

× coalescence within the element per unit time]

+ [No. of drops of size v to v + d v appearing by drop-drop

× coalescence within the element per unit time] = 0 (1)

I
Organic phase I
.............................................................. Act.iveinter[aee\

z Dispersionband

x . ......................................... 6z ....................
L
/
i/
/
• ......................................................... Pas~ve interface ..............................
.. " Aqueousphase /

Fig. I. S c h e m a t i c d i a g r a m o f thc h o r i z o n t a l g r a v i t y settler s h o w i n g the differential v o l u m e c l e m c n t o f

t N c k n e s s gz.
284 M.C.Ruiz,R. Padilla/ HydrometaUurgy42 (1996)281-291
This balance can be expressed mathematically as follows:
aS( z ) n( v, z )dvlz

6z Frv
k
-QS(z)n(v'z)dvlz+~z- N(z---'-ff A(v,v',z)n(v,z)n(v',z)dv' dv
]
]
+ 2N--~Z) [)o A( v - v',v,z)n( v - v ' , z ) n ( v',z)dv' ] d r = 0 (2)

where: QS(z) = Qr/A = specific volumetric flow rate of dispersion entering the volume
element; Qr = total flow rate of dispersion; A = total settling area; n(v, z)dv = number
of drops of size v to v + dv per unit volume of the dispersion band at position z;
A(v,v',z)=drop-drop coalescence frequency at position z (time-I); N(z)
= L n(v,z)dv = total number of drops per unit volume at position z.
~d

The forms given to the third and fourth terms in Eq. (2) were based on the
experimental finding that the drops in the dispersion band are closely packed and their
motion is restricted by the high population density. Under such conditions any drop can
only coalesce with the drops that immediately surround it.
Considering that:

OS(z) = ~/( z-----ff (3)

where: "q(z)= dispersed phase hold-up (volume fraction of dispersed phase); Q~ =

Qd/A = specific volumetric flow rate of dispersed phase.
At steady state Q~ is a constant throughout the dispersion band since all of the
dispersed phase entering the settler will eventually coalesce at the active interface.
Replacing Eq. (3) in Eq. (2), dividing it by g z and taking the limit as g z ~ 0 the
following equation was obtained:
n(v,z)dv
d n(z)
a~d dz

- N(z) '[So 1 1
X [foVA(v - v',v',z) n( v - v',z) n( v',z) dv'] dv (4)

Carrying out the differentiation of the left hand side and rearranging we have:
d[n(v,z)dv]
dz
n(v,z)dv dr/(z)
r/(z) dz
QdsN(z) A(v,v',z) n(v,z)n(v',z)dv' dv

"o(z) z) [foVA(v_v,,v,,z) n(v_v,,z)n(v,,z)dv,]dv

-t 2Q~N( (5)
 114.c. Ruiz, R. Padilla/ Hydrometallurgy42 (1996)281-291 285

The first term in the right hand side of this equation represents the change in the number
of drops of size v to v + dv per unit volume due to the variations in the dispersed phase
hold-up ('q). The second term represents the death rate or rate of disappearance of drops
of size v to v + dv by drop-drop coalescence, and the third term represents the birth
rate or rate of appearance of drops of size v to v + dv due to coalescence of smaller
drops.
This model equation was solved with the following boundary conditions:(1) At the
passive interface (z = 0):
n( v, z) = n ( v , 0 ) = inlet drop size distribution
This condition implies that the distribution of the incoming dispersion at the level of the
passive interface takes place rapidly with negligible growth of the dispersion drops. The
experimental determination of drop sizes in the band showed that this assumption is
reasonable.(2) At the active interface (z = H):

Ap( H ) N ( H)
fo v;t* ( v,H) n( v,H) dv = Q~d (6)
where: H = thickness of the dispersion band; " q * ( H ) = surface fraction of dispersed
phase; X* (v,H) = drop-interface coalescence frequency (time- l); Ap(H) = average
projected area of the drops.
This condition merely states that the volumetric interracial coalescence rate per unit
area must be equal to the specific flow rate of dispersed phase fed to the settler.
For spherical drops:

(6)2J3 o v '3n vH,dv (7)

Ap(H) = ~ N(H)

3. Solution of the model equation

Eq. (5) is a non-linear integro-differential equation which does not have an analytical
solution; therefore, it was solved numerically by a discretization method originally
proposed by Sastry and Gaschinard [8]. This method has also been used by Ruiz [5] to
solve a similar equation and found to give very accurate results with a minimum
computational effort.
The set of differential equations, which was obtained from the discretization of the
model equation, was solved by using a fourth-order Adams Moulton predictor-corrector
method. The computer program was written in FORTRAN code and the simulations
were carried out on a personal computer.

4. Parameters of the model

The dispersed phase hold-up, "q, the surface fraction of dispersed phase at the active
interface, "q*, the drop-drop coalescence frequency, X, and the drop-interface coales-
286 M.C. Ruiz, R. Padilla / HydrometaUurgy 42 (1996) 281-291
1.0

0,9

0.8

0.7

0.6

. - ............. +..--.= ......... , + - - + . I ................. *

~ o5

~4
0.3
0.2 •
O/A ratio
0.6
I
• 0.8
• 1.0

0.0 = i
0.8 112 ' 11.6 21.0 2.4

QJA,~ m
Fig. 2. Dispersedphase hold-upat the passiveinterfaceversusthe specificdispersedphase flow rate.

cence frequency, h*, are the parameters of the model. For the system studied here, the
dispersed phase hold-up within the dispersion band, "q(z), as reported in part I of this
series, was found to increase linearly from the passive to the active interface. Therefore,
a linear dependency on z was used:
n ( z ) = n(0) + z (8)
where "q(0) is the dispersed phase hold-up at the passive interface.
The value of "q(0) was determined from the experimental data, extrapolating the
linear relationship obtained for various specific flow rates and organic/aqueous ratio,
O / A . The corresponding values were around 0.53 for the condition in which the
hold-up of the incoming dispersion was less or equal to 0.53, as illustrated in Fig. 2,
otherwise the "q(0) was equal to the hold-up of the feed. The slope A'q was found to be a
function of the specific flow rate of dispersed phase ( Q a / A ) , as reported in part I.
The surface fraction of dispersed phase (or surface-packing efficiency) in the active
interface, "q* (H), was considered equal to 1.0, since the drops in the active interface are
very closely packed and distorted in such a way that they covered the whole interfacial
area. The only continuous phase present in the active interface was a very thin film that
separated the individual drops of dispersion.
The drop-drop coalescence frequency h ( v , v ' , z ) and drop-interface coalescence
frequency h* ( v , H ) were not amenable to direct determination but had to be inferred
from experimental data by using the model. The following expression was used for the
drop-drop coalescence frequency:

A( v , v ' , z ) = AoZ( V-1/3 + v ' - ' / 3 ) 2 (9)

where h o is a constant specific to the phase system under consideration.
Eq. (9) implies that the drop-drop coalescence frequency increases as the drops
 M.C. Ruiz, R. Padilla / Hydrometallurgy 42 (1996) 281-291 287

i • i • i , i • i • i • i • i •

10

%=0.13E-4¢m/=)
Expedmental: /~e
• l=gcm
8 • I= 18cm /

• i . I , i . i , i , i

2 4 6 8 10 12 14 16 18
Distance over the passive interfao~, cm

Fig. 3. Comparisonof the predicted and experimental values of the average drop size within the dispersion
band. I = horizontal distance from the settler inlet, Q d / A = 2.06 m3/h m2, organic/aqueous ratio, O/A =
0.8, stirring rate = 300 rpm, temperature= 20"C.

advance from the passive to the active interface and it is a function of the size of the
drops undergoing coalescence. Allak and Jeffreys [8], in their study of coalescence in
thick dispersion bands, also reported that the drop-drop coalescence frequency increased
as the drops passed through the dispersion band. The functional dependency on the size
of the drops of Eq. (9), initially proposed by Ruiz [5], has been found to describe the
coalescence phenomena well.
The value of the constant ho was determined by simulating a selected experiment and
minimizing the deviations between the experimental and predicted average volumes of
the drops within the dispersion band. A value of h o = 0.13 × 10 -4 c m / s was obtained
by this method. Fig. 3 shows the comparison of the simulated values of drop sizes by
using Eq. (9) and the experimentally measured values.
The drop-interface coalescence frequency was found to be a constant, independent of
the size of the drops and the thickness of the dispersion band:

A" ( v , H ) = A o (10)

It is known that for drop-interface coalescence to occur it is necessary that the film
of continuous phase that separates the drops from the bulk phase drains to a critical
thickness. It is also known that, when the dispersion band gets thicker the force pressing
the drop against the interface increases, since at least part of the weight of the band will
be transmitted to the drop at the interface. The higher the force the larger the velocity of
drainage of the film of the continuous phase; which means that, under these conditions,
h* should increase. On the other hand, as the band gets thicker, the drop size at the
active interface gets larger. The high force exerted by the thicker band will increase the
deformation of these large drops, which, in turn, will increase the area of the film to be
288 M.C Ruiz, R. Padilla / HydrometaUurgy 42 (1996) 281-291

drained. Under this condition h* should decrease. The independence of h* of the band
thickness obtained for this system can be attributed to a balance between these two
opposite effects.
The value of h o for the phase system under consideration was determined by
simulating the same selected experiment used for the determination of h o and matching
the predicted and measured dispersion band thickness. A value of h o = 0.305 s-: was
obtained.

5. Inlet drop size distribution

The sizes of the drops entering the settler were determined experimentally for various
conditions and are reported in part I. The results indicated that the size (volume)
distribution of drops entering the settler could be represented accurately by a log-normal
distribution. Consequently, in the simulation work a log-normal distribution was used.
The parameters of the log-normal function were calculated from the average volumes of
drops and standard deviations obtained experimentally.

6. Validation of the mathematical model

For the steady-state behavior of the settler, simulations for various dispersed phase
throughputs were carded out using the parameters determined. Based on the experimen-
tal evidence (presented in part I) that the average size of the drops generated in the
mixer was essentially independent of the dispersed phase flow rates, a single log-normal

: ! ! i : : :

g : i
c
10 ! : i
r--

g m 0.30
0.3S
0.116
0.110
0.42 0.1t6
....... • 0.48 0.110
._w • 0.54 0.116 :
a o 0.30 ~0~
0 0.36 0.0~
A 0.42 O.(:W
: 0 0.48 0,0~

10

Qd~ m3/h rn2

Fig. 4. Prediction of the dispersion band thickness as a function of the specific dispersed phase flow rate.
 M. C Ruiz, R. PadiUa / HydrometaUurgy 42 (1996) 281-291 289

18 oj, ,]
o~ /
~ ' ~ ~* *"/ /
16 1.54 1.0
0-~ 1.54
a 1.o~18
gl
1.54 1.0 30 II
14 • 2,TM 08 9
• 2.08 0,8 18 II
• 2.08 0.8 30
II 2.76 1.0 9
12 m Zm 1.0 18

- - 10

Q.
o 8

0 ~am,~lP~. , , , . , . , . , .
0 4 8 12 16 20 24 28

Oistanoe over the I ~ interface, on

Fig. 5. Predicted values of the average drop volume within the dispersion band compared to experimental
values for various flow rates, stirring rate = 300 rpm, temperature = 20°C.

drop size distribution was used for all the simulations. This distribution had an average
volume of 0.041 mm 3 and a coefficient of variation of 1.4. The results of the simulations
are depicted in Fig. 4, where the predicted and experimental dispersion band thickness
are shown. As can be seen in this figure, the model of the settler is able to predict
accurately the thickness of the dispersion band for all the tested conditions.

16

14

6 12
d
10

m
8
¢,1

6
4

2
I Prad~ted I
~.0
Average inlet drop diameter (do), m m

Fig. 6. Predicted dispersion band thickness as a function of the inlet drop size. Q a / A = 2.06 m 3 / h m 2.
290 M. C. Ruiz, R. Padilla / HydrometaUurgy 42 (1996) 281-291

Additional support of the validity of the model is shown in Fig. 5, which compares
the profile of the dispersion drop sizes predicted by the settler model and the values
determined experimentally under different conditions. The agreement is excellent in all
cases. Therefore, the adequacy of the fundamental approach taken for the modeling of
the settler is also confirmed.

7. Effect of the inlet drop size distribution

In an industrial settling process the sizes of the drops entering the settler are rarely
known with precision. Therefore, it is interesting to know the sensitivity of the process
to changes in the inlet drop sizes. The mathematical model developed here was used to
simulate the operation of a gravity settler using different inlet drop size distributions
with increments in the average drop diameter equal to 0.2 mm. The results of the
simulations are shown in Fig. 6, which plots the dispersion band thickness against the
average inlet drop diameter. It can be observed that the dispersion band thickness
decreases as the drop size increases. It is interesting to note that the dispersion band
thickness is more sensitive to the inlet drop size in the large size range. For the operating
conditions of this study, the inlet drop diameter was about 0.4 nun. In this range the
effect of inlet drop size on the thickness of the dispersion band is small.

8. Conclusions

A mathematical model for the steady-state separation of phases in a deep-layer

horizontal gravity settler has been developed by using a population balance approach.
Experimental data obtained in a continuous laboratory mixer-settler over a range of
operating conditions were used to evaluate the parameters of the model and for model
validation.
It was found that the following expression for the drop-drop coalescence frequency
described well the rate of growth of the drops from the passive to the active interface:

v,v', z) = Ao z( v-,/3 + v,-,/3)2

with h o = 0.13 X 10 -4 c m / s for the chemical system considered: 10% Acorga M5640
in Escaid 103-0.25 M Na2SO 4 aqueous solution.
The drop-interface coalescence frequency was found to be independent of the size of
the drops and the thickness of the dispersion band; that is, h * ( v , H ) = h o. With
h o = 0.305 s-1 for the chemical system under consideration.
The simulations carried out under different operating conditions showed that the
model was able to predict accurately the thickness of the dispersion band as well as the
growth of the dispersion drops within the dispersion band. This excellent agreement
between simulated and experimental results supports the validity of the model. Finally, it
is important to point out that the general framework of this model is applicable to other
systems, providing appropriate parameters are available.
 M.C. Ruiz, R. PadiUa / Hydrometallurgy 42 (1996) 281-291 291

Acknowledgements

S u p p o r t f r o m the F o n d o N a c i o n a l de C i e n c i a y T e c n o l o g i a ( F O N D E C Y T ) o f Chile,
u n d e r Grant No. 1930479 is gratefully a c k n o w l e d g e d .

References

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[2] BlaB, E., Meon, W., Rommel, W. and Lobmann, A., Is hydrodynamic modeling a sound approach for the
design of gravity settlers without coalescing aids? Int. Chem. Eng., 32(4) (1992): 601-618.
[3] Jeffreys, G.V., Davies, G.A. and Pin, K., Rate of coalescence of the dispersed phase in a laboratory
mixer-settler unit: Part II, The analysis of coalescence in a continuous mixer-settler. AIChE J., 16(5)
(1970): 827-831.
[4] Jeelani, S.A.K. and Hartland, S., The continuous separation of liquid/liquid dispersions. Chem. Eng. Sci.,
48(2) (1993): 239-254.
[5] Ruiz, M.C., Mathematical modeling of a gravity settler. Ph.D. Thesis, Univ. Utah (1985).
[6] Barnea, E. and Mizrahi, J., Separation mechanism of liquid-liquid dispersions in a deep-layer gravity
settler: Part IV - - Continuous settler characteristics. Trans. Inst. Chem. Eng., 53 (1975): 83-90.
[7] Ryon, A.D., Daley, F.L. and Lowrie, R.S., Scale-up of mixer-settlers. Chem. Eng. Prog., 55(10) (1959):
71-75.
[8] Sastry, K. and Gaschignard, P., Discretization procedure for the coalescence equation of particulate
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