Ind. Eng. Chem. Res.

1990,29, 1901-1907 1901

Performance of a Large-Scale Packed Liquid-Liquid Extractor

A. Frank Seibert, Bob E. Reeves, and James R. Fair*
Separations Research Program, The University of Texas at Austin, Austin, Texas 78712

T h e performance of commercial-size high-efficiency packings was determined by using a 42.5-cm-

diameter (i.d.) liquid-liquid extractor. Both random and ordered packings were studied to determine
their effects on the fluid hydraulics and mass-transfer efficiency in a larger diameter extractor. These
packings included no. 25 and 40 metal Intalox saddle (IMTP) random packing and Norton 2T ordered
packing. Physical property effects were studied for three test systems, Isopar-M/water, toluene/ water,
and toluene/acetone/water. The influence of packed height was also investigated and was observed
to have a significant effect on the mass-transfer efficiency of the random packings. The experimental
results were compared with models based on data obtained in small-scale columns. For the ordered
packing, these models agreed favorably with the larger scale data; such was not the case with random
packings. Based on these experimental results, it is evident that significant maldistribution can
occur in larger diameter towers containing random packings. T h e apparent maldistribution was
observed to increase with increasing packed height and column diameter. Maldistribution did not
appear to be a problem with the ordered packings.

As a result of improving chemical and petrochemical
markets, debottlenecking of existing processes has become
attractive. In this connection, many older liquid-liquid
extractors are being reevaluated to take advantage of
newer, more efficient contacting devices. This has created
a need for more reliable flooding and mass-transfer cor-
relations for commercial-scale columns, since previous
correlations have been verified only with data from
small-diameter columns.
There has always been a great deal of uncertainty
whether data obtained from small packed extractors can
be scaled up reliably to commercial sizes, since conven-
tional wisdom has dictated at least an 8 1 co1umn:packing
diameter ratio if channeling is to be avoided. In order to
meet this requirement, smaller packing elements, pos-
sessing a large surface area:volume ratio, must be used.
Under these conditions, the type of drop movement may
deviate substantially from that occurring in larger columns,
where a low surface area:volume packing ratio is a logical
choice. Accordingly, significant differences in efficiency
can arise, which may not be predicted by presently
available mathematical models. The objectives of this
study were to obtain flooding and mass-transfer efficiency
performance data from a 42.5-cm-diameter extractor
containing commercial-size packing materials and then to
compare this performance with that predicted by pub-
lished flooding and mass-transfer correlations.
Packings for extraction are the same as those used in
distillation and absorption service. These packings are
classified as random or ordered. The familiar ring and
saddle packings are examples of random packings. They
are generally dumped into the tower, whereas ordered
packings are assembled and stacked in a particular ar-
rangement. Ordered packings (also called structured
packings) are usually in the form of corrugated metal
sheets that are arranged carefully for controlling the flow
of the phases. A particular objective of this work was to
ascertain the performance of these packings relative to that
of random packings. While earlier studies have shown that
high-efficiencyrandom packings perform as well as ordered
packings in small-diameter columns, there was concern
over whether this would be the case a t larger scales of
design.
Previous Work
Raschig rings and Berl saddles have been studied rather
extensively under extraction conditions, but this has not
0888- 5885 / 9012629-1901$02.50 / 0
been the case for commercial-size high-efficiency random
or ordered packings. Surprisingly, little has been reported
on the efficiency of traditional commercial-size random
packings. In the 1950s, Gayler and Pratt published an
extensive group of studies of random packings in liquid-
liquid extraction. In 1957, they reported on the efficiency
and holdup for the transfer of acetone between water and
four immiscible solvents in a 10.2-cm column with 1.27-cm
Raschig rings at bed heights of 61, 122, and 305 cm.
Further data were obtained in 15.2- and 30.5-cm columns
with Raschig rings ranging in size from 1.27 to 3.81 cm.
Gayler and Pratt observed a significant effect of the di-
rection of mass transfer, which they attributed to mi-
crooscillation of the interface for the transfer of acetone
from the continuous (aqueous) phase and to enhanced
droplet coalescence for the opposite direction of mass
transfer. They concluded that for the case of mass transfer
into a dispersed solvent phase, the ratio of the column
diameter to packing diameter should be greater than eight
if channeling were to be avoided. This was also verified
by Leibson and Beckmann (1953). Gayler and Pratt ob-
served a negligible effect of column diameter on the
mass-transfer efficiency when comparing operations in
10.2- and 23-cm-diameter columns. However, they also
observed a decrease in mass-transfer efficiency with in-
creasing packing height, as observed later by Nemunaitis
et al. (1971) and Eckert (1976). This phenomenon was
attributed to end effects that provided a larger relative
mass-transfer contribution with shorter packing heights.
Leibson and Beckmann also studied the effect of column
diameter and packing size on mass transfer in a counter-
current packed liquid-liquid extractor. They used 7.6-,
10.2-, and 15.2-cm-diametercolumns filled with 0.38-, 0.64-,
1.27-, 1.63-, 1.91-, and 2.54-cm unglazed ceramic Raschig
rings. The transfer of diethylamine from a continuous
water phase to a dispersed toluene phase was found to
improve with increasing column diameter.
Nemunaitis et al. and Eckert investigated the perform-
ance of 2.54-cm Raschig rings, ceramic Intalox saddles, and
copper Pall rings in a 42.5-cm-diameter column. They
observed that the column packed with saddles yielded the
highest mass-transfer efficiency, followed by Pall rings and
Raschig rings. The height equivalent to a theoretical stage
(HETS) for the kerosene/methyl ethyl ketone/water
system was found to decrease with increasing continu-
ous-phase rates and to increase with increasing dis-
persed-phase flows. Nemunaitis et al. reported that
0 1990 American Chemical Society
1902 Ind. Eng. Chem. Res., Vol. 29, No. 9, 1990
condeF=
cw
Steam
b
Reboiler
I -
Condensate
I
I
i
.
Figure 1. Flow diagram of experimental equipment.
flooding of their packed column occurred at loadings only
20% of those predicted by the flooding correlation of
Crawford and Wilke (1951).
Recently, Seibert and Fair (1988) reported on the hy-
drodynamic and mass-transfer behavior of packings in a
10.2-cm extractor. Their packings included 1.27-cm ce-
ramic Raschig rings, 1.59-cm metal Pall rings, no. 15 metal
Intalox saddles (IMTP), of the random variety, and or-
dered packings of corrugated sheet metal and corrugated
metal gauze. Mechanistic flooding and hydraulic models
were presented and verified with data obtained in their
small-diameter column. The present paper may be con-
sidered to be a companion to the one published in 1988
by two of the present authors.
Experimental Equipment and Procedure
A flow diagram of the extraction/distillation system is
shown in Figure 1. In the mass-transfer mode, distilled
light-phase solvent was fed and dispersed near the bottom
of the extractor into the heavy continuous phase. The
operating interface was maintained at the top of the ex-
tractor by controlling the flow of the exiting heavy phase
(raffinate). The exiting light-phase (extract) stream was
sent to the distillation column feed tank. The solute was
separated from the solvent by distillation; the purified
solvent flowed to the extraction feed tank whereas the
purified solute was collected in the overhead accumulator.
The solute was blended with the aqueous feed to give a
feed mixture in the vicinity of 6.0 wt % solute. The inside
Hold-Up
Tank
diameter of both the extraction column and the distillation
column was 42.5 cm.
In the non-mass-transfer mode, the light (dispersed)
phase was collected at the top of the column and was
recycled to the solvent feed tank, bypassing the distillation
tower. The heavy (continuous) phase was fed near the top
of the extractor. The operating interface was maintained
a t the top of the extractor by controlling the heavy-phase
flow out of the tower. The exiting heavy phase was re-
cycled to the heavy-phase feed tank.
Three test systems were chosen for study: (1)Isopar-
M/water, (2) toluenelwater, and (3) toluene/acetone/
water. The first two systems were used for non-mass-
transfer flooding studies only. The latter system was in-
vestigated for both mass transfer and flooding. The
physical properties of each of the systems are given in
Table I. The equilibrium and transport data for systems
2 and 3 were reported by Misek et al. (1985). The physical
properties of Isopar-M were obtained from the manufac-
turer. Technical-grade solvents and solutes of at least 99.2
wt % purity were used in order to minimize contamination.
Compositions of all streams were determined by using
a gas chromatograph with a thermal conductivity detector.
Flow rates were measured with calibrated orifice meters.
Experimental mass-transfer runs with material balance
closures of less than 92% were discarded. With acceptable
closure, the extract composition was checked to ascertain
taht the equilibrium approach of the extract acetone
composition to that of the entering feed was less than 90%.
The experimental runs were designed so that the operating
 Ind. Eng. Chem. Res., Vol. 29, No. 9, 1990 1903

Table I. Physical Properties of the Systems Studied Table 111. Flooding Data
(Temwerature = 25 "C) packing systemn redistribution UCacm/s U,,, cm/s
toluene/ Norton TAW yes 1.58 0.31
Isopar- toluene/ acetone/ 1.27 0.62
Miwater water watef 1.14 0.72
Aqueous Phase 1.01 0.93
viscocity, CP 0.89 0.89 1.05 0.90 1.13
density, g/cm3 0.994 0.994 0.989 no. 25 IMTP TAW yes 11.49 0.41
solute diffusion coeff, cm2/s 1.01x 10-5 1.23 0.72
1.14 0.93
Organic Phase 0.88 1.23
viscocity, CP 2.24 0.55 0.53 0.66 1.44
density, g/cm3 0.784 0.864 0.853 no 1.40 0.72
solute diffusion coeff, cmz/s 2.51 x 10-5 1.58 0.41
slope of equilibrium lineb 0.82 1.31 0.93
interfacial tension, dyn/cm 24.8 30.0 22.0 1.05 1.32
nConcentration of acetone in the feed = 6 wt %. b(wt % of no. 25 IMTP TW no 1.75 0.51
solute in organic phase)/(wt % of solute in aqueous phase). 1.58 0.72
1.40 0.93
1.05 1.32
Table 11. Packing Characteristics 0.79 1.44
specific surface no. 40 IMTP TAW yes 2.28 0.31
packing type area, cm2/cm3 void fraction 1.93 0.62
1.58 0.93
no. 25 IMTP random 2.26 0.95
1.40 1.13
no. 40 IMTP random 1.71 0.97
no. 40 IMTP IMW yes 2.50 0.45
Norton 2T ordered 2.13 0.97
2.23 0.57
2.05 0.71
line was approximately parallel to the equilibrium curve 1.79 0.87
to maximize the accuracy of the data. 1.61 1.00
The distillation column contained two beds of corru- 1.56 1.12
gated sheet metal structured packing, each with a height 1.34 1.28
of 330 cm. This type of packing was chosen because of its 1.16 1.41
1.12 1.54
high-capacity characteristics. The typical feed to the 0.85 1.66
distillation column contained between 3 and 6 wt 7% ace- 0.71 1.80
tone. The column was operated at 2-3 times the minimum
reflux to ensure that pure (99.8+ wt 5%) toluene and ace- TAW = toluene/acetone/water system. TW = toluene/water
system (no mass transfer). IMW = Isopar-M/water system (no
tone were recovered. The feed to the column was a t the mass transfer).
center, between the packed beds. Care was taken to
prevent flooding of the distillation column before the ex- 2.0
tractor capacity was reached.
I I
1
The extraction column contained two beds of packing
-
'.
with a total packed height of 640 or 700 cm. Since the
packings were of type 316 stainless steel, the organic phase
1.5 L A Norton2T
was dispersed while the aqueous phase preferentially \
A
-
.\
wetted the packing surfaces. Normally, two beds of 350-cm \
height were used, with intermediate redistribution of the
dispersed phase. In one set of runs with no. 25 IMTP
packing, a 640-cm (23-ft) continuous bed was used to de-
1.0

0.5 -
4 A
termine the effect of redistribution. The main distributor
was a perforated pipe type containing 110 holes with a hole \
\
diameter of 0.32 cm and fabricated from 304 stainless steel.
The light-phase distributor was located 16.5 cm below the
packing. The packed beds were supported by open
0.0
0
' I

1
I

stainless steel grids. The redistributor was an orifice riser
type containing 152 holes with a hole diameter of 0.64 cm.
It was also fabricated from 304 stainless steel. Four 7.6-cm
(0.d.) risers allowed redistribution of the heavy (continu-
ous) phase.
Three packings were studied, the characteristics of which
are shown in Table 11. These packings are classified as
"high efficiency" for gas-liquid service because of their high
void fractions and their ability to provide a large amount
of interfacial area for mass transfer.
Experimental Results
Flooding. Flooding in packed towers occurs when true
countercurrent flow no longer exists. Examples of flooding
situations include entrainment of drops by the continuous
phase; the dispersed phase being unable to penetrate
packing, resulting in buildup of the dispersed (light) phase
below the packing support; and phase inversion. None of
2
1
3
Superficial Flooding Velocity of the
Continuous Phase cm/s
Figure 2. Flooding rates for the packings tested. Toluene/ace-
tonelwater system with toluene dispersed. Column diameter 42.5
cm, with redistributor.
these phenomena can be tolerated and will eventually
upset downstream processes.
Windows located on the extractor allowed visual de-
tection of flooding. Samples were also collected to verify
that two phases were exiting together in either the raffmate
or the extract streams. The effects of packing size varia-
tion, redistribution, and system properties were investi-
gated in these studies. Flooding data are given in Table
111. The effect of packing size and type on the capacity
of the liquid-liquid extractor is shown in Figure 2. The
no. 40 IMTP packing yielded the highest capacity, which
was expected because of its lower packing area per volume.
This lower area results in a less tortuous path for the phase
1904 Ind. Eng. Chem. Res., Vol. 29, No. 9, 1990

2.0 I i

0 0)
c
f
I

0 1.5 - I
1.5 -
1.0 - 1.0 -
0.5 - 0.5 -
"."
0.0 0.5 1 .O 1.5 2.0 2.5 3.0 0.0 0.5 1.o 1.5
Superficial Flooding Velocity of the Superficial Flooding Vebcity of the
Continuous Phase cm/s Continuous Phase CWS
Figure 3. Flooding rates for no. 40 IMTP packing. Continuous Figure 5. Flooding rates for toluene/acetone/water system. Col-
phase = water. Column diameter 42.5 cm; single bed for Isopar- umn diameter 2.5 cm for no. 25 IMTP packing; column diameter 10.2
M/water, two beds for toluene/acetone/water. cm for no. 15 IMTP packing (Seibert and Fair, 1988).
6 I 1

3.0 I A/ A
I I I
1

:1/
0.5

-0.0 0.5 1 .o 1.5

0.0 L I I I I
Superficial Velocity of the Dispersed Phase (cm/s)
0.0 0.5 1.o 1.5 2.0
Figure 6. Volumetric mass-transfer coefficients for toluene/ace-
Superficial Flooding Velocity of the tone/water system with toluene dispersed. Column diameter 42.5
Continuous Phase cm/s cm, with redistributor.
Figure 4. Flooding rates for no. 25 IMTP packing. Toluene/ace-
tone/water system with toluene dispersed. Column diameter 42.5 Table IV. Mass-Transfer Data for the
cm. Toluene/Acetone/Water System
uc, ud 9 (HTU),,
flows, which promotes a capacity approaching that of a packing redistribution cm/s cm/s cm
spray column. The Norton 2T structured packing and the Norton 2T Yes 0.21 0.26 125
no. 25 IMTP packing had about the same capacity, as 0.33 0.41 116
would be expected from their similar surface areas. The 0.49 0.62 95
flooding rates were observed to be approximately inversely 0.66 0.82 119
proportional to the packing surface area. 0.90 1.13 162
Figure 3 shows the effect of the chemical system. no. 25 IMTP Yes 0.21 0.26 186
0.33 0.41 204
Greater capacities were obtained with the Isopar-M/water 0.49 0.62 241
system. This is attributed to the greater phase density 0.66 0.82 277
difference and interfacial tension, which results in a greater 0.82 1.03 305
drop velocity and consequently a greater capacity. The 0.99 1.23 308
toluene/acetone/water system had the lower capacity, 0.21 0.41 171
which may be attributed to its lower interfacial tension. 0.32 0.62 183
0.42 0.82 189
The use of a redistributor caused a lower flooding capacity 0.53 1.03 189
as shown in Figure 4. The relative reduction in capacity 0.58 1.13 207
was constant over the range of flow rates studied. no. 25 IMTP no 0.21 0.26 277
It is apparent that there is relatively little static dis- 0.33 0.41 329
persed-phase holdup in the larger packings. The lack of 0.49 0.62 357
holdup equates to greater volume availability for flow and 0.66 0.82 387
0.82 1.06 445
thus a greater capacity. As shown in Figure 5, and earlier 1.05 1.32 390
in Figure 2, the flooding rates for the larger packings are 0.32 0.62 292
significantly greater than for the smaller packings, which 0.42 0.82 253
confirms the conclusion of negligible static dispersed-phase 0.53 1.03 290
holdup. 0.63 1.24 280
Mass Transfer. The mass-transfer efficiencies of the no. 40 IMTP Yes 0.21 0.26 302
0.33 0.41 235
no. 25 IMTP, no. 40 IMTP, and the Norton 2T packings 1.49 0.62 232
are compared in Figure 6. The supporting mass-transfer 0.66 0.82 214
data are given in Table IV. The overall volumetric 0.90 1.13 220
 Ind. Eng. Chem. Res., Vol. 29, No. 9, 1990 1905

Table V. Key Hydraulic a n d Mass-Transfer Models

Hydraulic
Sauter mean drop diameter, d,

dv, = 1 . 1 5 4 &) 112

q
q
= 1.0, c
= 1.4, d c
--
d, no mass transfer
characteristic slip velocity, U,

0.0 0.5 1.o 1.5

Superficial Velocity of the Dispersed Phase (cm/s)
Figure 7. Volumetric mass-transfer coefficients for toluene/ace-
tone/water system with toluene dispersed. Packing = no. 25 IMTP. pw = 0.009 g/(cm s)
Column diameter 42.5 cm.
-Re
- - 0.94H0.757- 0.857, H I59.3
p0.149
6 I I

5 -
-p0.149
- - 3.42H0.441- 0.857,
Re H > 59.3

-
.
0
4 - Rw
. Uso= 2
K,a(sS1) dV&C
-1000 3 -
- 0 dispersed-phase holdup
2 - - = a,d,/2 (7)

1 -

I
0

slip velocity

u, = u,, exp(-1.92&) cos }{ ; + (1 - cos { :})( &)

(9)
mass-transfer coefficient increases approximately linearly
with increasing dispersed-phase rate until flooding is ap- continuous-phase flooding velocity, Ucf
proached. The improved efficiency is a result of a linear
increase in interfacial area. The ordered packings per-
formed very well, yielding significantly greater overall
u
s0 1 + 0.925(
Ucf = E(
2- $)[ cos (10)

volumetric mass-transfer coefficients. The reason why the interfacial area

random packings performed so poorly is not completely
understood. One likely explanation is that there was a a. =
6cbd
- (11)
significant maldistribution of the phases due to column dv,
size. Further evidence supporting this reasoning may be
seen in Figure 7, where a redistributor placed in the middle Mass Transfer
of the random packing bed improved the efficiency by continuous-phase-film mass-transfer coefficient
about 40%. Maldistribution in the ordered packing ap-
pears to be absent, since the mass-transfer efficiency of (12)
the ordered packing scaled up quite well with column
diameter as shown in Figure 8. The slight differences in dispersed-phase-film mass-transfer coefficient
efficiency may be due to variations in surface treatment
of the ordered packings; for the smaller column, a smooth
surface SMV packing (Sulzer Brothers) with 3.2 cm2/cm3
area was used, whereas the Norton 2T has a surface area
of 2.1 cm2/cm3. O.O0375U,
kd = @<6
- kd/k
Correlation of Data
The models used for comparison with the experimental
data are summarized in Table V, as eqs 1-17. The equa-
tions are taken directly from the paper by Seibert and Fair overall continuous-phase mass-transfer coefficient
(1988), with nomenclature retained. These models include
the fundamental prediction of the Sauter mean drop di- _1 - -1 1
+-
Km kc mdckd
ameter, dispersed-phase holdup, interfacial area for mass
transfer, slip velocity, and mass-transfer coefficients. The
.,
flooding velocities and mass-transfer efficiency may then
1906 Ind. Eng. Chem. Res., Vol. 29, No. 9, 1990
0,
m ference of 16.5% was obtained for the random packings
E and 8.8% for the ordered packings, giving an overall dif-
G structured packing in a 42.5-cm-diameter column, and a
G 1 2 3
Experimental SuperficialContinuous Phase
Flooding velodty cnvs
Figure 9. Parity plot for flooding capacity, all packings.
L
3 -
2 - 0 no. 251MTP
1 -
A Notton2T
0 1 2 3 4 5
Experimental Overall Volumetric Mass
Coefficient (s -,)-I OOG
Figure 10. Parity plot, model vs experiment for mass-transfer
coefficients. Toluene/acetone/water system, toluene dispersed,
42.5-cm column.
be calculated. The derivations of these mathematical
models are given by Seibert and Fair (1988).
The flooding model was found to predict the large-di-
m e t e r flooding data with very good accuracy. An average
relative difference of 15% was obtained for the Isopar-
M/water system, 16% for the toluene/water system, and
12% for the toluene/acetone/water system. It may be
noted that the static hold-up model utilized in the earlier
Seibert and Fair work was found not to be valid for the
larger packings studied in this work and was not used in
the data correlation. A parity plot illustrating the general
accuracy of the data, Figure 9, indicates that the model
provides somewhat conservative estimates of flooding ca-
pacity.
The mass-transfer models given in the previous work
were found not to agree with experimental data for random
packings in the larger column. An empirical correction
factor cf, shown in eq 18, was added to the list of models
to account for the phase maldistribution in random
packings.
Kocai = Cf(Kocai)plug
The correction factor was correlated empirically:
cf = 1 - exp{-28/dc\ 0 < d, < 42.5 cm
cf = 0.5 d, > 42.5 cm
No correction was necessary for the mass-transfer effi-
ciency prediction for the ordered packings. The resulting
efficiency models were found to predict the experimental
data with reasonable accuracy. An average relative dif-
ference of 15%. A parity plot illustrating the general
accuracy of the mass-transfer data is given in Figure 10.
Conclusions
For packed liquid-liquid extraction columns, data
presented here should aid the process designer in pre-
dicting flow capacity and mass-transfer efficiency of com-
mercial-scale installations. Flow capacity tests have been
run for two high void fraction random packings and one
model has been developed that permits estimation of flow
capacity for systems, column sizes, and packing types other
than those tested. Unlike the case for small extraction
columns, where packing openings can restrict flow of
dispersed-phase drops, the packing sizes appropriate for
larger columns permit higher phase flow rates. In general,
for different packing sizes, the capacity appears to be in-
versely proportional to the specific surface area of the
packing. On this basis, the ordered, or structured packing,
had about the same capacity as the random packing.
Mass-transfer rates for the packings tested were found
to fit models developed earlier on the basis of smaller scale
tests. There was a slight effect of column diameter on
efficiency, with a constant factor needed to account for the
reduced efficiency at larger column sizes. Thus, unlike the
case for flooding, the diameter did appear to have an in-
fluence on mass transfer. It was found, however, that for
the random packings there is a height effect on mass-
transfer efficiency, with deterioration for longer packed
6 beds correctable through the use of dispersed-phase re-
distributors. This problem of maldistribution did not
appear to be present when structured packings were used.
Acknowledgment
This work was supported by the Separations Research
Program at The University of Texas at Austin.
Nomenclature
ai = interfacial area, cm2/cm3
a p = total packing area per volume of column, cm2/cm3
cf = correction factor for flooding (eq 19)
C = concentration, g/cm3
C * = equilibrium concentration, g/cm3
d, = column diameter, cm
d,, = Sauter mean drop diameter, cm
D = diffusion coefficient, cmz/s
g = gravitational constant, cm/s2
HTU, = overall height of a transfer unit based on the con-
tinuous phase, cm
k , = individual film coefficient for the continuous phase, cm/s
hd = individual film coefficient for the dispersed phase, cm/s
K , = overall mass-transfer coefficient based on the continuous
phase, cm/s
mdc = distribution coefficient based on a concentration driving
force, dCd*/dC,
Re, = drop Reynolds number based on the continuous phase,
(18) P c Usdvsl M c
Sc, = Schmidt number based on the continuous phase, p c /
(PP,)
(19) Scd = Schmidt number based on the dispersed phase, pd/
TPdDd)
(20) Sh, = Sherwood number based on the continuous phase,
kcdvslDc
U = superficial velocity, cm/s
Vi, = interstitial velocity of the continuous phase, cm/s
U s = slip velocity, cm/s
 Ind. Eng. Chem. Res. 1990,29, 1907-1914 1907
U , = characteristic slip velocity, slip velocity at low dis- Gayler, R.; Pratt, H. R. C. Liquid-Liquid Extraction V. Further
persed-phase flow rate, cm/s Studies of Droplet Behaviour in Packed Columns. Trans. Inst.
Chem. Eng. 1953,31,69.
Greek Symbols Gayler, R.; Pratt, H. R. C. Liquid-Liquid Extraction X. Overall
Ap = density difference, g/cm3 Mass Transfer Coefficients on an Area Basis for Extraction of
e = void fraction of packing Acetone in Packed Columns. Trans. Inst. Chem. Eng. 1957,35,
{ = dimensionless tortuosity factor, a,d,,/2 273.
Grace, J. R.; Wairegi, T.; Nguyen, T. H. Shapes and Velocities of
p = liquid viscosity, g/(cm s)
Single Drops and Bubbles Moving Freely Through Immiscible
7 = drop size correction factor Liquids. Trans. Inst. Chem. Eng. 1976,54,167.
p = liquid density, g/cm3 Handlos, A. E.; Baron, T.Mass and Heat Transfer from Drops in
u = interfacial tension, dyn/cm Liquid-Liquid Extraction. AZCh J. 1957,3,127.
& = fraction of dispersed-phase holdup in the contacting Laddha, G. S.;Degaleesan, T. E. Transport Phenomena in Liquid
section Extraction; McGraw-Hill: New York, 1978.
3 = criterion for determining the applicability of either the Leibson, I.; Beckmann, R. B. The Effect of Packing Size and Column
Handlos and Baron or the Laddha and Degaleesan dis- Diameter on Mass Transfer in Liquid-Liquid Extraction. Chem.
persed-phase-film mass-transfer coefficient model Eng. Prog. 1953,49 (S), 405.
Misek, T.; Berger, R.; Schroter, J. Standard Test Systems for Liq-
Subscripts uid-Liquid Extractions; Institution of Chemical Engineers:
Rugby, England, 1985.
c = continuous phase Nemunaitis, R. R.; Eckert, J. S.; Foote, E. H.; Rollison, L. H. Packed
d = dispersed phase Liquid-Liquid Extractors. Chem. Eng. Prog. 1971,67 (ll),60.
w = water Seibert, A. F.; Fair, J. R. Hydrodynamics and Mass Transfer in
Spray and Packed Liquid-Liquid Extraction Columns. Znd. Eng.
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1976,55 (31,117. Accepted J u n e 9, 1990

Extraction of Mercury(I1) with Sulfurized Jojoba Oil

Jaime Wisniak,*it Gal Schorr,t Dov Zacovsky,+and Sofia Belferl
Department of Chemical Engineering and The Institutes for Applied Research, Ben-Gurion University of the
Negev, Beer-Sheva, Israel

Sulfurized jojoba oil containing 12% by weight S has been tested as an extractant for Hg(1I) from
aqueous solutions. Experiments have been performed with the extractant dissolved in a solvent
(liquid-liquid extraction) or adsorbed in an appropriate resin matrix (solid-liquid extraction). The
extraction characteristics of both systems have been measured and show that sulfurized jojoba oil
exhibits very good possibilities as an extractant. T h e performance of several resins treated with
sulfurized jojoba oil for adsorbing mercury(I1) was studied. T h e morphology of the different resins
was examined by using scanning electron microscopy. The sulfurized oil is attached to the resin
sites through the sulfur atoms; it is estimated that there are about 2 mol of S active sites per kilogram
of resin.

Introduction without introducing large amounts of other contaminants.

Mercury metal and most of its compounds are poisons
that can be fatal to all living organisms. In the context
of present-day governmental regulations, the control, re-
covery, and disposal of mercury-bearing wastes are as im-
portant as the manufacturing process. EPA regulations
normally require that liquid effluents contain no more than
5 ppb. The most significant source of pollution is the
mercury-containing brines from chloralkali industries.
Cleaning procedures include the use of activated carbon
impregnated with silver, contact of the brine solution with
a strong anion-exchange organic resin of the quaternary
ammonium cross-linked type, precipitation of mercury
salts from alkaline solutions with soluble sulfides or
water-soluble reducing agents, etc. Solvent extraction and
separation techniques using liquid membranes are con-
sidered to be the most effective and energy-saving sepa-
ration techniques for the purpose mentioned above
(Kirk-Othmer, 1981). Swanson et al. (1973) have sug-
gested that treating solutions containing Hg(I1) ion with
starch xanthate-polycation complex can reduce the re-
sidual mercury content to extremely low levels (3.8 ppm)
0888-5885/9012 629- l907$02.50/0 0 1990 American Chemical Society
In the past, solvent extraction of mercury(I1) has been
investigated using extractants like trioctylphosphine oxide,
tributyl phosphate, trioctylamine, and tricaprylmethyl-
ammonium chloride (Aliquat 336). Some of these ex-
tractants contain nitrogen or oxygen as a donor atom and
have only poor selectivity to mercury(I1)over other metals;
much effort is being spent today on the possible use of
extractants containing sulfur as a donor atom, since some
such as dialkyl sulfides and trialkyl thiophosphate are
known to be very powerful and selective extractants for
mercury( 11).
The medium-to-low selectivity of neutral oxygen-con-
taining extractants of metal complexes with inorganic
ligands is due to the fact that these extractants may extract
the metal both in the form of coordinately solvated com-
pounds and in the form of complex metal acids. The
selectivity of sulfur-containing neutral extractants must
be higher. They are usually protonized with difficulty;
therefore, their solutions in inert diluents do not extract
complex metal acids. On the other hand, these extractants
give coordinately solvated neutral complexes only with