j o u r n a l of

MEMBRANE
SCIENCE
ELSEVIER Journal of Membrane Science 99 (1995) 197-203

Short communication

Novel techniques for oil/water separation

U. Daiminger, W. Nitsch *, P. Plucinski, S. Hoffmann
Technische Universittit Mffnchen, Institut fiir Technische Chemie, Lichtenbergstr. 4, D-85748 Garching, Germany
Received 27 May 1994; accepted in revised form 15 September 1994

Abstract

In this work two novel methods of separation of oil/water dispersions are proposed. In both methods wetting plays an essential
role. It has been found that during the flow of a dispersion through thin microporous hydrophobic membranes with pore size
similar to drop size, a spontaneous droplet enlargement takes place. This was manifested by very fast gravitational phase
separation after one passage of the dispersion through the membrane. The fraction of separated oil was independent of initial oil
concentration and also independent in a broad range from the flow rates. As an alternative to the gravitational separators, the
enlarged droplets can be removed using hollow fiber modules. The dispersion is led through the lumen of the hollow fibers, the
oil phase permeates through the porous membrane. A simplified mechanism is proposed to explain the influence of residence
time and flow rate on the efficiency of the hollow fiber separation.

Keywords: Oil/water separation; Microporous membrane; Coalescence; Wetting; Hollow fiber module

1. Introduction in fibrous bed coalescers has become popular because

Oil/water separation plays a crucial role in many
technological processes as well as in environmental
engineering [ 1-4]. One interesting application con-
cerns the phase separation on the end of solvent extrac-
tion processes, which in spite of extensive studies in
the last years is not fully solved [ 1-6]. Especially in
the field of metal ion extraction the use of surface active
chelating agents can pose many difficulties for phase
separation.
Besides chemical dispersion break up [ 1,2 ], various
physical methods including gravity settling, centrifu-
gation, air flotation, ultrafiltration and fibrous or packed
beds coalescence have been applied [ 1,2,4].
Gravity settlers are often inefficient, specially in the
case of small droplets. Coalescence of small droplets
* Corresponding author.
these devices are easy to design and reasonably efficient
[ 1,2,4-6]. The basic principle in such units is that,
when dispersions flow through the bed, the filter mate-
rial captures the droplet because of wetting, and retains
it until a large number of droplets have been captured
and then coalesces them to form large drops [ 1,2,4-
6]. The large drops can now be economically separated
by gravity settlers. Different fibrous and packed beds,
with a thickness in the cm range, have been investigated
[ 1,2,4] and patented [ 1,2,4].
The general purpose of this work is to use thin hydro-
phobic, porous membranes instead of cm-range beds
for the separation of oil-in-water dispersions. Usually,
the application of membranes for phase separation is
directed to ultrafiltration, which means the continuous
aqueous phase is the permeate.
In this work the ability of coalescence at hydrophobic
membranes should be studied in order to separate the

0376-7388/95/$09.50 © 1995 Elsevier Science B.V. All rights reserved

SSD10376-7388(94)0021 8-5
198 u. Daimingeret al. /Journal of Membrane Science 99 (1995) 197-203
dispersed organic phase as the permeate. Compared to
usually applied packed or fibrous beds as coalescence
aids, the novel aspects concern the operation of thin
membranes to aggregate oil dispersions as well as to
separate them. The first goal is the use of a microfiltra-
tion membrane as a coalescing aid, to enlarge the diam-
eter of droplets. In this case the entire dispersion is
forced to pass the membrane coalescer. As a second
goal we want to use the ability of spreading oil droplets
on the hydrophobic surface of porous hollow fibers, in
order to separate the organic phase.
2. Experimental
2.1. Experimental set-up.
Fig. 1 shows the schematic view of our separation
unit. The dispersion was transferred from the tank 1 by
pump (gear wheel pump M 838, Schwinherr, Ger-
many) to the membrane coalescer 2 (filter holder SM
165 08 B, Sartorius, Germany). A split stream 3 could
be taken for sedimentation analysis (21 glass cylinder).
iiiiiiiiiijili
Fig. 1. Schematicview of separation unit: (1) dispersionreservoir; (2) membranecoalescer; (3) samplingdevice; (4) hollow fibermodule;
(5) bypass.
The dispersion then was led through the separation unit
4 (Liqui-Cel ® hollow fiber module (HFM), Hoechst/
Celanese, USA). The separated organic phase was col-
lected in a beaker mounted on the analytical balance
(Kern 510-37, Kern, Germany).
The emulsion was prepared as follows: the appro-
priate amount of the organic phase was added to dis-
tilled water, emulsification occurred due to shear forces
in the gear wheel pump under standard conditions (56
1 of dispersion were circulated by the pump through
bypass 5 for 4 h with the volumetric flow 130 l/h).
2.2. Membranes.
The characteristics of membranes used as coalescing
aids, all with 50 mm diameter (40 mm active diame-
ter), are summarised in Table la. Hollow fibers made
of Celgard ® X-10 polypropylene membrane have 0.3
mm diameter, 0.03 mm wall thickness, porosity 30%,
and effective pore size 0.05 /zm. In the work three
different HFMs were used whose dimensions are pre-
sented in Table lb.
 U. Daiminger et al. / Journal of Membrane Science 99 (1995) 197-203 199

Table 1
Characteristics of membranes and hollow fiber modules used

(a) Membranes:

No. Membrane Material Pore size/xm Thickness/zm Producer

1 SM 11842 PTFE 5.0 110 Sartorius

2 FALP PTFE 1.0 90 Millipore
3 GVHP polivinylidene fluoride 0.22 125 Millipore
4 SM 11302 cellulose nitrate 3.0 140 Sartorius

(b) Hollow fiber modules:

No. Type Number of HFs Length cm HFM diameter cm

1 5 PCM-106 2100 16 2.5

2 5 PCM- 104 9000 24.1 5.1
3 5 PCM- 105 9000 54.6 5.1

2.3. Chemical system as described [8]. Preliminary measurements of the

For the organic phase a technical grade isododecane
(WBC-15, Biesterfeld, Germany) was taken, and the
emulsion was stabilised by bis(2-ethylhexyl)-phos-
phate (DEPA) (for synthesis, Merck, Germany), a
commonly known surface active extracting agent [ 7 ].
All chemicals were used without purification.
droplets diameter using laser diffraction (Coulter LS
130 / 100, Coulter Electronics GmbH, Germany) were
performed too (cf. Fig. 2). The residual amount of
isododecane was measured chromatographically (GC/
MS, Carlo Erba Instruments, FID detector, Carbowax).
The interfacial tension was determined by a ring
method (K 10 tensiometer, Kriass, Germany).

2.4. Analytical methods.

The diameter of droplets was determined using a
photographic method after stabilising the oil droplets
in an aqueous solution (5 wt%) of polyvinyl alcohol
(PVA, W28/60, M W = 7 2 kDa, Wacker, Germany)
- - initial dispersion
7
3. Results
3.1. Membrane coalescence
By passing the entire dispersion through the PTFE
filter membrane (2 cf. Fig. 1; 5/zm pore diameter) a
remarkable enlargement of the droplet size was

6
........... after membrane filter
- - - - - after HFM /."~..! observed. This was manifested by the immediate grav-
itational settling of the organic phase (cf. Fig. 3 ), taken
as a split stream at 3 (cf. Fig. 1). Without the membrane
"5
coalescer a phase separation was not noticed in the
> 4 range of days, which is probably due to the presence of
" 3 surface active DEPA ~. In the tube between the outlet
a}
~2 of the membrane coalescer 2 and the entry of the HFM
4 (cf. Fig. 1) a streamlet of the organic phase was
..'" \i
1 '" N observed during each experiment. This streamlet
o , ~'~ resulted from the coalescence of the enlarged oil drop-
10 100 1000
droplet size ~m]
1 Addition of 0.10 k m o l / m 3 DEPA to the system resulted in the
reduction of the value of interfacial tension from 45.8.10 - 3 ( p u r e
Fig. 2. Change of droplets size measured by laser diffraction. isododecane/water) to 22.3.10 -3 N/m.
200 U. Daiminger et al. / Journal of Membrane Science 99 (1995) 197-203

1oo o ~, ~, droplets mentioned above could not be measured due

....... * ................ ® ~ ~ ........
8O
13 60
.~_
40
20
o , , , , f,f,,
0 1 2 3 4 5
superficial velocity t h r o u g h m e m b r a n e * 102 [m3s-lm -2]
Fig. 3. The influence of the superficial velocity on the separated
fraction of oil by the membrane coalescer: II, dispersion concentra-
tion 5 g/l, 1 membrane filter No. 1; O, dispersion concentration 25
g/I, 1 membrane filter No. 1, active filter area: 12.57 cruZ; O, dis-
persion concentration 25 g/l, 1 membrane filter No. 1, active filter
area: 2.27 cmZ; v , dispersion concentration 25 g/l, 5 membrane
filters No. 1.
lets. It is this part of the dispersed phase, which forms
this streamlet, that is responsible for the fast separation
in gravity settlers.
Apart from the macroscopic streamlet achieved by
membrane induced coalescence, the enlargement of
original dispersed phase was measured with laser dif-
fraction. The initial drop size was approximately 5/xm,
determined by both methods (photographic and laser
diffraction) .The evident change of droplet diameter,
caused by the passage through the membrane, may be
seen in Fig. 2. It is worth noting that the very large
~ o to spontaneous phase separation and the detection limit
of the apparatus.
The measured results of organic phase separation by
gravity settling to a clear layer (up to 2 min) after one
passage of the dispersion through the membrane are
shown in Fig. 3. Remarkable are the following features:
a high degree of separation "r/( 80-90%, defined as
o
the fraction of separated organic phase) is observed
for one passage,
the degree of coalescence seems to be independent
,
15 20 25 of the oil concentration (first order process),
the fraction of separated oil remains constant in the
measured range of flow rates (10<I;'< 190 l/h)
which correspond to superficial velocities (the quo-
tient of volumetric flow rate and active membrane
area) in the range: 0.003 < w <0.15 m3/m 2 s.
Additionally, specific experiments show that:
separation does not occur in a gravity settler, if mem-
branes with rather small pore diameters (0.22 resp.
1.0/xm compared to 5/zm, the standard pore size in
this work) are used,
the increase of 'membrane thickness' (5 mem-
branes, each 5 /xm pore diameter pressed together
instead of one sheet) does not influence the sepa-
ration efficiency,
the increase of superficial velocity to w = 0,23 m3/
m 2 s realised by reducing the active membrane area
(Fig. 4, 80% reduction of the active membrane area:
from 12.57 to 2.27 cm z) leads to a decrease of sep-
aration efficiency (see Fig. 3),

membrane ~ _
t _~ O-ring E
support . . . . . . . . _50 mm_......... / ,,sive

membrane

normal operation operation with

of membrane coalescer reduced membrane area
Fig. 4. Schematic view of the membrane coalescer.
 U. Daiminger et al. / Journal of Membrane Science 99 (1995) 197-203 201

Table 2
The comparison of efficiency of fibrous bed and membrane coalescers

Fibrous beds

System Conc. Fibers Length cm Velocity c m / s Recovery % Ref.

vol%

Kerosene / water 0.01 Glass 1.27 0.51 > 95 4

Kerosene / wate] ~' 2-5 PTFE, Glass 0.6--3.2 0.07-1.8 C~ 5
Toluene/water 0. I Glass 0.5--3.0 0.25-1.25 90-98 6

Membrane coalescer

lsododecane / water~ 2.5 PTFE 0.011 0.3-- 15.0 ca. 90 this work

" Surfactants: Tergitol TMN or Sarkosyl O.

h DEPA.
c C, complete (no visual turbidity in aqueous phase after coalescence).

100 The very thin membrane should guarantee a rather

low pressure drop, but first of all the appropriate high
80 flow velocity promises a much higher specific through-
put than encountered in conventional fibrous bed sep-
t $
60 I * arators.
• II i
g
40 O 3.2. Hollow fiber phase separator
g
20
Leading the standard dispersion through the lumen
of the hollow fibers, without any precoalescence, it was
0
o , p ~, Q ,o indeed possible to separate a clear organic phase, how-
0,0 0,1 0,2 0,3 0,4 0,5 0,6
ever the separation factor -q was very low (see Fig. 5 ).
superficial velocity through hollow fibers [m3s -lm -2]
Using the membrane coalescer in line, which increases
100
Fig. 5. The dependence of the separation factor "q in the HFM on the
superficial velocity, dispersion concentration 25 g/I, module No. 2,
without membrane coalescer, O, p] = 3.0 bar; with membrane coal- 80
escer, O, p~ = 1.0 bar; A, p~ = 2.0 bar; O, Pt = 3.0 bar; il, pj =4.0
bar: v,p~ =5.0 bar.
'~ 60

coalescence was not observed with hydrophilic vv • •

Vm •
membranes. 4o
g~
The efficiency and the range of application of the
membrane coalescence is demonstrated in Table 2, in 2O

comparison to typical fibrous bed separators. Two

advantages of the new membrane operation are evi- 0 i i i f i
dently: 0,0 0,1 0,2 0,3 0,4 0,5 0,6
t h e s e p a r a t i o n z o n e is e x t r e m e l y s h o r t ( l e s s t h a n t h e superficial velocity through hollow fibers [mas -~m -2]
m e m b r a n e t h i c k n e s s o f 110 > m ) ,
Fig. 6. The comparison of the separation efficiency of gravitational
the possibility of high superficial velocities, being
settler and HFM, dispersion concentration 25 g/l, p] = 3.0 bar; dotted
an o r d e r o f m a g n i t u d e higher compared with the line, mean separation factor for gravitational settling taken from Fig.
fibrous bed coalescers (see Table 2). 3; O, module No. 1; i , module No. 2; v , module No. 3.
202 U. Daiminger et al. / Journal of Membrane Science 99 (1995) 197-203
Fig. 7. The proposed mechanism of oil separation in a hydrophobic hollow fiber.
the droplet size, augments the separation rate at least
one order of magnitude (Fig. 5).'This basically agrees
with the measured reduction of enlarged droplets in the
dispersion after the hollow fiber module, because of
phase separation, which can be seen in Fig. 2.
It is remarkable, that the separation degree does not
depend on the total membrane area of the HFM, as can
be seen by comparing module No. 2 and module No. 3
(Fig. 6). Also the change of the static pressure in the
module ( 1. 105-5 • 105 Pa) does not influence the sep-
aration efficiency.
Fig. 6 shows the comparison of the fraction of sep-
arated oil phase r/vs. superficial velocity w between
gravitational settler and hollow fiber modules, both
after membrane coalescence. The yield of separation
using hollow fiber module decreases with the superfi-
cial velocity of the dispersion. For small velocities of
the emulsion flow the efficiencies of both methods are
rather comparable, for higher velocities the efficiency
of the hollow fiber module is much lower.
In a few test runs for complete oil removal the dis-
persion was recycled to tank 1 (ca. 10-20 times). Two
clear phase were obtained and in the aqueous phase the
oil concentration was below the detection limit of GC.
4. Discussion
4.1. Membrane coalescence
The presented results justify some conclusions con-
cerning the function of the membrane:
the enlargement of droplet size after one passage
through the PTFE membrane points at the role of
wetting,
N Nfi a,m
i0 pm
4 0 ~tm . . . .
the constant value of the separation factor 77for one
respectively five membranes shows, that the passage
of one sheet suffices for the observed coalescence,
the constancy of r/for different membrane areas (cf.
Fig. 3) allows to exclude a surface process, being
responsible for the enlargement,
the complete ineffectiveness of a small pore
membrane points at the relation of pore size and
droplet size as the decisive feature for coalescence.
The residence time of the dispersion inside the
membrane shows, that the process of coalescence
occurs very fast, i.e. in the time scale of milliseconds
(from 7 to 37 ms depending on f'). This should be the
reason for the independence of r/from the flow rate in
the range 10 < I?< 190 l/h corresponding to superficial
velocities in the range 0.003 < w < 0.15 m3/m 2 s. Fur-
ther experiments will show whether the decrease of the
separation factor r/for w=0.23 m3/m 2 s can be re-
compensed by an increase of residence time, achieved
by stacking several membranes.
4.2. Hollow fiber phase separation
The conducted experiments make clear, that the sep-
aration by means ofa HFM does not operate adequately
without prior droplet enlargement by the membrane.
This means, that only the large droplets are separated
as the dispersion passes through the hollow fibers.
The remarkable result is, that the degree of 77
decreases with the flow rate in spite of a constant por-
tion of enlarged droplets (see Fig. 6). The influence of
the cross section can be understood because of maldis-
tribution of the enlarged droplets at the entry of the
HFM. On the other hand, the decrease of the separation
factor "r/with superficial velocity must be caused by the
 U. Daiminger et al. / Journal of Membrane Science 99 (1995) 197-203
mechanism of separation during the flow of the
enlarged dispersion through the hollow fibers.
The decrease of r/can be explained by a model,
which regards the relation between the contact time t~
of an individual large droplet at the orifice of an indi-
vidual pore and the time tw needed for wetting the
individual pore with the organic phase. This is sche-
matically shown in Fig. 7. As tw is expected to be
constant, the residence time tR = l/w determines the
separation factor ~7.
The increase of the superficial velocity w and
decrease of the length l of an oil droplet imply a
decrease of tR and if tR and tw are in the same order of
magnitude, the separation efficiency deteriorates.
The assumed importance of a wetting process for the
hollow fiber phase separation is supported by the
observed independence of r/from the applied pressure.
This means that the flux of organic phase through the
pore system of the hollow fiber membrane is not the
rate determining step.
5. Conclusions
The thin hydrophobic membrane with a appropriate
pore diameter (dp= de) can be successfully used for
droplet coalescence, similar to conventional equip-
ment, i.e. fibrous or packed beds. Such enlarged oil
droplets can then be removed in hollow fiber separators.
This approach for dispersion separation, in our opinion,
can replace commonly used techniques. More work is
needed to understand the underlying mechanism, how-
ever our preliminary results point at wetting as the most
decisive step of separation. Further experiments con-
cerning the influence of droplet size and pore size seem
to be very important for the evaluation of the operation
range of the membrane coalescer as well as for inves-
tigation of the mechanism of phase separation by wet-
ting.
6. List of symbols
d diameter m Styrene, in K.-H. Reichert and W. Geisler (Eds.), Polymer
l length m Reaction Engineering, Hiithig and Wepf, Heidelberg, 1986, pp.
Pl inlet pressure bar
203
~" flow rate l/h
w superficial velocity m3/m 2 s
r/ separation factor %
6.1. Indices
e emulsion
fb fiber bed
p pore
Acknowledgements
The authors thank the Coulter Electronics Gmbh,
Germany for possibility of measurements of droplet
size with Coulter LS 130/100. We express also our
thanks to Hoechst AG (Germany) for discount on the
hollow fiber modules.
References
[ 1] V.B. Menon and D.T. Wasan, Demulsification, in P. Becher
(Ed.), Encyclopedia of Emulsion Technology, Vol. 2, Marcel
Dekker, New York, 1985, pp. 1-75.
[2] D.F. Sherony, R.C. Kinmer and D.T. Wasan, Coalescence of
Secondary Emulsions in Fibrous Beds, in E. Matijevic (Ed.),
Surface and Colloid Science, Vol. 10, Plenum, New York, 1978,
pp. 99-161.
[3] R.E. Treybal, Liquid Extraction, McGraw-Hill, New York,
1963.
[4] W.M. Langdon and D.T. Wasan, Separation of Organic
Dispersions from Aqueous Medium by Fibrous Bed
Coalescence, in N.N. Li (Ed.), Recent Developments in
Separation Science, Vol. 5, CRC Press, West Palm Beach, USA,
1979, pp. 159-183.
[5] S.S. Sareen, P.M. Rose, R.C. Gudesen and R.C. Kintner,
Coalescence in Fibrous Beds, AIChE J., 12 (1966) 1045-1050.
[6] R. Magiera and E. Blass, Droplet Coalescence of Toluene-in-
Water Dispersions by Flow through Fibre Beds, in D.H. Logsdail
and M. J. Slater (Eds.), Solvent Extraction in the Process
Industries, Vol. l, Elsevier Applied Science, London, 1993, pp.
134-139.
[7] J.A. Walter, F. Kneissl and W. Nitsch, Modelling of Pulsed
Sieve-Plate Columns on the Basis of Mass Transfer Kinetics
using the System H20/ZJISOJH2SO4-Dodecane/HDEHP, in
D.H. Logsdail and M.J. Slater (Eds.), Solvent Extraction in the
Process Industries, Vol. 2, Elsevier Applied Science, London,
1993, pp. 1206-11213.
[8] H. Samarian, Ph. Hess, R. Janekovic, E. Rucker and R. Kerber,
The Influence of Stabilisers on Suspension Polymerisation of
171-174.