Novel Techniques For Oil/water Separation: U. Daiminger, W. Nitsch, P. Plucinski, S. Hoffmann
Novel Techniques For Oil/water Separation: U. Daiminger, W. Nitsch, P. Plucinski, S. Hoffmann
MEMBRANE
SCIENCE
ELSEVIER Journal of Membrane Science 99 (1995) 197-203
Short communication
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
dispersed organic phase as the permeate. Compared to The dispersion then was led through the separation unit
usually applied packed or fibrous beds as coalescence 4 (Liqui-Cel ® hollow fiber module (HFM), Hoechst/
aids, the novel aspects concern the operation of thin Celanese, USA). The separated organic phase was col-
membranes to aggregate oil dispersions as well as to lected in a beaker mounted on the analytical balance
separate them. The first goal is the use of a microfiltra- (Kern 510-37, Kern, Germany).
tion membrane as a coalescing aid, to enlarge the diam- The emulsion was prepared as follows: the appro-
eter of droplets. In this case the entire dispersion is priate amount of the organic phase was added to dis-
forced to pass the membrane coalescer. As a second tilled water, emulsification occurred due to shear forces
goal we want to use the ability of spreading oil droplets in the gear wheel pump under standard conditions (56
on the hydrophobic surface of porous hollow fibers, in 1 of dispersion were circulated by the pump through
order to separate the organic phase. bypass 5 for 4 h with the volumetric flow 130 l/h).
2.2. Membranes.
2. Experimental
iiiiiiiiiijili
Fig. 1. Schematicview of separation unit: (1) dispersionreservoir; (2) membranecoalescer; (3) samplingdevice; (4) hollow fibermodule;
(5) bypass.
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:
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
membrane ~ _
t _~ O-ring E
support . . . . . . . . _50 mm_......... / ,,sive
membrane
Table 2
The comparison of efficiency of fibrous bed and membrane coalescers
Fibrous beds
Membrane coalescer
lsododecane / water~ 2.5 PTFE 0.011 0.3-- 15.0 ca. 90 this work
N Nfi a,m
i0 pm
4 0 ~tm . . . .
the droplet size, augments the separation rate at least the constant value of the separation factor 77for one
one order of magnitude (Fig. 5).'This basically agrees respectively five membranes shows, that the passage
with the measured reduction of enlarged droplets in the of one sheet suffices for the observed coalescence,
dispersion after the hollow fiber module, because of the constancy of r/for different membrane areas (cf.
phase separation, which can be seen in Fig. 2. Fig. 3) allows to exclude a surface process, being
It is remarkable, that the separation degree does not responsible for the enlargement,
depend on the total membrane area of the HFM, as can the complete ineffectiveness of a small pore
be seen by comparing module No. 2 and module No. 3 membrane points at the relation of pore size and
(Fig. 6). Also the change of the static pressure in the droplet size as the decisive feature for coalescence.
module ( 1. 105-5 • 105 Pa) does not influence the sep- The residence time of the dispersion inside the
aration efficiency. membrane shows, that the process of coalescence
Fig. 6 shows the comparison of the fraction of sep- occurs very fast, i.e. in the time scale of milliseconds
arated oil phase r/vs. superficial velocity w between (from 7 to 37 ms depending on f'). This should be the
gravitational settler and hollow fiber modules, both reason for the independence of r/from the flow rate in
after membrane coalescence. The yield of separation the range 10 < I?< 190 l/h corresponding to superficial
using hollow fiber module decreases with the superfi- velocities in the range 0.003 < w < 0.15 m3/m 2 s. Fur-
cial velocity of the dispersion. For small velocities of ther experiments will show whether the decrease of the
the emulsion flow the efficiencies of both methods are separation factor r/for w=0.23 m3/m 2 s can be re-
rather comparable, for higher velocities the efficiency compensed by an increase of residence time, achieved
of the hollow fiber module is much lower. by stacking several membranes.
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 4.2. Hollow fiber phase separation
oil concentration was below the detection limit of GC.
The conducted experiments make clear, that the sep-
aration by means ofa HFM does not operate adequately
without prior droplet enlargement by the membrane.
4. Discussion
This means, that only the large droplets are separated
as the dispersion passes through the hollow fibers.
4.1. Membrane coalescence The remarkable result is, that the degree of 77
decreases with the flow rate in spite of a constant por-
The presented results justify some conclusions con- tion of enlarged droplets (see Fig. 6). The influence of
cerning the function of the membrane: the cross section can be understood because of maldis-
the enlargement of droplet size after one passage tribution of the enlarged droplets at the entry of the
through the PTFE membrane points at the role of HFM. On the other hand, the decrease of the separation
wetting, factor "r/with superficial velocity must be caused by the
U. Daiminger et al. / Journal of Membrane Science 99 (1995) 197-203 203
mechanism of separation during the flow of the ~" flow rate l/h
enlarged dispersion through the hollow fibers. w superficial velocity m3/m 2 s
The decrease of r/can be explained by a model, r/ separation factor %
which regards the relation between the contact time t~
of an individual large droplet at the orifice of an indi- 6.1. Indices
vidual pore and the time tw needed for wetting the e emulsion
individual pore with the organic phase. This is sche- fb fiber bed
matically shown in Fig. 7. As tw is expected to be p pore
constant, the residence time tR = l/w determines the
separation factor ~7.
The increase of the superficial velocity w and Acknowledgements
decrease of the length l of an oil droplet imply a
The authors thank the Coulter Electronics Gmbh,
decrease of tR and if tR and tw are in the same order of
Germany for possibility of measurements of droplet
magnitude, the separation efficiency deteriorates.
size with Coulter LS 130/100. We express also our
The assumed importance of a wetting process for the
thanks to Hoechst AG (Germany) for discount on the
hollow fiber phase separation is supported by the
hollow fiber modules.
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 References
rate determining step.
[ 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.
5. Conclusions [2] D.F. Sherony, R.C. Kinmer and D.T. Wasan, Coalescence of
Secondary Emulsions in Fibrous Beds, in E. Matijevic (Ed.),
The thin hydrophobic membrane with a appropriate Surface and Colloid Science, Vol. 10, Plenum, New York, 1978,
pp. 99-161.
pore diameter (dp= de) can be successfully used for
[3] R.E. Treybal, Liquid Extraction, McGraw-Hill, New York,
droplet coalescence, similar to conventional equip- 1963.
ment, i.e. fibrous or packed beds. Such enlarged oil [4] W.M. Langdon and D.T. Wasan, Separation of Organic
droplets can then be removed in hollow fiber separators. Dispersions from Aqueous Medium by Fibrous Bed
This approach for dispersion separation, in our opinion, Coalescence, in N.N. Li (Ed.), Recent Developments in
Separation Science, Vol. 5, CRC Press, West Palm Beach, USA,
can replace commonly used techniques. More work is 1979, pp. 159-183.
needed to understand the underlying mechanism, how- [5] S.S. Sareen, P.M. Rose, R.C. Gudesen and R.C. Kintner,
ever our preliminary results point at wetting as the most Coalescence in Fibrous Beds, AIChE J., 12 (1966) 1045-1050.
decisive step of separation. Further experiments con- [6] R. Magiera and E. Blass, Droplet Coalescence of Toluene-in-
cerning the influence of droplet size and pore size seem Water Dispersions by Flow through Fibre Beds, in D.H. Logsdail
and M. J. Slater (Eds.), Solvent Extraction in the Process
to be very important for the evaluation of the operation
Industries, Vol. l, Elsevier Applied Science, London, 1993, pp.
range of the membrane coalescer as well as for inves- 134-139.
tigation of the mechanism of phase separation by wet- [7] J.A. Walter, F. Kneissl and W. Nitsch, Modelling of Pulsed
ting. 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,
6. List of symbols 1993, pp. 1206-11213.
[8] H. Samarian, Ph. Hess, R. Janekovic, E. Rucker and R. Kerber,
The Influence of Stabilisers on Suspension Polymerisation of
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 171-174.