Macromol. Symp.

118,413-418 (1997) 413

MEMBRANE MICROFILTRATION OF OILY WATER

Jae-Jin Kim*

Membrane Laboratory, Korea Institute of Science and Technology (KIST),

P. 0.Box 131 Cheongryang, Seoul 130-650, Korea

A. Chinen and K Ohya

Dept. of Material Science and Chem. Eng., Yokohama National University,

156 Tokiwadai, Hodogaya-ku, Yokohama 240,Japan

Abstra Separation of oil in water emulsion was camed out by crossflow microfiltration using 3
typesof microporous glass tubular membrane with different pore size of 0.27,0.75,and 1.47B m.
The effect of pore size. on permeate flux and oil rejection was investigated and the filtration
mechanismswere analyzed based on various types of filtration models.

INTRODUCTION have been mainly used. But organic membranes are

Oily water in inland waterways and coastal zone has
become a big issue of water pollution to be solved
urgently. There are several sources of oily water
discharged from several industries such as steel
industry, machine industry, petroleum refinery,
petrochemical industry, textile industry, metal
industry, etc. These oily waters exists as a film on
the water surface(floating oil), in the form of a
dispersion with water(dispersing oil) or an emulsion
with water(emulsifying oil).
Regulations imposed on oily water pollution have
become tight to be coped with the conventional
treatment methods. The investigation of other
treatment methods has been extensively carried out
and the membrane separation process has been one
of the candidates. There are many reports
patticularly using ultrafiltration0lF) and reverse
osmosis(R0). Recently, there are several reports
using microfiltration(MF), and organic membranes
sensitive to both polar and chlorinated solvents, as
well as some high oil fractions. Therefore, highly
hydrophilic and solvent resistant materials should be
applied to oily water treatmentmfs. 1.2, 31.
EXPERIMENTAL
Membranes:
Membranes used in this study are 3 tubular type
microporous glass membranes with dfierent pore
size of 0.27,0.75,and 1.47/I m with inner and outer
diameters of 8 nun and 10 nun, respectively. The
physical properties of the membranes are shown in
Table 1.
Emulsion:
Oil in water emulsion is prepared by emulsifying
1000 mL of distilled water, 1.0mL of mineral oil and
0.1 mL of surfactant(Polyoxyethylene(20) Sohitan
Trioleate[Tween 851).

0 1997 Hiithig & Wepf Verlag, Zug CCC 1022-1360/97/$04.00

 41 4

Experimental apparatus: Tnblc 1

Mcmbi:~nc piopcnics
The experimental apparatus is shown in Fig. 1.
I SlOl I 75-80
The MF module(6) consisted of a membrane tube( 12)
of effeaive length 8 cm assembled in a glass tube( 11)
of 20 m m in inner diameter and fitted with Teflon
joint(l3). The temperamre was kept at 50P: and
the trans-membrane pressure at 35.3 P a .

Analytical methods:
Particle size distribution of the oil in water emulsion
was measured by Coulter Counter. Total organic
carbon(T0C) C Tof
~ oil plus surfactant in emulsion
was measured with TOC meter. Surfactant
concentrationin the emulsion C;was determinedby
tetrakis(4-fluomphenyl) borate titrationkf. 41, and
multiplication of by 0.65 gives TOC value of
surfactant C, TOC corresponding to oil particle
C., can be expressed by the following equation.
-
C,,= CT, 0.65 C,

Rejection and passage:

TOC and oil rejections are defined as follows.
RTCC= I - C T , ~CTJ
/ %,I = 1 - Co,p/Co,r
Surfactant passage is defined as follows.
p. = ChP1 C,J

Interfacial tension:
Interfacial tension between oil and water with
different surfactant concentration were measured
using a surface-tension apparatus.

1
RESULTS

Oil particle size .distribution:

Fig. 2 shows volume based particle size distribution
of oil in water emulsion.
- 032.8
l

Flux and rejection:

Fig. 3 shows the time dependence of filtration flux
and rejection of TOC. In every experimental run,
the filtration flux decreased rapidly within 10 min by
one third to sixth, and gradually reached a constant
value depending upon the pore size of the membrane.
With the increase of the pore size, initial filtration
flux increases, and rejection of TOC decreases.

DISCUSSIONS

Microfiltration model:
It is interesting to apply filtration models to the flux
decline of these membranes to estimate the filtration
characteristics. For the filtration models at constant 4111111

pressure difference, Hermans and Bredeemefs. 5, 61

proposed, complete blocking filtration, intermediate
blocking fdtration, standard blocking filtration and
cake filtration. Figures 4 to 7 show the results of
applying the data for the membrane with pore size of
0.27 m to the filtration models by plotting the
filtration flux(J, root J, or 1N) against the filtration
volume(V) or filtration time(t) depending on the
model. From these figures the whole filtration
process can be divided into two stages. The first stage
is expressed by some blocking filtration model which IJ 20 40 611 110 11ll1 1211
describes the plugging of the membrane, and the v x 1* [m'l

second is by cake filtration model. 1:zg. 4 Mulling oi 1 apninsl V in complete blwhnp. filtration model
J=-(K,iA)V+J,, dy=0.27wni

0
U ZU 411 611 RO 101l 120 11 101111 211110 311llll 4lIOll
416

First stage:
Fig. 8 shows the relationship between the filtration
time and the filtrate volume estimated from each
blocking filtration model, together with the
experimental data of membrane with pore size 0.27
w. The lines in Fig. 8 are calculated from the
equations of blocking filtration models, using the
filtration constants Kb.K, and K,which are obtained
by assuming linearity of the data shown in figures 3
- 5 within first 10 min of filtration time. From Fig.
8 the complete blocking filtration model may explain
the experimental resultsvery well.
The experimental data of membrane with pore size of
0.75 w is well correlated by the intermediate 50 -

blocking filtration model, with pore size of 1.47m K,J.LII*IC 3

1

40 - I-

by the standard blocking filtration model, as shown

in Fig. 9 and 10.
- .-
E 30
comparing with the particle size distribution of oil
emulsion and average pore size, smaller pore of 0.27 -Con~plclc blurking
.m might be blocked by oil emulsion completely, - Intcrincdialc blocking
S1;indard blocking
medium size of pore of 0.75 f l partially blocked 0 Espcrinicnlal dnln

and larger pore of 1.47 m might let allow oil

U 2uu 400 6011 sou
emulsion permeate through the pore and be subjected
t Is1
to the shrinkage of pore size by the adsorption of Fig. X Applicahilily o l hlocking fillralion mudcl
al lhc firs1 stage ol fillralion process.
small oil emulsion. Fur symhols 01 porc size 0.27 pm

350 , I

Coniplete hlocklng
Cuiiiylclc blncking
- Inlcnncdialc blocking
.lntrrincdinlc hlocklng
Slandard blerkliig
Slandnrd blocking
0 Eipcriincii1:d drila
Espcrinicnttil dnla
 417

0.27 m membrane:
Fig. 11 shows the increase of the filtrate volume with 130

filtration time expressed by complete blocking model

100
in the first stage until 700 s and by cake filtration
model in the second stage there after. The agreement -
2
80

of the experimental data with the theoretical line is I

60
very good. "
X

> 40
0.75 m membrane:
10
Fig. 12 shows the increase of the filtrate volume with
3
filtration time expressed by intermediate blocking 0 ~ " ' ~ " " ' " " "
model in the first stage until 700 s and by cake 0 1000 2000 3000 4000

filtration model in the second stage there after. 1 Is1

Fig. 1 I 13clwecii liltralioii liiiic i d liltrate VOIUIIII:
logether wit11cnlculiileil cliitii dl,=0.27 ~ t i i i

1.47 .m membrane:
Fig. 13 shows the increase of the filtrate volume with 300
E .,.OJ.l*' I".,

filtration time expressed by standard blocking model

in the first stage until 900 s and by cake fillration
200
model in the second stage there after.
150
x
Oil rejection: #
IOII
The volume percents of oil particles are estimated as
50
1.9 vol% for less than 0.27 m, 5.7 vol% for 0.75 m
It
and 11.6 vol% for 1.47 m from particle size
distribution. If the pore in the membrane let pass
through oil particles of which the diameter is less
than that of the pore and block oil particles greater
6110
than, the rejection of oil particle may be estimated as K . 4 llx10\* d s

98.1%. 94.3% and 88.4% for membranes having son - n-

D...o I
pore size 0.27,0.75 and 1.47 m. The oil rejections
extrapolated at the beginning of the filtration, show 2
almost same as the estimations which are shown by 4 30'

the dotted lines. Then the oil rejections decrease >

.........Cake fillralioii
and take almost constant value after about 1,OOO s,
0 Esperinienlal daln
when the second stage of the cake filtration starts.
Using the interfacial tension and the trans-membrane
0 1000 2000 3000 4000
pressure 35.3 H a , the critical pore size beyond
t bl
which oil may permeate through the pore, is Rg.19 Between fillralion time and filtrate volume
logelher with calculated data dp=1.47 pm
calculated as 0.59 m. This type of glass
410
membrane has a very sharp distribution of pores, the
smallest limit is half of the average pore size and the
largest twice. Even, in the membrane of 0.27 VIM
are some fraction of pores larger than the critical
pore size of 0.59 PI.Therefore, some amount of
oil accumulated on the surface. of the membrane
might permeate through the largest 'pore.
measured oil rejections for the three membranes are
always smaller than that estimated on the hypothesis
of blocking by the pore. The difference becomes
larger with the increase of pore size, as Fig. 14.
Surfactant passage:
As Table 2, with the increase of pore size, surfactant
passage increases and reaches 99% with membrane
of 1.47 m, but oil rejection decreases. It seems
difficult to find membrane having both high oil
rejection and high surfactant passage.
CONCLUSIONS
(1) The membrane with larger pore shows higher
flux and lower oil rejection, and vi& versa.
100
.................................................
...... 0.................. ....... 0 ........
--
pe YO
........ .o............... .. ............... 0.........
E
- Reinhold, N.Y., 1991, p.275
.-
g nu
L
I I
70
(2) The transition of separation mechanism from
blocking to cake formation occu~saround 10
min for the membranes used in this study at the
individual characteristic filtration times.
(3) The filtration mechanism in the first stage can
be explained by 3 tspes of blocking filtration
The model; complete blocking for 0.27 w
membrane, intermediate blocking for 0.75 VIM,
standard blocking for 1.47 /no, and in the
second stage by cake filtration model.
(4) With the increase of pore size, oil rejection
decreases and surfactant passage increases. It
is difficult to find membrane having both high
oil rejection and high surfactant passage.
ACKNOWLEDGEMENTS
This work was supported by Foundation of River and
Watershed Environment Management, Japan and
Environmental Conservation Project Fund of
Kanagawa Prefecture, Japan.
REFERENCES
(1) P. Gallagher, Water Waste Treat., August,
??L?.. 42( 1992)
(2) R. R. Bhave, J. Guibaud, R Rumeau,
"Inorganic Membranes", Van Noarand
0 0.27 ;;;;;I
(3) A. B. Koltuniewicz,R. W. Field, T. C. h o t , J.
ofMembrane Science, 102, 193(1995)
(4) M. Tsubouchi, N. Yamasaki, K. Yanagisawa,
Anal. Chem., 57,783(1985)
(5) P. H. Hermans, H. L. Bredee, Rec. Trav. Chim.
des PaysBas, 54,680(1935)
(6) J. Hermia, Trans. Insritu. Chem. Eng., 60,
183(1982)