iournalof

MEMBRANE
SCIENCE
ELSEVIER Journ~ of Membrane Science 129 (1997) 221-235

Crossflow microfiltration of oily water

Jeffrey Mueller 1, Yanwei Cen 2, Robert H. Davis*
Department of Chemical Engineering, University of Colorado at Boulder, Boulder, CO 80309-0424, USA

Received 19 July 1996; received in revised form 12 November 1996; accepted 14 November 1996

Abstract

Two a-alumina ceramic membranes (0.2 and 0.8 jam pore sizes) and a surface-modified polyacrylonitrile membrane
(0.1 jam pore size) were tested with an oily water, containing various concentrations (250-1000 ppm) of heavy crude oil
droplets of 1-10 ~tm diameter. Significant fouling and flux decline were observed. Typical final flux values (at the end of
experiments with 2 h of filtration) for membranes at 250ppm oil in the feed are ~30--40kg m -2 h -1. Increased oil
concentrations in the feed decreased the final flux, whereas the crossflow rate, transmembrane pressure, and temperature
appeared to have relatively little effect on the final flux. In all cases, the permeate was of very high quality, containing <6 ppm
total hydrocarbons. The addition of suspended solids increased the final membrane flux by one order of magnitude. It is
thought that the suspended solids adsorb the oil, break up the oil layer, and act as a dynamic or secondary membrane which
reduces fouling of the underlying primary membrane. Resistance models were used to characterize the type of fouling that
occurs. Both the 0.2 jam and the 0.8 jam ceramic membranes appeared to exhibit internal fouling followed by external fouling,
whereas external fouling characterized the behavior of the 0.1 jam polymer membrane from the beginning of filtration.
Examination of the external fouling layer showed a very thin hydrophobic oil layer adsorbed to the membrane surface. This oil
layer made the membrane surface hydrophobic, as demonstrated by increased water-contact angles. The oil layer proved
resistant to removal by hydrodynamic (shear) methods. By extracting the oil layer with tetrachloroethylene, followed by IR
analysis, its average thickness at the end of a 2 h experiment under typical conditions was determined to be 60 ~tm for the
0.2 jam ceramic membrane and 30 jam for the 0.1 jam polymer membrane. These measured amounts of oil associated with the
membrane at the end of the experiments are in good agreement with those determined from a simple mass balance, in which it
is assumed that all of the oil associated with the permeate collected is retained on or in the membrane, indicating that the
tangential flow did not sweep the rejected oil layer to the filter exit.

Keywords: Fouling; Water treatment; Produced water; Microfiltration

1. Introduction

*Corresponding author. Tel.: (303) 492-7314; fax: (303) 492-
4341, e-mail: davisr@spot.colorado.edu.
tPresent address: Harrison-Western Environmental, 1208 Quail
Street, Lakewood, CO 80215, USA.
2present address: Chusei, Inc., 12500 Bay Area Boulevard,
Pasadena, TX 77507, USA.
Wastewaters containing dispersed oils and sus-
p e n d e d particles are p r o d u c e d f r o m diverse industrial
sources, such as general metal-working, f o o d proces-
sing, transportation, and gas and oil production. Waste
streams f r o m onshore and offshore oil and gas opera-

0376-7388/97/$17.00 © 1997 Elsevier Science B.V. All rights reserved.

PII S0376-7388(96)00344-4
222 J. Mueller et al./Journal
tions are among the largest sources of oily waste-
waters. The volume of oily waste or 'produced' water
generated annually in the US onshore oil and gas
operations is estimated at 33 billion barrels [1]. These
produced wastewaters cannot be reinjected to oil wells
or discharged to receiving waters, because they con-
tain high concentrations of oil, grease, and suspended
particles. Typical composition ranges include 50-
1000 ppm total oil and grease, and 50-350 ppm total
suspended solids [2,3]. Oil and particulate concentra-
tions >10 ppm in water can plug injection wells, foul
equipment, or form heat-insulating films. Moreover,
regulations require that maximum total oil and grease
concentrations in discharge waters be 5-40 ppm, with
a typical requirement of 10-15 ppm [4]. Thus, sub-
stantial removal of small oil droplets and particles
from produced waters is required prior to reuse or
discharge.
Since conventional-treatment technologies such as
gravity separators and coalescer plates cannot meet
the high purity requirements for discharge or reinjec-
tion, new or improved technologies have been inves-
tigated. Among them, membrane microfiltration (MF)
has been used in a growing number of cases for
successful treatment of oily wastewaters [5-7]. Sys-
tems have already been pilot-tested on offshore oil
platforms and onshore facilities [3,8-10]. These tests
have shown that membrane systems can be successful
in the field for treating produced water.
Distinct advantages of membrane technology for
treatment of produced water include reduced sludge,
high quality of permeate, and the possibility of total
recycle water systems. When considering these advan-
tages along with the small space requirements, mod-
erate capital costs, and ease of operation, membrane
technology provides a very competitive alternative to
conventional technologies.
Although MF membranes can successfully treat
produced waters, they experience a decline in perme-
ate throughput or flux as a result of fouling. This flux
decline is due to the adsorption and accumulation of
rejected oil, suspended solids, and other components
of produced water on the membrane surface (external
fouling) or in the membrane pores (internal fouling).
This fouling can be irreversible or resistant to clean-
ing, making the original flux unrecoverable. Fouling
can be reduced through the use of different or surface-
modified membrane materials, various operating stra-
of Membrane Science 129 (1997) 221-235
tegies and pretreatments, and hydrodynamic techni-
ques [8]. However, specific fouling mechanisms and
reduction strategies during microfiltration of produced
water are not well understood.
Although there is relatively little understanding of
fouling mechanisms for oily wastewaters in microfil-
tration processes, some results have been reported for
ultrafiltration (UF) membranes used for the removal of
lubricating and cutting oils used in the metal industry.
Bhattacharyya et al. [11] observed internal and exter-
nal fouling during UF of a lubricating oil-nonionic
detergent-water solution through noncellulosic, tub-
ular membranes. They noted that membrane fouling
and cleaning requirements depend on the type of oily-
water systems and membranes. Lee et al. [12] studied
concentration polarization and fouling during UF of a
soluble oil-surfactant-water emulsion through a poly-
meric membrane in a stirred filtration cell. They found
that fouling was due to adsorption of oil on the
membrane structure. Lipp et al. [13] studied UF of
soluble oil-in-water emulsions through a batch cell
containing various polymeric and cellulosic mem-
branes. They stated that fouling followed a gel-polar-
ized, film-model behavior, with the oil droplets
coalescing into the surface-fouling oil film. Koltunie-
wicz et al. [14] analyzed and compared the perfor-
mance of various ceramic and polymeric membranes
operated in crossflow and dead-end filtration modes
during microfiltration of a n-dodecane/water emul-
sion. They observed that the membranes initially
fouled internally (described by a pore-blocking
model), and then external fouling began to dominate
(described by a cake-filtration model). Finally, Bha-
numurthy et al. [15] studied UF of cutting oil with
polysulfone membranes. They presented the results of
changing various operating variables, including the
increase in flux observed at higher crossflow velocities
due to washing away of the polarized layer. They also
proposed a model for the prediction of the permeate
flux which incorporates droplet coalescence and shear
rate.
Our study was focused on understanding and char-
acterization of the type of fouling occurring during
MF of a model-produced water, containing crude-oil
droplets and, in some cases, suspended solids. Experi-
mental results on flux decline and permeate quality for
ceramic and polymeric membranes are reported for a
variety of process- operating conditions. Simple mod-
 J. MueUer et al./Journal of Membrane Science 129 (1997) 221-235 223

els have also been employed to help analyze the
membrane-fouling process.
2. Materials and methods
2.1. M o d e l - p r o d u c e d w a t e r a n d c h a r a c t e r i z a t i o n
Synthetic-produced water was developed for use in
this study. A heavy crude oil (API 12 weight, density
0.972 g cm-3), supplied by UNOCAL from the Hue-
neme field in California, was added at various con-
centrations to tap water. A blender (Osterizer Model
890-28M) mixed the oil and water at high shear rates
for ~ 2 min.
An Horiba (Model OCMA-220) oil-content analy-
zer was used to determine the total oil and grease
content of the feed and the permeate. The Horiba
analyzer uses tetrachloroethylene to extract oil and
grease from water, and then measures absorbance at a
single IR wavelength, 2930 cm -1 [16]. The instru-
ment was calibrated for the Hueneme heavy crude oil
emulsion used in the experiments.
Oil-droplet size distributions for the feed emulsions
were determined using a Coulter Multisizer. A hema-
cytometer slide and optical microscope were also used
to confirm these measurements. Results showed that
most of the droplets were 1-10 ~tm in diameter, with a
number-averaged droplet diameter of ,-~2~tm and
volume-averaged droplet diameter of ~ 4 ~tm
(Fig. 1). Natural surfactants in the heavy crude oil
stabilized the emulsion sufficiently for the purpose of
these experiments, although some of the oil gradually
came out of solution and formed a ring at the water
level in the reservoir.
Feed-emulsion samples were also centrifuged for
60min at 1850rpm in 100ml pear-shaped, glass
centrifuge tubes using an International Portable Cen-
trifuge Model IPC-2. Under these conditions, all
droplets >0.5 ~tm in diameter are predicted to be
removed. Starting with a feed concentration of
250 ppm total hydrocarbon, the concentration remain-

1600 2.5
N u m b e r Distribution
1400

2.0 A
1200 E
I i tvo,o.oo,= , =,oo Q.
i._

J~ Q.
E 1000 O
:3 1.5 E
t--
m 800 O
>
o
I,,.
a 600 1.0 --~
Q.
2
a
400
0.5
200

0.0
0 5 10 15 20 25 30

Droplet size (ixm)

Fig. 1. Oil-dropletnumber (solid curve) and volumeversus diameter (shaded histogram) size distributions for the heavycrude oil-in-water
emulsion.
224 J. Mueller et al./Journal of Membrane Science 129 (1997) 221-235

ing in solution after centrifugation was ~20 ppm. The
remaining concentration is due to soluble hydrocar-
bons and finely dispersed, submicron-sized droplets.
The viscosity of the crude oil was measured using a
rotating viscometer (Brookfield Model DV-1 with the
Brookfield Model 74R temperature controller). The
measured viscosity of the heavy crude oil is
5.3 g cm -1 s -1 at 40°C, and 135 g c m -1 s -1 at 23°C.
2.2. Membranes
Two a-alumina ceramic membranes marketed by
the Membralox division of US Filter, and a surface-
modified polyacrylonitrile (PAN) membrane marketed
by Zenon Environmental, were used. The two ceramic
membranes are of 0.2 and 0.8 ~tm nominal pore dia-
meters, and each has 35% porosity and an asymmetric
surface layer which is 4-5 lam thick. The ceramic
membranes have a tubular geometry, with an i.d. of
0.7 cm, a useful length of 20.6 cm, and a surface area
of 45.3 cm 2. The membranes carried a negative charge
at pH levels typical of produced water (pH 6.6-7.8)
[17]. The PAN membrane has a nominal pore diameter
of 0.1 ~tm, and its surface layer is 150 ~tm thick. It also
has a tubular geometry, with an i.d. of 2.1 cm, a useful
length of 27.9 cm, and a surface area of 185 cm 2.
2.3. Experimental apparatus
Fig. 2 shows the apparatus constructed for the
experiments. It is capable of operating in a variety
of flow patterns, temperatures, and pressures. A gear
pump (Liquiflow Model CF8M) circulated the feed
emulsion from the jacketed, temperature-controlled
glass-feed reservoir through the vertically aligned
membrane unit. The retentate was returned to the feed
reservoir. A diaphragm valve was used to control the
pressure in the system. An electronic balance inter-
faced with a personal computer was used to collect
permeate mass versus time data, and the computer
controls a regeneration pump simultaneously which
maintains a constant liquid level in the feed vessel.

retentate line
~? _| ~?,

1
diaphragm
membrane ] valve
module
backflush line
Ii

permeate backflush
. make-up line line reservoir
jacketed
feed vessel
permeate
vessel | ,
level
, , control
I---q ~ [1circuit
--~

temperature make-up microbalance I

computer I
controller water
reservoir
Fig. 2. Produced water experiment apparatus.
 J. MueUer et al./Journal of Membrane Science 129 (1997) 221-235 225

The feed solution was changed every 30 rain to pre-
vent possible depletion of oil concentration due to
coalescence and deposition on the side of the reservoir.
A backflush line was included to aid membrane clean-
ing and for future studies of backflushing and back-
pulsing.
2.4. Experimental procedures
The experiments were repeated three times for each
set of conditions. Tap water was run through the
membrane for the first 1500 s, followed by the
crude-oil emulsion for 7200 s, and then by a second
water flux for an additional 1300 s. A single ceramic
membrane was reused (after cleaning) for all experi-
ments for the corresponding membrane type. One
polymeric membrane was used for the first three sets
(11-13) of conditions, and a second one was used for
the other two sets (14 and 15). Experimental condi-
tions used in testing the three membranes are given in
Table 1. Baseline or 'benchmark' conditions were
10psig (69.4kPa) transmembrane pressure, 40°C,
2 5 0 p p m heavy crude oil in the feed, and a
0.24 m s - I mean crossflow velocity. The Reynolds
numbers are 2500 and 7600, respectively, for the
ceramic and polymer membranes.
The apparatus containing the ceramic membranes
was cleaned after each experiment with tap water, then
with 0.2 wt% sodium hydroxide, and finally with 1.0%
nitric acid at 40°C. For the PAN membrane, tap water,
then an anionic caustic detergent (pH 12.1, Zenon),
and finally citric acid (pH 1.4), were used after each
experiment. After the wash cycle, the PAN membrane
was removed and soaked in the anionic caustic deter-
gent followed by water for several hours as a final
cleaning step. The method of using an alkaline-acidic-
alkaline wash cycle was found to be the most effective
cleaning method by us and by others [18] for similar
situations involving organic fouling.
2.5. Determination o f foulant amount
The fouling layers were too thin to be determined
accurately by weighing the fouled and unfouled mem-
branes. Instead, organic solvent was used to extract the
oily foulants from the membranes. After an experi-
ment, the membrane was removed from its module
and immersed in tetrachloroethylene. The oil was

Table 1
Experimental conditionsused in testing three microflltrationmembranes
Experiment number Description Temperature Pressure Flow-rate Velocity Coil.feed
(°C) (psig) (ml min- 1) (m s- 1) (ppm)
0.8/am ceramic
1 Baseline 40 10 549 0.24 250
2 High zS,P 40 20 549 0.24 250
3 High flow 40 10 2094 0.91 250
4 High conc. 40 10 549 0.24 1000

0.2 ~tm ceramic

5 Baseline 40 10 549 0.24 250
6 High AP 40 20 549 0.24 250
7 High flow 40 10 2094 0.91 250
8 High conc. 40 10 549 0.24 1000
9 SS 40 10 549 0.24 250
10 SS, high flow 40 10 2094 0.91 250

0.1 ~tm PAN

11 Baseline 40 10 4929 0.24 250
12 High Ap 40 20 5036 0.24 250
13 Low T 24 10 4929 0.24 250
14 High conc. 40 10 4929 0.24 1000
15 SS 40 10 4929 0.24 250
226 J. Mueller et al./Journal of Membrane Science 129 (1997) 221-235
partitioned into the known volume of solvent, and the
solvent was placed in the Horiba analyzer for the
measurement of its oil content.
3. Experimental results and discussion
Water-flux experiments were run on each mem-
brane before testing began. Results at 10 psig trans-
membrane pressure are shown in Fig. 3. The 0.8 gm
ceramic membrane experienced a significant water-
flux decline of 50% in 1.5 h, while the PAN membrane
experienced a 35% water-flux decline, and the 0.2 ~tm
ceramic membrane experienced an 18% water-flux
decline, during the same time. The water-flux decline
may be attributed to the small particles in the tap
water, any residual oil which still remains in the
apparatus, and the formation of microscopic bubbles
on the permeate side of each membrane due to the
depressurization which occurs as water passes through
the membrane. The greater water-flux decline for the
0.8 gm ceramic membrane may be due, at least in part,
to its faster permeate flow carrying more micro-con-
taminants to the membrane.
1600
1400
1200
~1000
~ 0.8~I.Lm ceramic membrane
E
800
x
,T 600
4O0
200
0 I
0 1000
Fig. 3. Comparison of water flux decline at 40°C and 10 psig transmembrane pressure for the three different membranes
3.1. Fouling of the 0.8 gm ceramic membrane with
produced water
The 0 . 8 g m ceramic membrane experienced a
severe flux decline during the baseline experiments
at 10 psig transmembrane pressure, 40°C, 250 ppm
heavy crude oil, and a 0.24 m s -1 mean crossflow
velocity (see Fig. 4 and Table 2). A nearly steady flux
of only ,-~30 kg m -2 h -1 was achieved after 7200 s of
oil-emulsion filtration. The second water flux, run
after fouling by the oil emulsion, showed no recovery
of the flux. This implies that the fouling layer is
strongly adsorbed and resistant to shear. However,
the permeate quality was excellent, with < 1 ppm total
hydrocarbons.
After completing the baseline experiments, the
effects of three operating variables were investigated:
transmembrane pressure, oil concentration, and cross-
flow velocity. The results shown in Table 2 are the
mean values plus and minus one standard deviation.
The curves in Fig. 4, and in the subsequent figures, are
the averages of the flux versus time data for the
repeated experiments. The initial flux values in
Table 2 are those observed at the end of the 1500 s
0.2 pm ceramic membrane
0.1 pm PAN membrane
I I I I
2000 3000 4000 5000 6000
Time (seconds)
 J. Mueller et al./Journal of Membrane Science 129 (1997) 221-235 227

2500

2000
, High Pressure

1500 L H
igh Crossflow Velocity

lOOO
,-r
~ne
5O0 • . •

0 2000 4000 6000 8000 10000 12000

Time (seconds)
Fig. 4. Flux-decline curves for the 0.8 ktm c~-alumina ceramic membrane and heavy crude oil-in-water emulsion at various conditions.

Table 2
Summary of results for the three tested microfiltration membranes - the results are shown as the average of three repetitions, plus and minus
one standard deviation, with +, - and o representing positive, negative, and insignificant differences from baseline results at the 90%
confidence level

Experiment number Initial flux Final flux Flux change Coil, ee~a Con, p~rmeate Oil removal
(kg m -2 h -1) (kg m -2 h 1) (%) (ppm) (ppm) (%)
0.8 ~tm ceramic
1 6784-51 334-6 -95.1 250 0.35:0.2 99.9
2 998+500 40±22 (o) -95.6 250 0.64-0.3 (o) 99.7
3 8004-128 46+6 (+) -94.2 250 1.8+0.5 (+) 99.3
4 471+15 2 6 i l l (o) -94.5 1000 1.4d:0.2 (+) 99.4

0.2 ~tm ceramic

5 525+50 424-19 -91.9 250 3.7+1.9 98.5
6 6574-156 21±2 (o) -96.8 250 5.1+0.8 (o) 98.0
7 2114-19 324-13 (o) -84.8 250 4.64-0.2 (o) 98.2
8 3014-52 25±6 (o) -91.7 1000 5.84-1.0 (+) 99.4
9 305 312 +1.6 250 5 98.0
10 281 577 +105.4 250 5.4 98.5

0.1 ktm PAN

11 2044-27 344-3 (o) -83.3 250 1.84-0.6 99.3
12 2874-30 32+3 (o) -88.9 250 0.54-0.2 ( - ) 99.8
13 1635:5 314-3 (o) -81.0 250 2.84-1.4 (o) 98.9
14 4384-30 6.94-2 ( - ) -98.4 1000 0.94-0.3 (o) 99.9
15 455±30 226 -50.3 250 0.9 99.7
228 J. Mueller et al./Journal of Membrane Science 129 (1997) 221-235

800

¢-
700

600

500
~ ressure

High Oil Concentration

400

300

u. High Crossflow Velocity

200

100

0 I I I I I

0 2000 4000 6000 8000 10000 12000

Time (seconds)

Fig. 5. Flux decline curves for the 0.2 I.tm alpha-alumina ceramic membrane and heavy crude oil-in-water emulsion at various condition

periods of pure-water flux; the large variations of the
initial flux indicate that the cleaning procedures do not
yield a consistent state of the membrane. The higher
pressure gave a higher initial flux, but the final flux
after oil-emulsion filtration (~40 kg m -2 h -1) is not
significantly higher than that of the baseline experi-
ment. The higher crossflow velocity (0.91 m s -1)
resulted in a small increase in the final flux, whereas
the increased oil concentration (1000 ppm) resulted in
a slightly reduced final flux. In each of these tests, the
permeate oil concentration remained below 2 ppm.
3.2. Fouling of the 0.2 gm ceramic membrane with
produced water
The 0 . 2 g m ceramic membrane experienced a
severe flux decline during the baseline experiment
(Table 2 and Fig. 5). A nearly steady flux of
,-~40 kg m -2 h -1 was achieved during filtration of
the oil emulsion, and no recovery of flux was observed
when the feed was switched back to water. A higher
transmembrane pressure (20 psig) resulted in the most
fouling and the lowest final-flux value. The higher oil
concentration (1000 ppm) also resulted in a low final
flux. In all cases, the final flux values are not sig-
nificantly different at the 90% confidence level. The
higher crossflow velocity ( 0 . 9 1 m s -1) did not
improve the final flux. In each of these tests, the
permeate oil concentration remained below 6 ppm.
Fig. 5 shows that the initial membrane permeability
changed after the baseline experiments. An irreversi-
ble flux decline is the reason for the difference
between the starting water fluxes for the baseline
experiments and for the other experiments. The clean-
ing procedure was unable to remove all of the foulants.
Stronger acid, base, and detergent washes also failed
to fully recover the initial clean-membrane water flux.
However, the starting water fluxes or state of the
membrane do not appear to significantly affect the
final fluxes for the oil emulsion.
3.3. Fouling of the 0.1 ~am PAN membrane with
produced water
The PAN membrane experienced a large flux
decline during the baseline experiments (Table 2
and Fig. 6). A nearly steady flux of ~30 kg m -2 h -1
was achieved by the end of the 7200 s of oil-emulsion
filtration. Again, the second water flux, run after
fouling by the oil emulsion, gave no recovery of flux.
 J. Mueller et al./Journal of Membrane Science 129 (1997) 221-235
600
500
High Concentration
" ~ 400
gh Pressure
E
300
,-I
X
i, 200
1O0
0
0 2000 4000
Time (seconds)
Fig. 6. Flux-decline curves for the 0.1 ~tm PAN membrane and heavy crude oil-in-water emulsion at various conditions.
The final flux values were not changed significantly by
increasing the transmembrane pressure or lowering
the temperature. However, the PAN membrane fouled
very badly at a higher feed-oil concentration
(1000 ppm), and a thick external oil layer was evident
upon examination of the membrane. In all cases, the
permeate contained <3 ppm total hydrocarbons. From
the initial flux values in Table 2, and noting that one
membrane was used for experiments 11-13 and a
second one for experiments 14 and 15, it is apparent
that the variations in the initial membrane permeabil-
ity between the five different membranes used in the
five different sets of experiments is greater than the
variations in the initial membrane permeability of a
given membrane reused after cleaning for each repeti-
tion in a given set of experiments.
3.4. Comparison of results for the three different
membranes
The results for the three different membranes under
baseline conditions are shown in Fig. 7. The 0.8 jam
ceramic membrane has the highest original water flux
(1600 kg m -2 h-l), due to its high permeability. How-
229
6000 8000 10000 12000
ever, this membrane exhibited the quickest fouling
after the oil emulsion was introduced into the mem-
brane system. Its total transmembrane flux dropped
below that of the 0.2 ~tm ceramic membrane after only
a few minutes of oil-emulsion filtration. The flux
decline for the 0.2 ~tm ceramic membrane was much
slower. Even though the three membranes have sig-
nificantly different initial fluxes, the final fluxes after
2 h of oil-emulsion filtration are remarkably similar
(30-40 kg m -2 h -1) and much lower than the clean-
membrane fluxes. This indicates that the primary
resistance is provided by the fouling layer formed
on or in the membrane, and not by the membrane
itself. The fact that the permeate concentration does
not generally increase with membrane pore size pro-
vides further support for the filtration being controlled
by the fouling layer rather than the membrane.
3.5. Effects of suspended solids
In order to simulate produced water, containing
suspended solids as well as oil droplets, 250 ppm
diatomaceous earth was added to tap water along with
the 250 ppm heavy crude oil. The resulting suspension
230 J. Mueller et al./Journal of Membrane Science 129 (1997) 221-235

1400

1200

1000
ceramic membrane
800

600
E
~ . . ~ ~ 0 .'1~ llm PAN membrane
400

200 ~ ~ . . ' ~ g m ceramicmembrane

II I II
I I , I i'_l I I
0 I
0 2000 4000 6000 8000 10000 12000
Time(sec)
Fig. 7. Comparisonofbaseline fluxes(10psig ~ansmembranepressure, 250ppm heavy oil, 40°C, and 0.24 m s -1) ~ r thet~eedifferent
membranes.

1000

900

800

70o nd Oil
600

500
g ,

E
300

200

100 ~

0
0 2000 4000 6000 8000 10000 12000

Time (seconds)
Fig. 8. Flux-decline curve for the ceramic membrane at baseline and high crossflow-velocity conditions with suspended solids for the heavy
crude oil-in-water emulsion at 250 ppm oil and 250 ppm diatomaceous earth.
 J. Mueller et aL /Journal of Membrane Science 129 (1997) 221-235
500
\
200'--
F '-------
lOO
o I
0 2000
Fig. 9. Flux-decline curve for the PAN membrane at baseline conditions with suspended solids for the heavy crude oil-in-water emulsion at
250 ppm oil and 250 ppm diatomaceous earth.
was used with the 0.2 ~tm ceramic and 0.1 ~tm poly-
meric membranes. The results for the 0.2 ktm ceramic
membrane at 0.24 and 0.91 m s -1 crossflow velocities
are shown in Fig. 8. Even though the diaphragm valve
was specially designed to resist clogging, some sus-
pended solids accumulated there and in other parts of
the apparatus; this caused a jump in the transmem-
brane pressure and flux upon switching from water
feed to emulsion feed. The transmembrane pressure
then stabilized and relatively little flux decline was
observed. The final flux values are one order of
magnitude higher than the final flux in the absence
of suspended solids.
The results for the 0.1 ktm PAN membrane with
suspended solids are shown in Fig. 9. Again, the
suspended solids reduced the membrane fouling.
The final flux with suspended solids is about seven
times that of the baseline final flux in the absence of
suspended solids.
It is thought that the suspended solids enhance the
flux in two ways. First, they act as a dynamic mem-
brane layer which prevents oil from fouling the mem-
brane internally. Second, they adsorb the rejected oil
droplets and break up the continuous coalesced oil
layer that otherwise may form on the membrane sur-
face.
231
I I I I
4000 6000 8000 10000 12000
TIME (seconds)
4. Modeling and characterization of membrane
fouling
In order to better understand the nature and mechan-
isms of membrane fouling by oily water, several
methods of analysis and characterization were
employed. These include analyzing the flux-decline
data as total resistance versus time, comparing pre-
dictions and measurements of the oil-fouling layer
thickness, and comparing the water-contact angles for
the clean and the fouled membranes.
4.1. Total resistance versus time analysis
A resistance model is used to describe the transport
of solvent through the membrane due to transmem-
brane pressure, as described by Darcy's law:
Ap Ap
J - - vpR~ - - v p ( g m -~-Re) (1)
where J is the permeate mass flux (mass of permeate
per unit time per unit membrane surface area), A P is
the transmembrane pressure, Vp is the permeate kine-
matic viscosity, and g t is the total resistance to flow.
The permeate viscosity may be taken as that of pure
water (6.6x 10 -6 m 2 s -1 at 40°C). The resistance to
232 J. Mueller et al./Journal of Membrane Science 129 (1997) 221-235
flow may be further described as the sum of individual
resistances from the internally fouled membrane, R m ,
and from the external fouling or cake layer, R e . The
experimental data are used to determine whether
internal or external fouling is dominant, as described
previously [19].
In the case of internal fouling, Rm increases with
time. Flux decline due to internal fouling has been
described by two different models, a standard block-
ing model and a pore blocking model. The standard
blocking model assumes that the number of pores
remains constant, but that each pore becomes con-
stricted due to deposition of the foulant on the pore
walls in proportion with the permeate volume. This
results in the following expression for the resistance as
a function of time [19]:
Rm = R0(1 + KSBMQ0 t) 2 (2)
where Ro is the initial membrane resistance, Qo is the
initial volumetric permeate flow rate, KsBM is a con-
stant, and t is time. Plotting resistance versus time
using this equation will yield a curve that is concave
up.
The pore-blocking model assumes that the pore size
remains constant, but that the number of pores per
membrane unit surface area decreases due to blocking
or plugging, with the number of pores that become
plugged increasing in proportion with the permeate
volume. This results in an exponential decline in the
flux, or an exponential increase in the resistance [19]:
Rm = Ro e (KPBMt) (3)
where gpB M is a constant. The resistance versus time
curve is again concave up.
The decline in the flux may also be due to external
fouling. Assuming only external fouling, R m remains
constant at its initial value, Ro. The external resistance,
Re, is the product of a specific cake resistance, ke, and
a cake thickness, 6. In the cake filtration model, k~ is
assumed constant and ~ increases in proportion with
the permeate volume due to the deposition of foulants
on the top surface of the growing cake layer. This
model was developed for dead-end filtration; in cross-
flow filtration, the rejected foulants may also be swept
to the filter exit rather than continuing to accumulate
on the membrane surface. However, a recent theory
predicts that cake build-up for crossflow filtration
is described by dead-end filtration theory for short
times [20], and experimental results shown in the
next section indicate that sweeping of the rejected
oil layer to the filter exit was not significant for the
experiments described here. This results in the follow-
ing expression for the total resistance as a function
of time [19]:
Rt = R0(1 + 4 t K c ~ Q2)0.5 (4)
where K c ~ is a constant proportional to Re. Graphing
resistance versus time, using this equation, will yield a
curve that is concave down. Thus, the resistance
increases with time with a decreasing slope for exter-
nal fouling, and with an increasing slope for internal
fouling This provides a simple means for identifying
the fouling mechanism.
The total resistance versus time curves for the three
membranes at the baseline-experiment conditions are
shown in Fig. 10. The curve for the PAN membrane is
concave down, starting immediately after the first
water flux. This indicates that external fouling dom-
inates throughout the period of filtration of oily water.
For the ceramic membranes, the total resistance curves
are concave up for a short period after the start of oily-
water filtration, before becoming concave down. This
indicates that the ceramic membranes initially foul
internally and later external fouling begins to dom-
inate. It may be that the large pore sizes and perme-
abilities of the ceramic membranes allowed for
penetration of some of the smallest drops into the
membrane pores before they became sufficiently con-
stricted or plugged that external fouling became domi-
nant, whereas the lower pore size and permeability of
the polymeric membrane led to immediate external
fouling. During microfiltration of protein solutions,
Tracey and Davis [ 19] also observed immediate exter-
nal fouling for small pore sizes, and internal followed
by external fouling for large pore sizes.
4.2. Analysis of the fouling layer
Examination of the membranes after selected base-
line experiments showed very thin oil layers adsorbed
to the membrane surfaces. Apparently, a phase inver-
sion occurred at the membrane surface during filtra-
tion, with oil as the continuous phase and water as the
discrete phase which passed through the oil layer in
small drops or globules. The oil layers made the
membrane surfaces hydrophobic. For the 0.2 ~m cera-
 .L Mueller et al./Journal of Membrane Science 129 (1997) 221-235 233

14

12
0.1 gm PAN membrane

,-
04
10
o

¢ 8
tj
c

._¢ 6 2 gm ceramic membrane

4
O
I-
0.8 gm ceramic membrane
2

0 2000 4000 6000 8000 10000 12000

Time (seconds)
Fig. 10. Total resistance versus time curves for the three different membranes at baseline conditions.

mic membrane, the water droplet-membrane surface
contact angle increased from 50 ° to 60 ° after fouling
the membrane under baseline conditions. The contact
angle increased from 50 ° to 70 ° for the PAN mem-
brane.
Soaking the membranes in tetrachloroethylene to
remove the oil, followed by IR analysis, yielded oil
masses of 0.274-0.05 g for the 0.2 gm ceramic mem-
brane and 0.54±0.14 g for the 0.1 gm PAN mem-
brane. If it is assumed that the absorbed oil formed
uniform, consolidated layers, then these amounts cor-
respond to thicknesses of 60±10 and 3 0 ± 1 0 g m ,
respectively. These results may be compared with a
simple model which assumes that all of the permeate
that passes through the membrane deposits its oil on or
within the membrane, and that no oil passes through
the membrane or flows along its surface to the filter
exit. This situation is analogous to dead-end filtration
with complete rejection. Using the measured permeate
volumes collected during the 7200 s of oily-water
filtration, and the known feed concentration of
250 ppm oil, this yields predicted absorbed oil masses
of 0.29 and 0.57 g under baseline conditions for the
0.2 ~tm ceramic membrane and the 0.1 gm PAN mem-
brane, respectively, corresponding to consolidated
thicknesses of 66 and 32 gm. The good agreement
between the measured and predicted values indicate
that the rejected oil remained associated with the
membrane and did not experience any significant flow
to the filter exit under the action of shear forces from
the imposed axial flow. This result is substantiated by
the earlier observation that no flux recovery was
observed during the second pure-water flux, which
followed the 7200 s period of oily-water filtration. The
stagnant nature of the absorbed oil layer is related, at
least in part, to its high viscosity and small thickness.
In addition, any oil deposited internally within the
membrane pores would not be able to flow.
5. Concluding remarks
Each of the ceramic and polymeric microfiltration
membranes always produced a high-quality permeate,
containing <6 ppm total hydrocarbons, starting with a
synthetic-produced water, containing 250-1000 ppm
heavy crude oil. Since centrifugation tests indicated
that ~20 ppm of the oil in the feed was in the form of
234 J. Mueller et aL /Journal of Membrane Science 129 (1997) 221-235
submicron-sized droplets or soluble hydrocarbons, the
results indicate that the fouled membranes are able to
remove a substantial portion of these finely dispersed
or dissolved compounds. Typical final-flux values
measured after 2 h of filtration for 250 p p m oil in
the feed are of the range ~ 3 0 - 4 0 kg m -2 h - t , more
than a factor of 10 lower than the initial flux. Increased
feed concentrations decreased the final flux, but cross-
flow rate, temperature, and transmembrane pressure
had relatively little effect on the final flux. The addi-
tion of suspended solids to the feed significantly
increased the final flux. It is thought that the suspended
solids adsorb the oil, break up the oil layer, and act as a
dynamic membrane which reduces the fouling of the
underlying membrane.
Total resistance versus time curves from the flux-
decline data were used to identify fouling mechan-
isms. The 0.2 and 0 . 8 ~ m ceramic membranes
appeared to exhibit internal followed by external
fouling, while external fouling appeared to dominate
the behavior of the 0.1 ~tm PAN membrane from the
start.
The fouling-layer thicknesses measured experimen-
tally are in good agreement with those predicted by a
mass balance based on the assumption that all of the
oil originally associated with the volume of permeate
collected remained on or in the membrane. The good
agreement indicates that the rejected oil did not flow
along the membrane to the filter exit, presumably
because the heavy crude oil is extremely viscous or
sticky. Furthermore, no increase in flux was observed
after the oily-water feed was replaced with pure-water
feed.
Comparing the behavior of the 0.1 ~tm PAN mem-
brane and the 0.2 ~tm ceramic membrane under base-
line conditions leads to an interesting observation. The
0.2 ~tm ceramic membrane is more permeable and
exhibits a higher flux than does the 0.1 ~tm polymeric
membrane. As a result, twice as much rejected oil per
unit membrane surface area is deposited on it during
the 7200 s of oily-water filtration. However, the final
total resistance is lower for the ceramic membrane
than that for the polymeric membrane. This implies
that the specific resistance of the rejected oil from the
polymer membrane is more than two-fold higher than
that from the ceramic membrane. Apparently, the
morphology of the fouling layer is strongly affected
by the membrane material and morphology.
Acknowledgements
This research was supported by the US Bureau of
Reclamation, the US Environmental Protection
Agency, and the Center for Separations Using Thin
Films at the University of Colorado, Boulder. The
authors wish to thank Jennifer Bieker (supported by
the Colorado Commission on Higher Education) and
Nikki Sikes (supported by the National Science Foun-
dation's Research Experiences for Undergraduates
Program) for their help with the experiments, and
Jim Howard for determining the hydrocarbon content
after centrifugation. Appreciation is also extended to
Cliff Juengst of Unocal for providing oil samples and
Steve Kelley of N R E L for viscosity determination.
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