This article was downloaded by: [Erciyes University]

On: 31 December 2014, At: 00:57

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

Chemical Engineering Communications

Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gcec20

MODELING OF MEMBRANE FOULING AND

FLUX DECLINE IN MICROFILTRATION
OF OILY WASTEWATER USING CERAMIC
MEMBRANES
a b a
Mohsen Abbasi , Mohammad Reza Sebzari , Abdolhamid Salahi &
a
Behrooz Mirza
a
Department of Applied Chemistry, Faculty of Science, East Tehran
Branch , Islamic Azad University , Tehran, Iran
b
Research Centre for Membrane Separation Processes, Faculty of
Chemical Engineering , Iran University of Science and Technology ,
Narmak, Tehran, Iran
Published online: 29 Sep 2011.

To cite this article: Mohsen Abbasi , Mohammad Reza Sebzari , Abdolhamid Salahi & Behrooz
Mirza (2012) MODELING OF MEMBRANE FOULING AND FLUX DECLINE IN MICROFILTRATION OF OILY
WASTEWATER USING CERAMIC MEMBRANES, Chemical Engineering Communications, 199:1, 78-93, DOI:
10.1080/00986445.2011.570391

To link to this article: http://dx.doi.org/10.1080/00986445.2011.570391

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.

This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &
 Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions
Downloaded by [Erciyes University] at 00:57 31 December 2014
 Chem. Eng. Comm., 199:78–93, 2012
Copyright # Taylor & Francis Group, LLC
ISSN: 0098-6445 print=1563-5201 online
DOI: 10.1080/00986445.2011.570391

Modeling of Membrane Fouling and Flux

Decline in Microfiltration of Oily Wastewater
Using Ceramic Membranes

MOHSEN ABBASI,1 MOHAMMAD REZA SEBZARI,2

ABDOLHAMID SALAHI,1 AND BEHROOZ MIRZA1
1
Department of Applied Chemistry, Faculty of Science,
East Tehran Branch, Islamic Azad University, Tehran, Iran
Downloaded by [Erciyes University] at 00:57 31 December 2014

2
Research Centre for Membrane Separation Processes,
Faculty of Chemical Engineering, Iran University of Science and
Technology, Narmak, Tehran, Iran

One of the major problems in pressure-driven membrane processes is reduction of

flux far below the theoretical capacity of the membrane. The results of an experi-
mental study of fouling mechanisms of ceramic membranes in separation of oil from
synthesized oily wastewaters are presented. Mullite microfiltration (MF) mem-
branes were synthesized from kaolin clay as MF ceramic membranes. The rejection
of total organic carbon (TOC) for the synthetic feeds was found to be more than
94% by these membranes. Hermia’s models were used to investigate the fouling
mechanisms of membranes. The effect of pressure, cross flow velocity (CFV), tem-
perature, oil concentration, and salt concentration on flux decline were investigated.
The results showed that the cake filtration model can well predict the flux decline of
mullite ceramic membranes; average error of this model is less than 7%. The results
show that by increasing pressure from 0.5 to 4 bar, porosity of the cake layer on the
mullite membranes decreases from 25.68% to 14.98%. After the cake filtration
model, the intermediate pore blocking model was found to well predict the experi-
mental data with an average error less than 10.5%.

Keywords Ceramic membranes; Membrane fouling; Microfiltration; Pore block-

ing models

Introduction
A large volume of wastewater in the form of either oil-in-water (o=w) or water-in-oil
(w=o) emulsions is generated in different industries such as metallurgical, transpor-
tation, food processing, and petrochemical as well as petroleum refineries. Typical
composition ranges of ‘‘produced water’’ generated in the oily wastewater oil and
gas industrial processes include 50–1000 mg=L of total oil and grease and
50–350 mg=L of total suspended solids (TSS) (Kim, 1997). Environmental regula-
tions require maximum total oil and grease concentration in discharge waters of

Address correspondence to Mohsen Abbasi, Department of Applied Chemistry, Faculty

of Science, Islamic Azad University, East Tehran Branch, Tehran, Iran. E-mail: abbasi@
chemeng.iust.ac.ir

78
 Fouling in Microfiltration of Oily Wastewater 79

10–15 mg=L (Mueller et al., 1997). The major pollutant in wastewater (also known as
produced water) generated from oil fields is oil, which may range between 100 and
1000 mg=L or more depending on demulsification efficiency and crude oil nature
(Salahi et al., 2010; Abbasi et al., 2010a). Removing oil from oily wastewater is an
important aspect of pollution control. Many studies have been done on oily waste-
water treatment with different membranes (Daiminger et al., 1995; Chakrabarty
et al., 2008; Srijaroonrat et al., 1999; Kong et al., 1999; Salahi and Mohammadi,
2010; Abbasi et al., 2010b).
One of the major inhibiting factors for successful commercialization of the
membrane processes is fouling. During membrane filtration, some constituents of
the feed deposit on the membrane surface and=or in the membrane matrix. This
retention process is often referred to as fouling and results in flux decline, eventually
leading to membrane replacement. In order to enhance the economy and efficiency
of microfiltration (MF) membranes, understanding the membrane fouling mechan-
Downloaded by [Erciyes University] at 00:57 31 December 2014

isms is necessary for further development. When particle size of droplets is smaller
than or comparable to size of the membrane pores, the membrane blocking model
is commonly a useful tool to explain how and when the particles penetrate into or
block the pores (Hwang et al., 2008).
Membrane fouling in cross-flow MF is a key factor affecting the economic and
technological viability of MF processes, which essentially depends on the permeate
fluxes obtained and their stability with time. A typical variation of permeate flux
with time is an initial rapid decrease followed by a long and gradual decline. Conse-
quently, modeling of permeate flux decline (i.e., fouling) in MF of macromolecules is
important from the economic and technological point of view.
There are many studies focused on empirical models for the description of
permeate flux decline with time. Although empirical models are very precise, they
cannot adequately explain the fouling mechanisms involved in membrane filtra-
tion. Theoretical models can partially contribute to the understanding of fouling
phenomena. However, the completely theoretical models found in the literature fail
to accurately predict permeate flux decline with time without using experimental
data to estimate at least one of their model parameters. Therefore, semi-empirical
models whose parameters have a physical meaning represent a suitable solution
to achieve the accurate prediction of permeate flux decline in ultrafiltration (UF)
and explain the fouling mechanisms at the same time (Vela and Blanco, 2008;
Furukawa et al., 2008).
Ceramic membranes have been known for years; they are used in many differ-
ent applications due to their numerous advantages: high temperature and pressure
stability, good chemical stability, high mechanical stability, long life, and good
antifouling properties (Wong et al., 2001; Kumar and Roy, 2008). Among these
membranes, mullite ceramic membranes have very high chemical and thermal stab-
ility and are very cheap because they can be prepared by extruding and calcining
kaolin clay.
In the past two decades, there have been a large number of studies focused on
the effects of operating parameters on flux decline and membrane fouling mechan-
isms. In these studies, membrane filtration testes under different experimental
conditions were preformed to obtain data on permeation flux decline with time.
Although some advances in fundamental MF membrane fouling mechanisms have
been achieved, further research is needed to better understand the fouling mechan-
isms. One important reason that membrane fouling cannot be eliminated is that
 80 M. Abbasi et al.

many feed streams in membrane separation processes contain particles of sizes ran-
ging from nanometers to hundreds of micrometers (Wang and Waite, 2008).
From the analyses of blocking chart and resistance coefficients of fouling, the
filtration flux could then be predicted by using the blocking models (Hwang et al.,
2008).
In this work, Hermia’s models (Hermia, 1982) were used to investigate the
fouling mechanisms involved in cross-flow MF of synthesized oily wastewaters.
The fitted results of Hermia’s models for cross-flow MF are presented and compared
with the experimental data. Also, more detailed study of Hermia’s models was
provided for cross-flow MF to explain the fouling mechanisms in treatment of oily
wastewater.

Materials and Methods

Downloaded by [Erciyes University] at 00:57 31 December 2014

Membrane Preparation
In this research, mullite MF membranes were synthesized from kaolin clay. The kao-
lin material used obtained from the Zenooz mine in Marand, Iran. The chemical
analysis of kaolin is listed in Table I. Cylindrical-shaped (tubular) membranes (inner
diameter 10 mm, outer diameter 14 mm, and length 30 cm) were conveniently made
by extruding a mixture of about 62–69% kaolin clay and 31–38% distilled water
using an extruder. The cylindrical-shaped membranes were then dried at room tem-
perature for 48 h and temperature-programmed calcinated at 1250
C for 3 h, a suit-
able calcination temperature and period at which the clay converts to mullite and
free silica (Kazemimoghadam et al., 2002). Free silica was removed from the calcined
membranes by leaching with a strong alkali solution. Removal of this free silica
causes microporous created tubular ceramic membranes with good porosity. Free sil-
ica removal was carried out with aqueous solutions containing 20 wt.%. NaOH at a
temperature of 80
C for 5 h. The membranes were washed with distilled water for
12 h at a temperature of 80
C in order to remove NaOH. Porosity of the membranes
before leaching by the water absorption method was 32%, while after treatment it
increased to 41%. Permeation flux values of the membranes before and after free sil-
ica removal at a certain pressure (1 bar), temperature (25
C), and flow rate (1 m=s)
for distilled water were 18 and 35 L=m2 h, respectively. Characterization of mullite
membranes with mercury porosimetry shows that total cumulative volume was
0.803 cc=g and average pore radius of membranes was 0.476 mm.

Table I. Analysis of kaolin clay

Component Percentage Phases Percent

SiO2 61.62 Kaolinite 64
TiO2 0.4
Al2O3 24–25 Illite 2.4
Fe2O3 0.45–0.65
K 2O 0.4 Quartz 27
Na2O 0.5
LOI 9.5–10 Feldspar 6.6
Total 100 100
 Fouling in Microfiltration of Oily Wastewater 81

Figure 1. SEM micrographs of the mullite membrane: (A), surface, and (B), cross section.
Downloaded by [Erciyes University] at 00:57 31 December 2014

Figure 1 shows the surface and cross section of the synthetic mullite ceramic
membrane.

Setup
In order to carry out the experiments at almost close to an industrial scale, a pilot
plant was designed. The pilot was operated in cross-flow mode. The membrane sur-
face area in contact with the feed was equal to 110 cm2. The MF cell was installed in
the plant according to Figure 2 and all the industrial reservations were considered
during the experiments.
The plant was simple and had no complexity, however, it was designed in such
a way that all important operating parameters in the MF process such as tempera-
ture, operating pressure, and linear flow velocity could be tuned and controlled.
The system had a vessel with a capacity of 10 L. This vessel had a heater to heat
the feed or to keep it at a constant temperature and also a stirrer in order to keep
the feed uniform. The feed temperature was controlled by a digital thermometer
with an accuracy of  0.1 C. A tubular heat exchanger was used to control the feed
temperature.

Figure 2. Microfiltration setup.

 82 M. Abbasi et al.

Figure 3. Particle size distribution of oil droplets in oil-in-water emulsion with 1000 ppm oil.
Downloaded by [Erciyes University] at 00:57 31 December 2014

Process Feed
Synthetic oily wastewaters (oil-in-water emulsions) were prepared by mixing conden-
sate gas (C8-C12) and distilled water with addition of approximately 0.01 wt.%
Triton X-100 emulsifier to the mixture for stabilization. Condensate gas from Seraje,
Ghom, Iran, was used for preparation of the oil-in-water emulsions. A blender was
used to mix the mixture of oil, water, and Triton X-100 emulsifier at high shear rates
(6000 rpm) for 30 min to competent emulsification. Under these conditions, the
emulsions were stable for employing in the MF experiments because after 12 h,
no phase separation was observed in the emulsion. Droplet size distribution of the
emulsion (1000 ppm) is shown in Figure 3.

Modeling
In the present work, an approach followed by Hermia was used for description of
filtration phenomenon in cross-flow MF of oily wastewater. Hermia’s models are
the most useful and applicable models for MF flux decline prediction. The general
equation is (Vela and Blanco, 2008; Salahi et al., 2010a):

dj
¼ KðJ  Jo ÞJ2n ð1Þ
dt

where n ¼ 2.0 for ‘‘complete’’ blocking, n ¼ 1.5 for standard blocking, n ¼ 1.0 for
incomplete pore blocking (intermediate fouling), and n ¼ 0 for cake filtration (see
Figure 4). K is a constant and J0 is the limiting flux.

Cake Formation Model

Cake=gel formation usually occurs when particles=oil droplets larger than the
average pore size accumulate on the membrane surface, forming a ‘‘cake=gel.’’ As
time goes on, the cake=gel grows and provides an additional porous barrier through
which the liquid must permeate. As a result, the cake=gel may increase the particle=
oil droplet removal efficiency of the membrane; however, it also increases the
 Fouling in Microfiltration of Oily Wastewater 83
Downloaded by [Erciyes University] at 00:57 31 December 2014

Figure 4. Schematic representation of blocking mechanism: (a) complete pore blocking, (b)
intermediate blocking, (c) standard blocking, and (d) cake layer formation (Vela and Blanco,
2008).

membrane resistance and subsequently diminishes flux. For the cake filtration
model, it is assumed that:
a. Shear stress is proportional to shear rate (Newtonian).
b. All the particles=oil droplets are dimensionally similar; solute deposits on the
membrane surface by superimposition forming a compressible cake=gel layer of
uniform thickness.
c. The resistance offered by the cake=gel layer is directly proportional to the volume
filtered.
d. All the particles=oil droplets are retained on the membrane surface and the flux
decline phenomenon is solely dependent upon the cake=gel formation (i.e., no
sealing of pores).
As a result, the model can be described as follows:

1 1
2
¼ 2 þ Kg t ð2Þ
J Jo

where J0 and Kg are the initial permeate flux and the constant of the cake=gel
formation model, respectively (Vela and Blanco, 2008; Kosvintsev et al., 2002).
It is known that the most cakes=gels are compressible. The relation between
pressure and the specific resistance of the cake=gel layer can be represented as
follows (Srijaroonrat et al., 1999):

a ¼ a
DPn ð3Þ

where n and a
are the compressibility coefficient and a constant, respectively,

which can be derived from slope and intercept of line (ln a; ln(DP)), respectively.
The specific cake=gel resistance a is often used to characterize the hydrodynamic
resistance of cake=gel during the cross-flow filtration of particulate suspensions=
 84 M. Abbasi et al.

emulsions. The specific cake=gel resistance can be calculated using the following
equation:

t=V ¼ ðRm l=ADPÞ þ ðlCa=2A2 DPÞV ð4Þ

where l is the permeate viscosity and C is concentration of oil and grease in the
feed. Hence, a plot of t=V versus V should yield a straight line with a slope as
l Ca=2A2DP and an intercept as Rm l=A DP. The specific cake=gel resistance (a)
and the membrane resistance (Rm) can thus be calculated.
Cake=gel layers are normally porous. The layer is not completely solidified and
there are some spaces between the particles=droplets. Cake=gel porosity shows the
extent of porosity in the layer and can be calculated from the Carman-Kozeny
relationship:

a ¼ 180ð1  eÞ=ðq dp2 e3 Þ ð5Þ

Downloaded by [Erciyes University] at 00:57 31 December 2014

where e is the layer porosity, dp is the diameter of particles=droplets forming a layer,

and q is the permeate density (can be assumed to be the same as water density).

Standard Pore Blocking Model

The standard pore block is the most dominant phenomenon when retained particles=
droplets are dimensionally smaller than the average pore size of the membrane. It is
often called adsorptive fouling or pore narrowing. In this case, particles=droplets in
the fluid approach the membrane, enter into the pores, and adhere to the inner pore
walls. Unlike the complete pore blocking model, there is no complete blocking of
pores. In this case, the adhesion of particles=droplets to the walls decreases the avail-
able pore diameter and increases the membrane resistance. Over a period of time, the
pore diameter decreases, leading to complete pore blocking. For developing the model,
it is assumed that the fluid is Newtonian and only pore narrowing takes place and not
complete pore blocking. Permeate flux can be obtained by the following equation:
1 1
¼ þ Ks t ð6Þ
J 1=2 Jo1=2

where Ks is the constant in the standard pore blocking model (Vela and Blanco, 2008;
Kosvintsev et al., 2002; Bourgeous et al., 2001).

Complete Pore Blocking Model

Complete pore blocking typically occurs when particles=droplets are dimensionally
similar to the mean pore size of the membrane. In this model, particles=droplets plug
individual pores. As individual pores are plugged, the flow is diverted to other pores,
which plug successively. Eventually, this reduces the available membrane area and
increases the membrane resistance. Due to this fact, the membrane loses its filtration
performance and requires cleaning or replacement. The assumptions made for devel-
oping this model are:
a. Every particle=droplet participates in the plugging process by sealing one pore,
and once a pore is blocked, other particles=oil droplets do not enter that pore
and superimpose on that particle=droplet (i.e., no gradual pore blocking)
 Fouling in Microfiltration of Oily Wastewater 85

b. There is no cake=gel formation.

c. Feed is Newtonian.
Permeate flux can be simply represented by the following equation:

LnðJÞ ¼ LnðJ
Þ  KC t ð7Þ

where KC is the constant in the complete pore blocking model (Vela and Blanco,
2008; Kosvintsev et al., 2002).

Intermediate Pore Blocking Model

This model assumes each particle=oil droplet can block some membrane pores or
Downloaded by [Erciyes University] at 00:57 31 December 2014

settle on other particles=oil droplets previously blocking some other pores with
superposition of particles=oil droplets. Permeate flux can be obtained by the
following equation:

1 1
¼ þ Ki At ð8Þ
J Jo

where Ki is the constant in intermediate pore blocking model and A is membrane

surface (Vela and Blanco, 2008; Kosvintsev et al., 2002).

Results and Discussions

Effluent Characteristics
Effectiveness of the mullite ceramic membranes for treatment of synthetic oily waste-
water was assessed by quality of the permeate. Table II represents characteristics of
the outlet wastewater before and after MF. From the results presented in Table II, it
can be observed that the treatment efficiency is relatively high. This showed that the
membrane is able to effectively treat the synthesized oily wastewaters. Analysis of the
MF process showed that the permeate has high quality; total suspended solids (TSS)
are completely retained, turbidity reduction is greater than 97%, and there is also
high retention (94%) of total organic carbon (TOC). In addition to these results,
chemical oxygen demand (COD) level of the effluent was reduced up to approxi-
mately 88% after MF.

Table II. Characteristics of the wastewater and the treated wastewater

Permeate Unit Feed Parameter

Total suspended solids (TSS) mg=L 60 Trace
Total dissolve solids (TDS) g=L 25 23
Chemical oxygen demand (COD) mg=L 510 54
Total organic carbon (TOC) mg=L 1000 63
Turbidity NTU 89 2.3
 86 M. Abbasi et al.

Characterization of the Cake/Gel Specific Resistance

In cross-flow MF of oil-in-water emulsion, increase in the cake=gel specific resistance
with increasing pressure was found to be completely reversible. The cake=gel specific
resistance data for the oily wastewater are linear when plotted on a log-log graph.
The best fitted values of a
and n were determined by simple linear regression of
the data yielding n ¼ 0.79 and a
¼ 1.71  1015 m=kg for the mullite membranes.
The compressibility coefficient for the oily wastewater was quite high. This could
be attributed to the presence of a high quantity of particles=oil droplets in the oily
wastewater resulting in formation of a nearly incompressible cake=gel layer. Vari-
ation of the cake=gel layer porosity with pressure is presented in Figure 5. The results
showed that by increasing pressure from 0.5 to 4 bar, the porosity of cake=gel layer
over the mullite membranes decreases from 25.68% to 14.98%.
Downloaded by [Erciyes University] at 00:57 31 December 2014

Prediction of Permeation Flux by Pore Blocking Models

First, the relationship between time (t) and permeate flux (J) was decided for all the
pressure levels. In all cases, it was found that the permeate volume decreased with
time. In order to ensure precise analysis of the filtration mechanism and also to avoid
unsteady-state conditions, the collected permeate during the first 30 s of the filtration
process was neglected. The models defined by Hermia for the description of various
filtration mechanisms were applied to the obtained permeate flux data.
Linear relationships of 1=J2 versus t, 1=J0.5 versus t, Ln(J) versus t, and 1=J ver-
sus t were determined experimentally for the cake filtration, standard pore blocking,
complete pore blocking, and intermediate pore blocking models to calculate the con-
stant values (K) of the models. As represented in Figure 6(a)–(d) the filtration data at
different pressure levels were compared by prediction flux of the cake filtration,
standard pore blocking, complete pore blocking, and intermediated pore blocking
models. Membrane fouling increased with increasing pressure significantly. This
can be due to formation of a thicker cake=gel layer; this layer traps oil droplets
among sediment pores and does not let water pass through the membrane.

Figure 5. Variation of cake layer porosity percent with pressure (CFV 1 m=s, oil concentration
1000 ppm, temperature 25
C, and salt concentration 0 g=L).
 Fouling in Microfiltration of Oily Wastewater 87
Downloaded by [Erciyes University] at 00:57 31 December 2014

Figure 6. Variation of actual and predicted permeate flux at different pressures with time
(CFV 1 m=s, oil concentration 1000 ppm, temperature 25
C, and salt concentration 0 g=L):
(a) cake layer formation model, (b) intermediate pore blocking model, (c) standard pore block-
ing model, and (d) complete pore blocking model.

Deviations of all models were compared with each other to determine which
best predicted the data; the cake filtration model had the best prediction. The
results showed that average errors of predicated flux for the cake layer formation
model, the intermediate pore blocking model, the standard pore blocking model,
and the complete pore blocking model are 7.64%, 11.83%, 14.75%, and 16.70%,
respectively. The highest deviation between the experimental data and the predicted
flux decline was observed for the complete pore blocking model. The results indi-
cate that at early filtration (0.5–3 min), the cake layer formation model also shows
the best prediction.
Figure 7(a)–(d) shows fitting of experimental permeate flux of the mullite mem-
branes to the Hermia models for all the experimental conditions tested. The results
present effect of cross-flow velocity (CFV) on the flux decline. Increasing flow rate
reduces membrane fouling. This is due to removing the oil layer from the membrane
surface.
Figure 7(a) confirms very good fitting of the cake layer formation model to the
experimental data at dead-end MF (CFV ¼ 0). In this condition, average error of the
cake layer formation model is 2.62%. As observed, with increasing CFV and per-
meate flux, average error of all the models increases. The results indicated that at
early filtration (0.5–3 min), the intermediate pore blocking model shows better pre-
diction than the other models. As mentioned, the intermediate pore blocking model
well presents the fouling mechanism when the membrane pore size is similar to the
size of particle droplets (Vela and Blanco, 2008).
 88 M. Abbasi et al.
Downloaded by [Erciyes University] at 00:57 31 December 2014

Figure 7. Variation of actual and predicted permeate flux at different CFV with time (pressure
3 bar, oil concentration 1000 ppm, temperature 25
C, and salt concentration 0 g=L): (a) cake
layer formation model, (b) intermediate pore blocking model, (c) standard pore blocking
model, and (d) complete pore blocking model.

The membrane pores are blocked near their entrance in the feed side. Therefore,
the intermediate pore blocking model provides better agreement to the experimental
data than the complete pore blocking model and the standard pore blocking model,
as expected. After 120 min filtration at different CFVs, average error of predicated
flux for the cake layer formation, the intermediate, the standard, and the complete
pore blocking models are 9.32%, 17.49%, 22.42%, and 28.33%, respectively.
Figure 8(a)–(d) represents the effect of feed temperature on fouling mechanisms.
By increasing operating temperature, fouling resistance of mullite membranes
decreases because increasing temperature decreases the feed viscosity and reduces
internal attractive force between the cake layer and the membrane surface.
The results showed that the cake filtration and the intermediate pore blocking
models have better prediction than the standard and the complete pore blocking
models. The results illustrated that fitting of the standard blocking model to the
experimental data is not good enough for the mullite ceramic membrane. It must
be noted that the highest deviation between the experimental data and the predicted
flux decline were observed for the complete pore blocking model at the same experi-
mental conditions. Average error of the predicated flux for the cake layer forma-
tion, intermediate, standard, and complete pore blocking models are 5.9%,
6.55%, 7.5%, and 8.45%, respectively. As observed with increasing temperature,
due to higher flux, average error of the models decreases. For all the models con-
sidered in this research, the precision of the fitted results is high when permeate flux
slightly varies with time.
 Fouling in Microfiltration of Oily Wastewater 89
Downloaded by [Erciyes University] at 00:57 31 December 2014

Figure 8. Variation of actual and predicted permeate flux at different temperatures with time
(pressure 3 bar, CFV 1 m=s, oil concentration 1000 ppm, and salt concentration 0 g=L): (a)
cake layer formation model, (b) intermediate pore blocking model, (c) standard pore blocking
model, and (d) complete pore blocking model.

Figure 9(a)–(d) illustrates the fitting of the models to the experimental data for
the mullite ceramic membranes at different oil concentrations. Fouling resistance is
more severe at higher oil concentrations. This is because of higher growth rates and
thicker layers at higher concentrations.
As observed, the lowest deviation between the experimental data and the pre-
dicted flux decline is for the cake filtration model. The cake filtration model occurs
when particle=oil droplet sizes are much greater than the membrane pore size.
Consequently, they are unable to enter the membrane pores (Madaeni, 2001).
The results showed that average error of the predicated flux for the cake layer
formation model, the intermediate pore blocking model, the standard pore blocking
model, and the complete pore blocking model are 6.99%, 9.05%, 10.03%, and 11.84%
respectively. Figure 9 shows that the fitting of the cake layer model to the experi-
mental data at low concentrations is not very good, particularly for the experimental
conditions that correspond to high variation of permeate flux with time. It must be
noted that at early filtration (0.5–3 min), the flux predicted by the cake layer model
has the lowest deviation from the experimental data.
Figure 10(a)–(d) represents effect of feed salinity on fouling of the mullite cer-
amic membranes. It must be noted that there is still much debate on the effect of salt
(NaCl) concentration on permeation flux. It can be said that at low salt concen-
tration (25 g=L), high ionic concentration tends to diminish thickness of the double
layer around the emulsion droplets, thereby reducing the electrostatic barrier to
coalescence, causing high permeation flux and low fouling resistance. At high salt
concentration (50–200 g=L), viscosity of the emulsion increases and the salt crystals
 90 M. Abbasi et al.
Downloaded by [Erciyes University] at 00:57 31 December 2014

Figure 9. Variation of actual and predicted permeate flux at different oil concentrations with
time (pressure 3 bar, CFV 1 m=s, temperature 35
C, and salt concentration 0 g=L): (a) cake
layer formation model, (b) intermediate pore blocking model, (c) standard pore blocking
model, and (d) complete pore blocking model.

Figure 10. Variation of actual and predicted permeate flux at different salt concentrations
with time (pressure 3 bar, CFV 1 m=s, temperature 35
C, and oil concentration 1000 ppm):
(a) cake layer formation model, (b) intermediate pore blocking model, (c) standard pore block-
ing model, and (d) complete pore blocking model.
 Fouling in Microfiltration of Oily Wastewater 91

Table III. Average error of models for prediction of permeation flux

Cake Intermediate Standard Complete

filtration pore blocking pore blocking pore blocking
Item model model model model
Pressure 7.64% 11.83% 14.75% 16.70%
Cross-flow 9.32% 17.49% 22.42% 28.33%
velocity (CFV)
Temperature 5.9% 6.55% 7.50% 8.45%
Oil concentration 6.99% 9.05% 10.03% 11.84%
Salt concentration 6.56% 7.81% 8.57% 9.89%
Downloaded by [Erciyes University] at 00:57 31 December 2014

foul the membrane pores because of the salt concentration polarization on the mem-
brane surface; thus permeation flux decreases and fouling resistance increases.
The results showed that the cake filtration and intermediate pore blocking mod-
els better predict the experimental data than the standard blocking and complete
pore blocking models. Average error of the predicated flux for the cake layer forma-
tion model, the intermediate blocking model, the standard blocking model, and the
complete pore blocking model are 6.56%, 7.81%, 8.57%, and 9.89%, respectively. At
early filtration (0.5–3 min) the cake layer formation can well predict permeation flux
of mullite ceramic membranes.
These experimental results indicate that different filtration mechanisms could be
applied simultaneously for description of filtration data. It was found that cross-flow
MF of oily wastewater treatment using mullite ceramic membranes could be well
predicted using Hermia’s models. A summary of results is shown in Table III.

Conclusions
One of the treatment techniques used for oil separation from oil-in-water emulsions
is membrane filtration. In this work, mullite ceramic MF membranes were synthe-
sized for treatment of oily wastewaters and mechanisms of flux decline of the mam-
brane were investigated. The rejection of total organic carbon (TOC) was found to
be more than 94%. The results showed that by increasing pressure from 0.5 to 4 bar,
porosity of the cake=gel layer on the mullite ceramic membranes decreases from
25.68% to 14.98%. For analyzing the fouling mechanisms, Hermia’s models were
used. Experimental results of permeate flux versus time were compared to Hermia’s
fouling models. It was found that the best fit to the experimental data corresponds to
the cake layer formation model for all the experimental conditions tested. After the
cake formation model, the best predicted flux is for the intermediate pore blocking
model and the worst predicted flux is for the complete pore blocking model. For all
the models considered in this study, the precision of the fitted results is high when the
permeate flux varies slightly with time.

Nomenclature
A membrane area, m2
C concentration, mg=L
 92 M. Abbasi et al.

CFV cross-flow velocity, m=s

dp diameter of oil drops, m
J filtration flux, L=m2 h
J0 initial filtration flux, L=m2 h
Kc complete pore blocking model constant, 1=s
Kg cake filtration model constant, s=m6
Ki intermediate pore blocking model constant, 1=m3
Ks standard pore blocking model constant, 1=s3
n blocking index and compressibility coefficient
Dp pressure, bar
Rm membrane resistance, 1=m
t filtration time, s
T temperature,
C
Downloaded by [Erciyes University] at 00:57 31 December 2014

TDS total dissolved solids, mg=L

TOC total organic carbon, mg=L
TSS total suspended solids, mg=L
V filtrate volume, L
q density, kg=m3
m dynamic viscosity, Pa  s
a specific resistance of the cake, m=kg
a
constant of specific resistance of the cake, m=kg
e cake layer porosity

References
Abbasi, M., Mirfendereski, M., Nikbakht, M., Golshenas, M., and Mohammadi, T. (2010a).
Performance study of mullite and mullite–alumina ceramic MF membranes for oily
wastewaters treatment, Desalination, 259, 169–178.
Abbasi, M., Mirfendereski, M., Salahi, A., Mohammadi, T., and Pak, A. (2010b). Dimen-
sional analysis of permeation flux for microfiltration of oily wastewaters using mullite
ceramic membranes, Desalination, 252, 113–119.
Bourgeous, K. N., Darby, J. L., and Tchobanoglous, G. (2001). Ultrafiltration of waste-
water: Effects of particles, mode of operation, and backwash effectiveness, Water
Res., 35, 77–90.
Chakrabarty, B., Ghoshal, A. K., and Purkait, M. K. (2008). Ultrafiltration of stable oil-in-
water emulsion by polysulfone membrane, J. Membr. Sci., 325, 427–437.
Daiminger, U., Nitsch, W., Plucinski, P., and Hoffmann, S. (1995). Novel techniques for oil=
water separation, J. Membr. Sci., 99, 197–203.
Furukawa, T., Kokubo, K., Nakamura, K., and Matsumoto, K. (2008). Modeling of the per-
meate flux decline during MF and UF cross-flow filtration of soy sauce lees, J. Membr.
Sci., 322, 491–502.
Hermia, J. (1982). Constant pressure blocking filtration laws—Application to power law
non-Newtonian fluids, Trans. Inst. Chem. Eng., 60, 183–187.
Hua, F. L., Tsang, Y. F., and Wang, Y. J. (2007). Performance study of ceramic micro-
filtration membrane for oily wastewater treatment, Chem. Eng. J., 128, 169–175.
Hwang, K. G., Liao, C. Y., and Tung, K. L. (2008). Effect of membrane pore size on the
particle fouling in membrane filtration, Desalination, 234, 16–23.
Kazemimoghadam, M., Pak, A., and Mohammadi, T. (2002). Dehydration of water=1-1
dimethylhydrazine mixtures by zeolite membranes, Microporous Mesoporous Mater.,
56, 81–88.
Kim, J. J. (1997). Membrane microfiltration of oily water, Macromol. Symp., 118, 413–418.
 Fouling in Microfiltration of Oily Wastewater 93

Kong, J., and Li, K. (1999). Oil removal from oil-in-water emulsions using PVDF membranes,
Sep. Purif. Technol., 16, 83–93.
Kosvintsev, S., Holdich, R. G., Cumming, I. W., and Starov, V. M. (2002). Modelling of
dead-end microfiltration with pore blocking and cake formation, J. Membr. Sci., 208,
181–192.
Kumar, S. M., and Roy, S. (2008). Recovery of water from sewage effluents using alumina
ceramic microfiltration membranes, Sep. Sci. Technol., 43, 1034–1064.
Madaeni, S. S. (2001). The effect of large particles on microfiltration of small particles,
J. Porous Mater., 18, 143–148.
Mueller, J., Cen, Y., and Davis, R. H. (1997). Crossflow microfiltration of oily water,
J. Membr. Sci., 129, 221–235.
Salahi, A., and Mohammadi, T. (2010). Experimental investigation of oily wastewater treat-
ment using combined membrane systems, Water Sci. Technol., 62(2), 245–255.
Salahi, A., Mohammadi, T., Rahmat Pour, A., and Rekabdar, F. (2009). Oily wastewater
treatment using ultrafiltration, Desalination Water Treat., 6, 1–10.
Downloaded by [Erciyes University] at 00:57 31 December 2014

Salahi, A., Abbasi, M., and Mohammadi, T. (2010). Permeate flux decline during UF of oily
wastewater: Experimental and modeling, Desalination, 251, 153–160.
Srijaroonrat, P., Julien, E., and Aurelle, Y. (1999). Unstable secondary oil=water emulsion
treatment using ultrafiltration: Fouling control by backflushing, J. Membr. Sci., 159,
11–20.
Vela, M. C. V., and Blanco, S. (2008). Analysis of membrane pore blocking models applied to
the ultrafiltration of PEG, Sep. Purif. Technol., 62, 489–498.
Wang, X. M., and Waite, T. D. (2008). Impact of gel layer formation on colloid retention in
membrane filtration processes, J. Membr. Sci., 325, 486–494.
Wong, W. C., Au, L. T. Y., Ariso, C. T., and Yeung, K. L. (2001). Effects of synthesis para-
meters on the zeolite membrane growth, J. Membr. Sci., 191, 143–163.