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Biological treatment of oily wastewater from gas stations by membrane

bioreactor

Article in Journal of Environmental Engineering and Science · February 2011

DOI: 10.1139/s05-032

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 309

Biological treatment of oily wastewater from gas

stations by membrane bioreactor
P.T. Tri, C. Visvanathan, and V. Jegatheesan

Abstract: In many Asian countries, rapid industrialization and urbanization has led to an increased number of cars,
making wastewater from gas stations an important issue of concern in urban environment. This wastewater is characterized
by high concentration of oil–water emulsion, which cannot be effectively removed by a conventional gravity separator. An
experimental investigation on the treatability of oily wastewater from gas stations using a membrane bioreactor (MBR)
system revealed that MBR system could achieve good removal efficiency with stability against shock loading. Optimum
operating conditions were found to be at a hydraulic retention time of 4 h and an oil-loading rate of 1.8 kg oil m−3 ·d−1 .
It was anticipated that adding powdered activated carbon (PAC) in the MBR could help to adsorb the oils. However,
operating the MBR with only microbial flocs has an advantage over adding PAC particles into the MBR, since the former
condition could provide a prolonged cycle of filtration with a relatively lesser increase in transmembrane pressure.
Key words: activated sludge process, membrane bioreactor, membrane fouling, oily wastewater, powdered activated carbon,
transmembrane pressure.

Résumé : Dans plusieurs pays d’Asie, l’industrialisation et l’urbanisation rapides ont mené à une augmentation du nombre
de véhicules, rendant l’eau usée provenant des stations services une source d’inquiétude dans l’environnement urbain.
Cette eau usée est caractérisée par une forte concentration d’émulsion eau/huile, qui ne peut être efficacement retirée
en utilisant un séparateur par gravité conventionnel. Une étude sur la traitabilité des eaux usées huileuses provenant des
stations services en utilisant un système de bioréacteur à membrane (MBR) a montré que le système MBR obtiendrait une
bonne efficacité d’élimination en plus d’une stabilité contre une surcharge subite. Les conditions d’opération optimales
sont un temps de rétention hydraulique de quatre heures et un taux de chargement de l’huile de 1,8 kg huile m−3 ·j−1 . Il a
été prévu que l’ajout de charbon actif en poudre dans le MBR pourrait aider à absorber les huiles. Toutefois, l’opération
du MBR en utilisant uniquement des flocs microbiens est avantageuse par rapport à l’ajout de particules de charbon actif
en poudre puisque cette première opération pourrait prolonger le cycle de filtration avec des augmentations relativement
plus faibles de la pression transmembranaire.
Mots clés : procédé de boues activées, bioréacteur à membrane, encrassement de la membrane, eaux usées huileuses,
charbon actif en poudre, pression transmembranaire.
[Traduit par la Rédaction]

Introduction gas stations has become a major pollution contributor in urban

environment. Each gas station generates an average of 20 m3
In recent years, as a result of rapid industrialization and in- of wastewater per day. The carwash operation, which generates
creased living standards with an urban shift in population, the 300–600 L of water per car, is the primary source of pollution.
number of cars has significantly increased in the urban areas of This wastewater stream mainly consists of emulsifier, lubricat-
Thailand. This has led to the rapid increase in the number of ing oil, and suspended solids. The oil in the carwash wastewater
gas stations in the country, for instance, the number increased is mainly present as an oil–water emulsion in the presence of
from 9 000 to 14 000 from 1994 to 1997. Wastewater from these emulsifier. The conventional treatment systems for oily waste-
water from gas stations are parallel or corrugated plate inter-
Received 6 February 2004. Revision accepted 23 September 2005. ceptors (PPI or CPI), which are designed to treat only free oil
Published on the NRC Research Press Web site at [Link] and settled solid and therefore have little effect on the oil–water
on 11 July 2006.
emulsion. The effluent from these systems contains about 50–
P.T. Tri and C. Visvanathan.1 Environmental Engineering and 100 mg/L of oil. Consequently, the wastewater discharged from
Management Program, School of Environment, Resources and De- gas stations hardly meets the discharge standards of 15 mg/L
velopment,Asian Institute of Technology, Pathumthani 12120, Thai- for oil and 120 mg/L for chemical oxygen demand (COD) in
land.
V. Jegatheesan. School of Engineering, James Cook University, the effluent.
Townsville, QLD 4811, Australia. Physical treatment of oily wastewater, by such methods as
a gravity separator, dissolved air floatation (DAF), ultrafiltra-
Written discussion of this article is welcomed and will be received
tion etc., is not effective in removing the pollutants completely,
by the Editor until 30 November 2006.
instead they just transfer them to a more concentrated phase.
1
Corresponding author (e-mail: visu@[Link]). Moreover, the physical treatment cannot remove the soluble

J. Environ. Eng. Sci. 5: 309–316 (2006) doi: 10.1139/S05-032 © 2006 NRC Canada
310 J. Environ. Eng. Sci. Vol. 5, 2006

fraction of the wastewater, which may contain toxic compo- meate flux under steady-state condition of membrane filtration
nents such as polyaromatic hydrocarbons. Biological treatment has become an important factor to make the application of the
of gas station wastewater is feasible as it contains a portion of MBR process a success. This paper presents the experimental
easily biodegradable components and when mixed with domes- investigations that were conducted to find out the treatability of
tic wastewater, it receives the essential nutrients such as nitro- the oily wastewater from gas stations using a MBR system.
gen and phosphorus in the form of ammonia and phosphates,
which are favorable for the growth of microorganisms. How-
ever, removal efficiency of conventional biological processes
Materials and methods
is low due to the inhibitive effects of toxic substances and hy-
drophobic characteristics of oil components (Scholz and Fuchs Experiments were conducted in three segments. At first, the
2000) present in them. Large space requirements also limit the adsorption capability of powdered activated carbon (PAC) when
application of conventional biological treatment. applied to treat oily wastewater was determined through the
Recently, membrane bioreactor (MBR) process has become a isotherm experiments. This was followed by a series of batch
novel technology in treating wastewater from various sources. experiments to compare the performance of activated sludge
The MBR is a modification of conventional activated sludge process (ASP) and biological activated carbon (BAC) process
(ASP) process, in which solid–liquid separation is accomplished in treating the oily wastewater. These experiments were con-
by membrane filtration instead of a secondary sedimentation ducted to determine the kinetic parameters that are involved in
tank. One of the advantages of the MBR process is that it can the biodegradation of the oily wastewater in the AS and BAC
be operated at a very high sludge retention time (SRT) in com- processes. Finally, MBR was used with and without the addition
parison to conventional ASP. This creates favorable conditions of PAC to treat the wastewater in order to evaluate the effect of
for the growth of slow-growing microorganisms, which can PAC in removing oil and grease (O&G).
degrade recalcitrant and toxic substrates such as petroleum hy- The activated carbon used in this study was untreated pow-
drocarbons (Fuchs and Braun 2001), lubricant oil, and fuel oil dered activated carbon (PAC) supplied by Sigma Chemical
(Scholz and Fuchs 2000). Other advantages of the MBR system Company. Nominal size distribution of the PAC was in the
include stability against shock loading, low sludge production range of 100–400 mesh, which is equivalent to 37–150 µm.
rate, compact size, and high effluent quality, which is attractive The surface area, methylene blue adsorption, iodine number,
for water reuse (Visvanathan et al. 2000). Therefore, biologi- pH, and the ash content of the PAC are 750 m2 /g, 10–15 g/100g,
cal treatment such as the MBR process would be a prospective 800 mg/g, 9–11, and 6%, respectively (Source: SIGMA Chem-
option to treat oily wastewater from gas stations to produce an ical Co., CAS # : 64365-11-3). The PAC was boiled and washed
effluent that can meet not only the effluent standard but can also several times with distilled water to remove impurity and then
be reused in car washing operations. dried at 105 ◦ C. The dried PAC was kept in a desiccator before
However, membrane fouling that leads to the decline in the being used.
permeate flux and increase in transmembrane pressure (TMP) The oil fraction, provided in the form of oil–water emulsion,
has limited the application of the MBR process as it increases was prepared by adding 1.0 g of oil and 100 mL of emulsi-
the operating cost. Therefore, it is important to understand and fier solution (0.1% by volume) to the tap water to make one
control membrane fouling to make the MBR process econom- litre of the stock oil–water emulsion solution. The mixture was
ically viable for practical applications. The evolution of mem- blended by the Heidolph Stirrer RZR1 (Germany) at the speed
brane fouling in a bioreactor depends on various factors. For ex- of 1500 r/min for 4 h. Commercial lubricant Performa SAE
ample, compounds such as extracellular polymeric substances 20W-50, manufactured by Petroleum Authority of Thailand
(EPS) mainly composed of soluble organic matters excreted by (PTT), was the oil used in this study. The emulsifier used was
activated sludge are reported to be the main foulants. Further, Ter 10 12A, a non-ionic emulsifier, which is principally the
the operating conditions of a MBR system also play an impor- main component of commercial car wash detergents. The stock
tant role in controlling membrane fouling. Fouling occurs be- oil–water emulsion was then diluted to the desired oil concen-
cause of the deposition of particles and substances like EPS onto tration and glucose and nutrient salts were added to prepare the
the surface of membrane while the permeate flux passes through feed water.
the membrane. The deposition increases as the permeate flux
increases. However, the shear-induced diffusion could shift the Membrane bioreactor experiments
particles away from the membrane. Howell (1995) proposed a Figure 1 presents the schematic diagram of the experimental
theory of critical permeate flux in membrane filtration for which set-up. The reactor was made of transparent acrylic pipe with
the deposition is balanced by the shear-induced shift. Thus, if a diameter of 100 mm and a working volume of 6 L. A U-shaped
the permeate flux is below the critical flux, no deposition occurs. hollow fiber microfiltration membrane module (STERAPORE

However, application of this critical flux theory in MBR process manufactured by Mitsubishi Rayon Co., Ltd., Japan) with a pore
for treating wastewater is difficult due to the multi-component size of 0.1 µm and surface area of 0.42 m2 was immersed in
nature of the wastewater and the biological characteristics of the the reactor. Activated sludge collected from an aeration tank of
activated sludge. Therefore, understanding the sub-critical per- a wastewater treatment plant was used as the inoculum to the

© 2006 NRC Canada

Tri et al. 311

Fig. 1. Experimental setup for the MBR.

Timer

Hg manometer
Air backwash

Solenoid valve

Suction pump
Feed tank
Membrane
module

Level control
tank
Effluent tank

pH
controller

Inlet

Compressed air

Air diffuser

reactor. The activated sludge was acclimatized to the oily waste- Table 1. Composition of the feed wastewater.
water at an oil concentration of 150 mg/L in a batch reactor with
Component Concentrationa (mg/L)
fill and draw process for 2 months before being used as the in-
oculum. The reactor was continuously aerated by compressed Oil — commercial lubricant Performa 150b
air through stone diffusers placed at the bottom to maintain the SAE 20W-50, from the Petroleum Au-
concentration of dissolved oxygen (DO) between 2 and 4 mg/L. thority of Thailand
The pH of the reactor was maintained in the range of 6.5 to 7.5. n- and iso alkanes 50%, monocyclic alka-
nes 30%–40%, and aromats 5%–10%
The reactor was operated with periodic air backwashing. The
Non-ionic emulsifier — Ter 10 12A 13.6c
alternative operation of filtration and air backwashing was con-
Glucose 98.74d
trolled by an intermittent controller (timer) and solenoid valves.
K2 HPO4 880
Each operational cycle consisted of 25 min of filtration followed KH2 PO4 440
by 3 min of air backwashing at an air pressure of 300 kPa. Typ- NH4 Cl 105
ical composition of the feed wastewater is given in Table 1. MgSO4 ·7H2 O 150
The experiment was conducted in eight different operational ZnSO4 ·7H2 O 5
modes with different influent concentrations of oil and hy- FeSO4 5
draulic retention times (HRTs). Experimental conditions for MnSO4 5
each run are presented in Table 2. The first seven operational CaCl2 20
modes (especially run V, VI, and VII) were conducted to deter- (NH4 )6 Mo24 ·4H2 O 0.02
mine the ability of the MBR system to resist shock loading. In CuSO4 0.02
a real carwash operation, both O&G concentration and (or) the CoCl2 0.02
flow rate of the carwash wastewater may increase greatly within a Concentration of mineral salts was adjusted proportionally to COD of
a short period of a week. For example, the flow rate might be the feed wastewater.
very high during weekends when a large number of cars are b Oil concentration was varied from 150 to 600 mg/L.
washed. Therefore, the experiment was designed to include the c Emulsifier concentration was varied proportional to oil concentration.
d Glucose concentration was maintained constant in all experiments,
shock loading in terms of both flow rate and concentration in
providing a BOD value of approximately 100 mg/L.
the first seven runs. The eighth run was carried out to observe

© 2006 NRC Canada

312 J. Environ. Eng. Sci. Vol. 5, 2006

Table 2. Summary of various operational conditions used in the MBR experiment.

Run HRT Permeate flux Lubricant oil Emulsifier Influent COD Volumetric loading rate
(h) (L·m−2 ·h−1 ) (mg/L) (mg/L) (mg/L) (kg COD m−3 ·d−1 ) (kg oil m−3 ·d−1 )
I 8 1.79 150 13.6 555 1.66 0.45
II 6 2.38 150 13.6 582 2.33 0.60
III 4 3.57 150 13.6 575 3.45 0.90
IV 2 7.14 150 13.6 511 6.13 1.80
V 4 3.57 300 27.2 1049 6.29 1.80
VI 4 3.57 450 40.8 1336 8.02 2.70
VII 4 3.57 600 54.4 1813 10.9 3.60
VIII 4 3.57 300 27.2 993 5.96 1.80
IX* 4 3.57 300 27.2 971 5.83 1.80
*Note: 2 g/L of PAC was added at the beginning of Run IX; the values given are averages of each run.

the performance of the membrane when it was operated for out from the solution by adding three parts of solvent mixture
longer periods. In the first seven runs, no sludge was wasted ex- of acetone and ethanol (3:1 v:v) to one part of the extracted
cept what was taken for the purpose of sampling. In the eighth EPS solution and keeping at 4 ◦ C overnight for the precipita-
run, sludge was wasted daily to maintain a solid retention time tion to complete. The quantity of the extracted EPS was then
(SRT) of 50 d. determined by suspended solid analysis using filtration as de-
In an additional ninth operational mode, 2 g/L of powdered scribed in the Standard Method for the Examination of Water
activated carbon (PAC) was added to the reactor to develop and Wastewater (APHA et al. 1995). Carbohydrate and protein
BAC sludge in the MBR reactor. The purpose of the addition of contents in the extracted solution were determined using spec-
PAC and developing BAC was to reduce fouling of the mem- trophotometric method at wavelengths of 480 nm and 570 nm,
brane. This run (run IX) was carried out to evaluate the effect respectively, (Dubois et al. 1956; Lowry et al. 1951).
of PAC on the performance of the MBR in terms of reduction
in the rate of clogging of membrane pores and improvement in
Results and discussions
the quality of the permeate (Pirbazari et al. 1996). In this run,
PAC was supplemented into the reactor daily to compensate MBR experiments
the amount of PAC withdrawn along with the sludge. The pH Removal efficiencies of COD and O&G
of the reactor was maintained in the range of 6.2 to 8 by adding Figures 2 and 3 summarize the variation in the COD and
sodium hydroxide (NaOH) when necessary. The DO was main- O&G concentrations present in the influent and effluent through-
tained between 2 and 4 mg/L. After each run, the membrane was out the experimental runs. The MBR system showed good re-
subjected to chemical cleaning to restore its permeability. moval efficiencies with stability against shock loading. The sys-
tem produced an excellent effluent quality with COD and O&G
Analytical methods ranging from 11 to 86 mg/L and 0.2 to 7.3 mg/L, respectively.
The analyses of COD, biochemical oxygen demand (BOD), The removal efficiency was about 97.6%–99.9% for oil and
O&G, and mixed liquor suspended solids (MLSS) were based 90%–99% for COD. In the first seven runs when the oil-loading
on the procedures recommended in the Standard Methods for rate was continuously increased up to 3.6 kg oil m−3 ·d−1 with
the Examination of Water and Wastewater (APHA et al. 1995). the COD of the influent as high as 1835 mg/L, COD and O&G
For the determination of the concentration of oil in the reactors, of the effluent remained stable with low values. In the eighth
100 mL of the mixed liquor sample was filled in a 1 L extraction run, when the bioreactor was operated for a long period of time
funnel and allowed to settle for 30 min. The settled sludge was (21 d) at a HRT of 4 h, the biosystem was in a stable condition
withdrawn from the bottom of the funnel. The supernatant was with MLSS varying in a narrow range (8 340–10 020 mg/L).
analysed for O&G by Partition-Gravimetric method. In this run, no oil accumulation occurred in the reactor and the
Thermal extraction method was used to extract EPS (Morgan removal rate of the system was about 0.64 mg COD/(mg MLSS
et al. 1990). A measured volume of sludge solid was concen- d). A mass balance for oil was also carried out to obtain the rate
trated by a centrifuge at 2000 r/min (× 820g) for 10 min. The of degradation of oil by the sludge. The rate of degradation of
sludge was then re-suspended in distilled water before being oil by sludge was found to be 0.19 mg oil/(mg MLSS d).
heated at 80 ◦ C for 1 h. The solution that contained the extracted However, when the oil-loading rate was increased to 2.7 and
EPS was obtained by centrifuging first at 2000 r/min (× 820g) 3.6 kg·m−3 ·d−1 in run VI and run VII, respectively, there was
for 10 min and then at 5000 r/min (× 5500g) for 20 min to a sharp increase in the O&G concentration that was present
remove the sludge solids. The extracted EPS solution was then in the mixed liquor of the bioreactor. The O&G in the mixed
analysed for total EPS and its composition (carbohydrate and liquor reached 946 mg/L, which was higher than the influent
protein). Total EPS was determined by precipitating the EPS concentration of O&G. This indicates that the oil-loading rate

© 2006 NRC Canada

Tri et al. 313

Fig. 2. Variation of COD in the influent and the effluent throughout the experimental period.
2000
I II III IV V VI VII VIII
1800
1600
1400
COD (mg/L)

1200
1000
800
600 Influent COD
400 Effluent COD
200
0
0 5 10 15 20 25 30 35 40
Time (day)

Fig. 3. Variation of O&G concentration in the influent and the effluent in the MBR system.
1000
I II III IV V VI VII VIII
900
800
Influent O&G
700 Reactor O&G
O&G (mg/L)

600 Effluent O&G

500
400
300
200
100
0
0 5 10 15 20 25 30 35 40
Time (day)

was above the assimilative capacity of the system. Later, the pear to have an immediate effect on TMP, at least during runs
concentration of O&G in the mixed liquor gradually decreased I to IV. This was proved again during runs V to VII, which had
below the influent concentration of O&G in the first 7 d of run much higher oil concentrations but TMP remained stable.
VIII when the oil-loading rate was lowered to 1.8 kg·m−3 ·d−1 . The permeate flux of 3.57 L·m−2 ·h−1 was selected for run
The O&G in the mixed liquor for the rest of the period of runVIII VIII and to observe the variation in TMP during the course of
was below the influent O &G concentration. This shows that the the run. The TMP was very stable at 9.2–9.5 kPa for a period of
MBR system had the ability to keep the excess oil during high 18 d. It increased sharply from 11.7 kPa (19th day) to 15.3 kPa
oil loading in the system for later degradation when the loading (21st day) and the membrane clogged rapidly. This pattern was
comes back to normal without affecting the effluent quality. also observed by Ognier et al. (2001). The TMP did not in-
From the results it can be concluded that under normal operating crease gradually from the beginning; instead a sharp increase
conditions the oil-loading rate of 1.8 kg·m−3 ·d−1 would be the was noticed at a certain point in the filtration cycle. It could be
limiting value for the MBR system examined in this study. concluded that it is crucial to maintain the permeate flux below
a critical value to prolong the membrane operation. The sharp
Variation of transmembrane pressure increase of TMP at the end of the filtration cycle could be due to
From run I to run IV, the MBR system was operated with in- many reasons other than hydrodynamic conditions of the filter
creasing permeate fluxes of 1.79, 2.38, 3.57, and 7.14 L·m−2 ·h−1 operations.
(corresponding to the HRTs of 8, 6, 4, and 2 h). Variation of
TMP is presented in Fig. 4. Except for run IV, the TMP remained Membrane cleaning
unchanged for each run. In run IV, the TMP continuously in- The degree of ease of cleaning a membrane also plays an
creased from 12.1 kPa to 22.7 kPa and the membrane was easily important role in the application of MBR in real time situations.
clogged leading to difficulty in maintaining the permeate flux. In this study, chemical cleaning of the membrane was performed
Therefore, the critical permeate flux should be between 3.57 after the fourth, seventh, and eighth runs. During cleaning, the
and 7.14 L·m−2 ·h−1 . Further, the oil concentration did not ap- membrane was first flushed with tap water to remove the cake

© 2006 NRC Canada

314 J. Environ. Eng. Sci. Vol. 5, 2006

Fig. 4. Variation of transmembrane pressure during the eight experimental runs. ↓, denotes when chemical cleaning took place.
30 30
I II III IV V VI VII VIII
Transmembrane pressure (kPa)
25 ↓ 25

Permeate flux (L·m-3·h-1)

20 20
↓
15 15
↓ TMP
10 10

5 Permeate flux 5

0 0
0 5 10 15 20 25 30 35 40
Time (day)

layer attached to its surface. Next it was soaked in NaOH (2%) Fig. 5. Variation of COD in the influent and effluent during runs
solution for 12 h. Later, the membrane was washed with tap VIII and IX.
water and soaked in HNO3 (1%) solution for 4 h. Finally, the PAC addition

membrane was washed with tap water and its resistance was 1200
measured to monitor the efficacy of chemical cleaning.
1000
Membrane resistance was measured based on the resistance-
in-series model as given in eq. [1]. 800
COD (mg/L)

Influent COD

P 600
[1] J = Effluent COD
µRt
400
and Run VIII Run IX
200
[2] Rt = Rm + Rc + Rf
0
where J is the permeate flux (m3 ·m−2 ·s−1 ),

P is the trans- 1 3 5 7 9 11 13 15 17 19 1 3 5 7 9 11 13 15
membrane pressure (Pa), µ is the dynamic viscosity of the per- Time (day)
meate (Pa·s), Rt is the total resistance for filtration (1/m), Rm
is the intrinsic membrane resistance (1/m), Rc is the cake layer Freundlich isotherm (Tri 2002). Further, the batch MBR ex-
resistance, and Rf is the fouling resistance (1/m). The results periments conducted at higher HRTs (more than 10 h) with
showed that the resistances of the cleaned membrane were al- and without the addition of PAC showed similar performances
most close to its original value. The intrinsic membrane resis- in removing O &G and COD under both conditions (Tri 2002).
tances (Rm ) after chemical cleaning following runs IV, VII, and This information was used to evaluate the performance of MBR
VIII were in the range of 8.60 × 1011 – 8.98 × 1011 m−1 , which during runs VIII and IX.
differ by ±3.9% from the original value. It can be concluded The runs VIII and IX were conducted to determine the clog-
that the chemical cleaning could almost recover the membrane ging of the membrane in the case of long-term operation of a
to its original conditions. The cake layer attached to the mem- MBR under a given hydrodynamic and biological conditions
brane surface was removed mostly by flushing it with tap water. (HRT = 4 h; O&G = 300 m/L); 2 g/L of PAC was added to the
When the membrane was soaked in sodium hydroxide solution, reactor at the beginning of run IX. The results are presented in
the solution became turbid and brownish yellow particles could Fig. 5.
be observed in the solution. Both of these suggest that the oil The effluent quality was stable at low values for both run VIII
itself may have become foulant and these foulants can be effec- (20 d) and run IX (16 d), similar to previous runs. The effluent
tively removed with alkaline solution. COD ranged from 29.3 to 85.9 mg/L for run VIII and 22.8 to
48.8 mg/L for run IX. The range of O&G was 2.9–7.3 mg/L and
0.4–5.2 mg/L for runs VIII and IX, respectively. For run VIII,
Runs VIII and IX of the MBR the removal efficiencies of COD and O&G were 91.0%–96.3%
Results obtained from the standard isotherm experiments and 95.2%–97.5%, respectively. The corresponding values for
showed that adsorption of O&G by PAC reached equilibrium run IX were 95.0%–97.5% and 98.3%–99.9%. The average re-
at about 4 h and the adsorption phenomenon was modeled by moval efficiencies of COD and O&G for run VIII were 93.6%

© 2006 NRC Canada

Tri et al. 315

Table 3. Comparison of EPS content in the sludge of runs VIII to membrane system set-up. The total resistance (Rt ) was mea-
and IX. sured right after the run with the membrane still in its clogged
mg/g MLSS condition. The combined value of Rm and Rf was obtained by
measuring the resistance of the membrane after being washed
Sludge EPS Protein Carbohydrate with tap water to remove the cake layer. The membrane resis-
AS taken on the 15th day of run 31 4.8 14 tance at the beginning of the run (after chemical cleaning) was
VIII considered as Rm . The value of Rc was derived from Rt , Rm ,
BAC sludge taken on the 15th 27 4.0 13 and Rf using eq. [2].
day of run IX As presented in Table 4, for the clogged membrane, the resis-
tance of the cake layer was the highest component contributing
and 98.7%, respectively. The corresponding values for run IX to the total resistance in both runs VIII (39.1%) and IX (67.4%).
were 96.1% and 99.3%, respectively. It is noted that the effluent Removal of the cake layer could restore the intrinsic resistance,
quality obtained during run IX was slightly better than that of Rm , of the membrane back to its original value. The question
run VIII. This could be due to the addition of PAC, which could is whether the formation of the cake layer on the membrane
adsorb both COD and O&G. However, the difference was not surface happened gradually from the beginning of the run and
very significant because the improvement due to the addition of it became thicker with time or the formation of the cake layer
PAC was overshadowed by the enhanced effect of membrane just became significant at a critical point when hydrodynamic
separation. conditions became favorable for its formation. If the former
During the course of run VIII, the concentration of O&G in was the case, the TMP should have increased gradually from
the reactor varied significantly (see Fig. 3). Previous runs pro- the beginning. But this was not the case in both runs VIII and
duced a concentration of O&G in the range of 225–380 mg/L, IX. Moreover, the MBR system was operated at intermittent air
for the first 4 d of run VIII. However, this concentration reduced backwash, which was expected to remove the polarized cake
to the range of 147–207 mg/L for the remaining 16 d of run VIII. layer from the surface of the membrane for each filtration cy-
This indicates that once the oil-loading rate is returned to nor- cle. Therefore, one can conclude that there was a point when air
mal the MBR system has the ability to degrade the oil that has backwash became ineffective and the formation of the polariza-
been accumulated during the period of shock loading. tion became quicker resulting in a sharp increase in membrane
For run IX, the concentration of O&G in the reactor was very resistance. The possible cause of ineffective air backwash would
low on the second day after the addition of PAC into the reactor. be the plugging of pores by various organic and inorganic sub-
This would have resulted from the adsorption of oil by the PAC. stances in the suspension. As long as the pore spaces of the
The concentration of O&G in the reactor still remained at low membrane available for the permeate flux (and for air back-
levels (98–108 mg/L) from the fourth day to the eighth day and wash) were above a critical value, the TMP would not increase
then increased to the levels of 159–182 mg/L. This could be much and the air backwash would still remain effective. Below
due to the saturation of adsorption sites on the PAC as well as this critical value, the rapid formation of the polarization cake
the attached biofilm growth on it. However, the attached growth layer would cause the membrane to clog faster.
did not seem to be predominant in the reactor as most of the It is noted that the initial TMP of run IX (10.5 kPa) was higher
carbon particles were trapped within the bigger microbial flocs. than that of run VIII (9.2 kPa). The MLSS of runs VIII and IX
That could be the reason why the EPS concentration in the BAC was in range of 8 340 to 10 020 mg/L and 9 020 to 10 660 mg/L,
sludge from run IX showed little or no difference with what was respectively (Fig. 6). This slightly higher MLSS concentration
found for the activated sludge of run VIII (Table 3). Therefore, in run IX would not be the reason for the higher initial TMP
the initial enhancement in effluent quality could be attributable because it does not depend upon MLSS concentration. For ex-
to the adsorption property of the PAC. ample, in run VIII, although the MLSS concentration varied
However, the membrane clogged sooner than expected in run from 8 340 to 10 020 mg/L the TMP did not change signif-
IX, in which the TMP increased sharply after 13 d of operation. icantly. Therefore, the increase in the initial TMP of run IX
The membrane started to clog only after 18 d of operation in run would be attributed to the addition of PAC. The PAC used in
VIII. Since the two runs were conducted under similar hydrody- this study had a nominal size range of 37–150 µm and un-
namic conditions, the reason for the different rate of increase in der turbulent conditions those particles could have been broken
TMP could be attributed to the characteristics of the suspension. down to smaller sizes. The broken PAC particles could have
Membrane resistance was measured by filtering pure water been transferred and trapped in the pores of the membrane be-
through the membrane at different filtration fluxes and record- fore they could form BAC sludge. The chemical cleaning of the
ing the corresponding transmembrane pressures. Membrane re- membrane after run IX did not help much to restore it to its orig-
sistance was derived from the slope of the linear curve of
P inal condition, which suggests that the pores of the membrane
versus J as described by the following equation: must have been clogged with fine PAC particles. Further, one
could see that the resistance due to foulants, Rf , has doubled
[3]
P = Rt µJ +
Po
in run IX when compared with the Rf in run VIII. This indi-
where
Po is the initial pressure to overcome the resistance due cates the entrapment of PAC in the membrane. Therefore, the

© 2006 NRC Canada

316 J. Environ. Eng. Sci. Vol. 5, 2006

Table 4. Various components of membrane resistance contributing to membrane clogging.

Membrane resistance (m−1 )

Intrinsic membrane resistance Rm Cake layer resistance Rc Fouling resistance Rf Total membrane resistance Rt
Run VIII 8.98 × 1011 (32.8%) 10.69 × 1011 (39.1%) 7.68 × 1011 (28.1%) 27.35 × 1011 (100.0%)
Run IX 8.60 × 1011 (12.6%) 46.03 × 1011 (67.4%) 13.67 × 1011 (20.0%) 68.30 × 1011 (100.0%)

Fig. 6. Variation of transmembrane pressure and MLSS during the MBR, since the former condition could provide a prolonged
runs VIII and IX. cycle of filtration in the MBR with a relatively lesser increase
in transmembrane pressure.
25 12 000
Transmembrane pressure (kPa)

10 000
20 References
8 000

MLSS (mg/L)
15
APHA, AWWA, and WEF. 1995. Standard methods for the exami-
6 000
nation of water and wastewater. 19th ed. American Public Health
10
Association, American Water Works Association and Water Envi-
4 000 ronment Federation, Washington, D.C., USA.
Dubois, M., Gilles, K.A., Hamilton, J.K, Rebers, P.A., Smith, F. 1956.
5 2 000
Run VIII Run IX Calorimetric method for determination of sugars and related sub-
stances. Anal. Chem. 28(3): 350–356.
0 0
Fuchs, W., and Braun, R. 2001. Degradation of phenanthrene in a
1 3 5 7 9 11 13 15 17 19 1 3 5 7 9 11 13 15
membrane bioreactor. Institute for Agrobiotechnology Tulln (IFA).
Time (day) Available from [Link] [accessed
on 1 July 2006].
combination of PAC and microfiltration would not be suitable Howell, J.A. 1995. Subcritical flux operation of microfiltration, J.
to enhance the permeate flux. Membrane Sci. 107: 165–171.
Lowry, O.H., Resebrough, N.J., Farr, A.L., and Randall, R.J. 1951.
Protein measurement with the folin phenol reagent. J. Biol. Chem.
Conclusions
193(2): 265–275.
Application of MBR process to treat oily wastewater from Morgan, J.W., Forseter, F.C., and Evison, L. 1990. A comparative study
gas stations provided good effluent quality with an effluent of the nature of biopolymers extracted from anaerobic and activated
COD concentration of 11–86 mg/L and O&G concentration sludge. Water Res. 24(6): 743–750.
of 0.2–7.3 mg/L, which are well below the discharge standard Ognier, S., Wisniewski, C., and Grasmick, A. 2001. Biofouling in
membrane bioreactors: phenomenon analysis and modelling. In
of 120 mg/L of COD and 15 mg/L of O&G and can also be
Proceeding of the third MBR Conference for wastewater treatment,
reused for carwash activities. The MBR system also showed 3–16 May. Cranfield University. pp. 29–43.
good stability against shock loading. Pirbazari, M., Ravindran, V., Badriyha, B.N., and Kim, S.H. 1996.
Long-term run of the MBR system (without PAC addition) Hybrid membrane filtration process for leachate treatment. Water
at COD loading rate of 6.0 g COD/(L·d), oil-loading rate of Res. 30(11): 2691–2706
1.8 g oil/(L·d) and permeate flux of 3.6 L·m−2 ·h−1 showed Scholz, W., and Fuchs, W. 2000. Treatment of oil contaminated waste-
no accumulation of oil in the reactor. The removal efficiency water in a membrane bioreactor. Water Res. 34(14): 3621–3629.
was 91.0% to 96.3% for COD and 95.2% to 97.5% for O&G. Tri, P.T. 2002. Oily wastewater treatment by membrane bioreactor
The system was operated for 18 d before the TMP increased process coupled with biological activated carbon process. [Link].
sharply. The addition of 2g/L of PAC into the reactor showed thesis, Asian Institute of Technology, Thailand.
little improvement in effluent quality. Visvanathan, C., Ben Aim, R., and Parameshwaran, K. 2000. Mem-
brane Separation Bioreactors for Wastewater Treatment. Crit. Rev.
For the runs without PAC addition, membrane fouling was
Environ. Sci. Technol. 30(1): 1–48.
reversible as its resistance was reverted back to the initial value
after chemical cleaning. For the run with the addition of PAC,
the membrane resistance did not return to the original value.
The resistance of the cake layer was the highest component List of symbols
contributing to the total resistance of the clogged membrane in J permeate flux (m3 ·m−2 ·s−1 )
both cases. During filtration, there exists a critical time when Rc cake layer resistance (m−1 )
the blockage of the pores of the membrane reaches a level that Rf fouling resistance (m−1 )
makes air backwash ineffective and consequently the formation Rm intrinsic membrane resistance (m−1 )
of the cake layer becomes intensive leading to the clogging of Rt total membrane resistance (m−1 )
the membrane. Thus, operating the MBR with only microbial
P transmembrane pressure (Pa)
flocs has an advantage over adding very fine PAC particles into µ dynamic viscosity of the permeate (Pa·s)

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