Journal of Membrane Science 293 (2007) 161166

Feasibility study on petrochemical wastewater treatment

and reuse using submerged MBR
Jian-Jun Qin

, Maung Htun Oo, Guihe Tao, Kiran A. Kekre

Centre for Advanced Water Technology, Singapore Utilities International Pte Ltd., The Toh Tuck Complex,
80/82 Toh Guan Road East #C4-03, Singapore 608575, Singapore
Received 31 August 2006; received in revised form 2 February 2007; accepted 5 February 2007
Available online 13 February 2007
Abstract
Treatment of the wastewater from a petrochemical industry has been investigated using a submerged membrane bioreactor (MBR). A bench
scale MBRsystemwith an anoxic/aerobic concept and at sheet MF membranes were used in the study. The testing systemran continuously (24-h)
over 2 months. Trials on different membrane uxes and hydraulic retention time (HRT) were conducted and the effect of aeration on nitrication
was investigated. The results showed that the product quality consistently met the requirement for discharge while segregation of the streams with
high TDS was required to reclaim the water for reuse. A ux of 12.5 Lm
2
h
1
(LMH) was sustainable and HRT of 13 h was applicable. The
current anoxic volume ratio of 40% in this system might be further increased to reduce the energy consumption in the aeration tank. Membrane
permeability could be fully recovered after cleaning. In addition, there was no foaming issue in the process. It was concluded that it was feasible
to treat the wastewater using submersed MBR technology.
2007 Elsevier B.V. All rights reserved.
Keywords: Membrane bioreactor; Petrochemical wastewater; Water treatment and reuse; COD removal; Nitrication
1. Introduction
Advanced membrane bioreactor (MBR), a combination of the
conventional activated sludge process (ASP) and MF/UF mem-
brane separation, has been widely used in treatment of domestic
sewage. Since the membrane in MBRreplaces the clarier of an
ASPplant with an ultimate barrier for biomass control and solids
separation is achieved by means of ltration rather than gravity
settling, the quality of the MBR efuent is independent of the
settleability of the mixed liquor and that even if the biological
process is upset the membrane can ensure that there will be no
suspended solids in the efuent. Moreover, the mixed liquor sus-
pended solids (MLSS) concentration in MBR is typically 35
times as that in ASP, the bioreactor volume in MBR is one-third
to one-fth of that in ASP while the same biomass inventory
is maintained. As a result, MBR has advantages of small foot
print, reduced sludge production and consistently high quality
of efuent over ASP [111].

Corresponding author. Tel.: +65 63262914; fax: +65 63262929.

E-mail address: jjqin@cawt.sui.com.sg (J.-J. Qin).
Gander et al. [1] introduced various types of commercial
aerobic MBRs for domestic wastewater treatment with cost
considerations and concluded that the submerged conguration
would operate more cost effectively than the side-streamcong-
uration with respect to both energy consumption and cleaning
requirements. Stephenson et al. [3] reviewed a number of MBRs
for treatment of municipal wastewater. Different commercial
MBRplants have proven both reliable and simple to operate. Tao
et al. [9] have studied three types of submerged MBR pilots and
demonstrated the advantages of MBRtechnology for reclaiming
the domestic sewage under the tropical conditions.
Wastewater in petrochemical industry is currently treated by
ASP with pretreatment of oil/water separation. There are lim-
ited investigations on the treatment and reuse of petrochemical
wastewater using MBR technology [12]. Nevertheless, tighten-
ing efuent regulations and increasing need for reuse of treated
water have generated interest in the treatment of petrochemical
wastewater with the advanced MBR process. The objectives of
this study were to evaluate the feasibility of treating the wastew-
ater to meet the applicable discharge limits consistently using
submersed MBR technology and further to evaluate whether
the quality of the treated water would meet reuse requirements.
0376-7388/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2007.02.012
162 J.-J. Qin et al. / Journal of Membrane Science 293 (2007) 161166
Fig. 1. Schematic process ow diagram.
Bench scale studies were conducted under different conditions
with an anoxic/aerobic concept MBR. The results showed that
it was feasible to treat the wastewater using MBR technology.
The sustainable membrane ux and applicable hydraulic reten-
tion time (HRT) of the process were obtained. The treated water
quality consistently met the requirements for discharge while
segregationof the streams withhighTDSwas requiredtoreclaim
the water for reuse.
2. Materials and methods
2.1. Bench scale trials
Wastewater was taken daily in carboys from a point after the
equalization tank and before the conventional activated sludge
process at the wastewater treatment plant of a petrol chemical
industry. A bench scale MBR system was used in this study.
Fig. 1 shows a schematic process owdiagramand Fig. 2 shows
a picture of the system in operation. MF at sheet membranes
Fig. 2. Picture of the bench scale MBR system in operation.
Table 1
Specication of MBR system
Item Specication
Membrane type Flat sheet
Membrane material Chlorinated polyethylene
Membrane pore size 0.4 m
Membrane area per module 0.1 m
2
Number of modules 2 +1
Effective volume of anoxic tank 18 L
Effective volume of aeration tank 30 L
were used for the trials. Specication of the membrane is given
in Table 1. The operating conditions of MBR system are shown
in Table 2. In summary, the MBR system was seeded with bio-
logical sludge taken fromthe sludge return line at the wastewater
treatment plant of the petrol chemical industry. Therefore, the
seed was supposed to be acclimated to the wastewater. The
experiments were carried out at room temperature (26 1

C).
Table 2
Operating conditions of bench scale MBR system
Parameter Test 1 Test 2 Test 3 Test 4
Permeate ow rate (L/h) 2.5 2.5 3.0 3.75
HRT (h) 19 19 16 13
DO in the anoxic tank (mg/L) 0.3 4 0.4 0.3
Membrane area (m
2
) 0.2 0.2 0.2 0.3
Membrane ux (Lm
2
h
1
) 12.5 12.5 15 12.5
DO in the aerobic tank (mg/L) 4
Re-circulation ow ratio 3:1
pH of the feed 6.410.4
pH in the anoxic tank 7.88.6
pH in the aerobic tank 7.68.2
SRT (day) 25
Anoxic volume ratio (%) 40 (except Test 2)
MLSS (mg/L) 86009600
MLVSS (mg/L) 78408720
Viscosity of mixed liquor (mPa s) 18.522.5
Operation mode of membrane unit On: Idle =10 min: 1 min
Temperature (

C) 26 1
J.-J. Qin et al. / Journal of Membrane Science 293 (2007) 161166 163
The system was operated continuously (24-h) during the study.
Trials on different membrane uxes were conducted to obtain
the sustainable ux. The membrane ux was 9 LMH at the start
of the experiment, and then it was increased to 12.5 LMH and
further to 15 LMH, and nally reduced back to 12.5 LMH. Dif-
ferent tests on HRT were compared. Additionally, a test was
carried out with dissolved oxygen (DO) of 4 mg/L in the anoxic
tank over a period of 6 days in order to study the effect of aer-
ation to the removal of ammonia. MLSS in the membrane tank
was remained in the range of 86009600 mg/L during the study.
Also it should be mentioned that the HRTof the feed tank shown
in Fig. 2 was 4060 h, depending on the ltrate ow rate. Feed
samples were taken after the feed tank but before entering the
anoxic tank, in-line with the MBR.
2.2. Sample analysis
CODanalysis was conducted by HACHmethod 8000, which
was approved by USEPA as per Federal Register, April 21,
1980, 45(78)26811-26812, using low range vial (0150 mg/L)
and high range vial (01500 mg/L). Nitrate-N was measured
by HACH method 10020, which was approved by USEPA as
per Federal Register, July 8, 2004, 69(130) for the range of
0.230.0 mg/L. Nitrite-Nwas measuredbyHACHmethod8507,
which was approved by USEPA as per Federal Register, May
1, 1979, 44(85)25505, for the range of 0.0020.300 mg/L. All
HACH methods are described in detail in the HACH Odyssey
DR/2500 spectrophotometer manual.
Ammonia-Nwas analyzed using a Dimex DX-120 Ion Chro-
matograph following modied APHA 4500 NH3 H standard
method. MLSS and MLVSS were measured as per APHA
2540D and 2540E standards. Viscosity was measured by RION
viscometer VT-03E. Dissolved oxygen was measured by YSI
550DOmeter. Oil andgrease (O&G) was measuredas per APHA
5520Bstandard. TOCmeasurements were done usingShimadzu
TOC analyzer model 5000A as per USEPA 415.1 standard. GC
scan of volatile organic carbon (VOC) was conducted using
Agilent GC 6890. pH and conductivity were measured by
portable meters Oakton pH10 and Cyberscan CON10, respec-
tively. Turbidity was measured using HACH model-2100 N
turbidity meter. Cations were measured by Perkin-Elmer model
DB3000 Inductively Coupled Plasma Emission Spectrometer
as per USEPA 6010B. Anions were analyzed using a Dionex
DX-120 Ion Chromatograph following USEPA 300.0 standard.
Silica was measured as per APHA 4500-Si F.
3. Results and discussion
3.1. Effect of membrane ux in MBR operation
Fig. 3 shows transmembrane pressure (TMP) as a function
of time at different uxes throughout the study. When the oper-
ation started at the ux of 9 LMH, the initial TMP was 0.3 kPa.
TMP was stable at 0.30.5 kPa during Day 116. When the ux
was increased to 12.5 LMH, TMP was slightly enhanced in the
range of 0.60.8 kPa during the operation period of 17 days.
However, when the ux was further increased to 15 LMH, TMP
Fig. 3. TMP vs. time.
was almost linearly built up from 0.8 to 2.7 kPa during the test-
ing period of 10 days. The fouled membranes were took out
from the aeration tank and cleaned in the sequence of mechani-
cal cleaning with sponge, then 2% citric acid solution (soaking
for 7 h) followed by water ush, and then 0.5% NaOCl solution
(soaking for 16 h) followed by water ush. During the nearly
24-h period of membrane cleaning, the feed was shut off, how-
ever, the recirculation between anoxic and aeration tank and the
air supply in the aeration tank remained. Therefore, signicant
change in the microbial population during the membrane remove
for cleaning was not expected. Also the results as shown later
in Figs. 4 and 5 conrmed that the efuent COD and ammo-
nia before and after the membrane cleaning on Day 44 had
no much difference. When the operation resumed at the ux
of 12.5 LMH, TMP showed 0.3 kPa, which was close to that
of the new membrane. The result indicated that the membrane
permeability could be fully recovered after chemical cleaning.
During the nal 18 days of operation at the ux of 12.5 LMH,
TMP was stable at 0.3 kPa over the rst 10 days and gradually
increased to 0.7 kPa towards the end of operation. The rate of
TMP increase was acceptable. The above results showed that the
sustainable membrane ux could be 12.5 LMHunder the testing
conditions.
Fig. 4. COD concentration in the feed and product vs. time.
164 J.-J. Qin et al. / Journal of Membrane Science 293 (2007) 161166
Fig. 5. Ammonia concentration in the feed and product vs. time.
3.2. COD removal
Fig. 4 indicates COD concentration in the feed and MBR
product as a function of time throughout the study. COD in
the product was consistently less than 100 mg/L although feed
COD uctuated from 700 to 2000 mg/L. It is noted that COD in
the product was stable at below 50 mg/L over the nal 2 weeks
of operation while COD of feed COD varied in the range of
7001200 mg/L. The results indicated that COD in the MBR
product was well within the discharge limit of 100 mg/L.
3.3. Ammonia removal
Fig. 5 illustrates ammonia concentration in the feed and MBR
product as a function of time throughout the study. NH
4
-N in
the feed uctuated in the range of 56132 mg/L. In the rst 2
weeks of the operation start up, the nitrication efciency was
low as the ammonia reduction was only 2040%. In the next
three weeks, nitrication seemed to be inhabited. This could
be due to the start-up and acclimation effects. O&G concen-
tration in the feed versus time is plotted in Fig. 6. The high
O&G levels of 53153 mg/L in the feed during the rst 2 weeks
Fig. 6. O&G concentration in the feed vs. time.
Table 3
Effect of DO in the anoxic tank on the MBR product quality
Parameter Test 1 Test 2
HRT (h) 19 19
DO in the anoxic tank (mg/L) 0.3 4
COD in the product (mg/L) 41 48
NH
4
-N in the product (mg/L) 0.6 0.5
NO
3
-N in the product (mg/L) 10.9 52
could be one of the reasons. After 5-week operation, the nitri-
cation efciency started to increase. As a consequence, ammonia
concentration in the MBR product was signicantly reduced to
below5 mg/L. NH
4
-Nin the product was stable at <1 mg/Land a
complete nitrication was achieved over the nal 2 weeks. Also
it was observed that nitrication was good when oil and grease
concentration in the feed was below 20 mg/L.
3.4. Effects of DO in the anoxic tank and HRT
Table 3 shows effect of DO in the anoxic tank on the MBR
product quality. When DOin the anoxic tank was increased from
0.3 to 4 mg/L while HRT was remained at 19 h, the product
quality in terms of COD and NH
4
-N did not change obviously.
The results indicated that more aeration in Test 2 had no benet
on reduction of COD and ammonia. In other words, the current
anoxic volume ratio of 40% in this system might be further
increased to reduce the energy consumption in the aeration tank.
High NO
3
-N concentration in the product was observed in Test
2 because denitrifying organisms were depressed at the high DO
level in the anoxic tank and the accumulation of nitrate was seen
in the system. It should be pointed out that partial denitrication
happened in Test 2 since the sum (60.5 mg/L) of NH
4
-N and
NO
3
-N in the product was signicantly lower than that in the
feed (72 mg/L).
Table 4 shows effect of HRT on the MBR product quality.
WhenHRTwas reducedfrom19to13 h, concentrations of COD,
NH
4
-N and NO
3
-N in the product were in the range of 4065,
0.63.2 and 8.610.9 mg/L, respectively. There are considerably
different results for Test 3 compared to those for Tests 1 and 4.
This could be attributed to the fact that the process might not
reach the steady state after HRT was reduced from19 to 16 h for
Test 3 due to too short testing period (only 1 week). However,
the results indicated that both CODand NH
4
of the product well
met the requirement for discharge and water reuse when HRT
was in the range of 1319 h, which imply that HRTof 13 h might
be applicable.
Table 4
Effect of HRT on the MBR product quality
Parameter Test 1 Test 3 Test 4
HRT (h) 19 16 13
DO in the anoxic tank (mg/L) 0.3 0.4 0.3
COD in the product (mg/L) 41 65 40
NH
4
-N in the product (mg/L) 0.6 3.2 0.8
NO
3
-N in the product (mg/L) 10.9 8.6 9.3
J.-J. Qin et al. / Journal of Membrane Science 293 (2007) 161166 165
Table 5
Typical quality of feed and product
Parameter Feed Product Requirement for discharge Specication for water reuse
COD (mg/L) 7201590 3878 <100
BOD (mg/L) 35 <50 <5
Oil and grease (mg/L) 1420 14 <10
pH 6.410.4 7.68.6 69
TSS (mg/L) <2.5 <30 <5
Phosphate as PO
4
(mg/L) 8.510.1 3.34.6 <5
Turbidity (NTU) 0.200.35
NH
4
-N (mg/L) 56132 0.100.95 <5
NO
3
-N (mg/L) 0.51.2 7.411.8
NO
2
-N (mg/L) 0.040.05 0.10.5
TOC (mg/L) 23.336.5
TDS (mg/L) 14004900 14004900 <1000
GC scan (mg/L) no VOC
3.5. Analytical results of feed and product water
Typical quality of feed and MBR product water is shown in
Table 5. Requirement for discharge and specication for water
reuse in cooling towers are also given in Table 5. When the oper-
ation of MBRsystemwas stable, CODand BODconcentrations
in the product were 3878 and 35 mg/L, respectively. Oil and
grease of the product was 14 mg/L. The range of product pH
was narrow although the feed pH varied in a wide range of
6.410.4. TSS in the product was consistently below 2.5 mg/L.
Phosphate removal was 6567% and phosphate in the product
was 3.34.6 mg/L. As a result, the quality of MBR product met
the requirement for discharge. However, TDS in the product was
14004900 mg/L, which was higher than the specied limit for
water reuse. Further analysis of the MBR product for inorganic
parameters as shown in Table 6 indicates that sodium and sul-
phate in the product were the main components which caused
high TDS. Thus, segregation of the streams with high TDS is
required to reclaim the water for reuse. It should be pointed
out that the experimental results indeed demonstrated consis-
tently high quality of the efuent in the MBR process with
an anoxic/aerobic concept used in this study although the feed
quality uctuated signicantly.
Morphology of the MBR sludge was also examined and the
microbial photos are shown in Fig. 7. The sample was prepared
by wet smear on glass slide procedure with cover slip on top
of it. Then, it was read under light microscopy using Olym-
pus BX51 microscope with eyepiece magnication of 10 and
objective magnication of 40. Pictures were taken by Image
Pro-plus 5.1 software. All four images were taken fromthe same
Fig. 7. Microbial photos of MBR sludge.
166 J.-J. Qin et al. / Journal of Membrane Science 293 (2007) 161166
Table 6
Product quality (inorganic)
Parameter Unit Value
Aluminium mg/L 0.1460.523
Chloride mg/L 120143
Fluoride mg/L 0.140.16
Iron mg/L 0.0370.051
Nitrate (as N) mg/L 7.411.8
Nitrite (as N) mg/L 0.10.5
Sodium mg/L 15401750
Sulphate mg/L 29103090
Calcium mg/L 10.314.6
Magnesium mg/L 2.593.09
Silica as SiO
2
mg/L 3.984.07
Total phosphorous mg/L 1.151.50
sample collected on Day 34 of operation. It can be seen that
there are very little lamentous organisms but high amount of
live bugs. As a result, there was no foaming issue throughout
the study although foaming is a common issue in ASP.
3.6. Future work
Some key remaining issues need to be addressed in appli-
cation of the submerged MBR technology to the treatment of
petrochemical wastewater as follows.
Whether or not high concentration of oil and grease in the
feed has impacts on the biological process and membrane foul-
ing? If yes, it will require proper pre-treatment on oil before the
wastewater enters MBR system.
A pilot study on site is recommended to conrm the per-
formance of the MBR technology and to optimize the process
including different types of membranes, operating conditions
and analysis with economical assessment.
4. Conclusions
The conclusions from the study are summarized as follows:
(1) It is feasible to treat the wastewater using MBRand the prod-
uct quality consistently met the requirement for discharge.
(2) A ux of 12.5 LMH is sustainable for the at sheet mem-
brane used.
(3) HRT of 13 h might be applicable.
(4) Membrane permeability could be fully recovered after
chemical cleaning.
(5) Segregation of the streams with high TDS is required to
reclaim the water for reuse.
Acknowledgements
The authors would like to thank Mr. Nyunt Wai for his support
in the study and Dr. Yeshi Cao for helpful discussion.
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