OILY WASTEWATER TREATMENT BY MEMBRANE BIOREACTOR

PROCESS COUPLED WITH BIOLOGICAL ACTIVATED CARBON PROCESS

Title page
by

Phan Thanh Tri

A thesis submitted in partial fulfillment of the requirements for the degree of Master of
Engineering.

Examination Committee:

Prof. C. Visvanathan (Chairman)

Dr. Josef Trankler
Dr. Preeda Parkpian

Nationality:
Previous Degree:

Vietnamese
Bachelor of Chemical Engineering
Ho Chi Minh City University of Technology
Ho Chi Minh City, Vietnam

Scholarship Donor:

Japan - Asian Development Bank

Asian Institute of Technology

School of Environment, Resources and Development
Thailand
August 2002

Acknowledgement
The author wishes to express his deepest respect and profound gratitude to his
advisor, Prof. C. Visvanathan, for the valuable guidance, advice and encouragement
throughout this study.
Sincere thanks are extended to Dr. J. Trankler and Dr. P. Parkpian who served as
members of the thesis examination committee. Their suggestive and stimulating comments
are highly treasured.
The author gratefully acknowledges the Asian Development Bank and the
Government of Japan for the scholarship grant which allowed the author to pursue his
study at AIT.
Grateful thanks are given to the staffs of the Environmental Engineering
Laboratory, AIT for the precious assistances during this study.
The author would like to acknowledge the Research and Development Center for
Petroleum Safety and Environment, PetroVietnam, for providing favorable condition for
the author to pursue his study at AIT.
The author is very grateful to Dr. N.P. Dan and other friends at AIT for their helps
and encouragement. Special appreciations are given to Mrs. T.T.H. Nhien, who devotedly
stimulated and helped the author to pursue graduate study.
The author is most grateful to his darling wife, who encouraged and shared with the
author the difficulty times during the study. Finally, the author wishes to dedicate this
achievement to his respected and beloved mother, who has sacrificed her life for the
growing-up of her children.

ii

Abstract
Preliminary study of biodegradation of the oily wastewater was evaluated by
activated sludge (AS) process and biological activated carbon (BAC) process operated in
sequencing batch reactor (SBR) mode. In BAC process, powdered activated carbon (PAC)
was added into the reactors at different doses of 100 500 mg/L. The feed wastewater had
COD of 550 mg/L and Oil & Grease (O&G) concentration of 150 mg/L. The reactors were
experimented at hydraulic retention time (HRT) of 3, 6, 10, 13 and 16 h. The results
showed that the removal efficiency of AS process reached 80% for COD and 90% for
O&G at HRT=13h. There was a tendency of effluent quality improvement of the BAC
process at PAC dose = 500 mg/L and HRT = 3h in comparison with the AS process.
Lab scale submerged membrane bioreactor (MBR) system with microfiltration
membrane module was used to investigate the treatment of oily wastewater. The MBR
system provided excellent effluent quality with COD in range of 11.2 to 85.9 mg/L and
O&G in range of 0.2 7.3 mg/L when influent COD varied from 495 1835 mg/L and
O&G varied from 150 600 mg/L. The removal efficiency was 89.9 99.9 mg/L for COD
and 97.6 99.9 mg/L for O&G. The MBR system provided stable effluent quality against
shock loading. The system could stand for the COD loading of 10.5 g COD/L.day and oil
loading of 3.5 g oil/L.day without deteriorating the effluent quality.
Combination of MBR process and BAC process to treat oily wastewater was
investigated by adding PAC to the reactor at the dose of 2 g/L. The hybrid system showed
little improvement in effluent quality. Membrane clogging of the hybrid system occurred
more quickly in comparison with the same system without PAC addition about 5 days. The
reason would be due to the plugging of PAC particles in the pores of the membrane.
The membrane fouling in the MBR system was found reversible while that of the
hybrid system with PAC addition was partially irreversible. The resistance of the cake
layer was found the highest component contributing to the total resistance of the clogged
membrane. It is suggested that during operation there was a critical point when the
blockage of the membrane pores reached a level that made the air backwash ineffective,
the formation of the cake layer became intensive leading to the membrane clogging.

iii

Table of Contents
Chapter

Title

Page

Title page
Acknowledgement
Abstract
Table of Contents
List of Abbreviations
List of Figures
List of Tables

i
ii
iii
iv
viii
vi
vii

Introduction
1.1 General
1.2 Objectives of the study
1.3 Scopes of the study

1
1
2
2

Literature Review
2.1 Introduction
2.1.1 Sources of car wash wastewater
2.1.2 Characteristics of oil/water emulsion
2.1.3 Pollution of oil/water emulsion
2.1.4 Oily wastewater treatment system
2.2 Application of MBR process in wastewater treatment
2.2.1 MBR process
2.2.2 Advantages of MBR process
2.2.3 Membrane fouling
2.2.4 Application of MBR process in oily wastewater treatment
2.3 Biological activated carbon process
2.3.1 Activated carbon adsorption
2.3.2 Biological activated carbon process
2.3.3 MBR process coupled with BAC process

3
3
3
3
5
5
7
7
8
10
11
12
12
13
14

Methodology
3.1 Materials and microorganisms
3.1.1 Feed wastewater
3.1.2 Powdered activated carbon
3.1.3 Microorganisms
3.2 Overall experimental course
3.3 Adsorption isotherm experiments
3.4 Batch experiments
3.5 Membrane bioreactor experiments
3.5.1 Membrane bioreactor set-up
3.5.2 Experimental conditions
3.5.3 Measured parameters in the MBR experiments
3.5.4 Membrane cleaning
3.5.5 Membrane resistance measurement
3.6 Analytical methods

16
16
16
17
17
17
19
19
20
20
20
23
23
24
24

iv

Results and Disscussions

4.1 Adsorption isotherm of the PAC
4.2 Batch experiments
4.3 MBR experiments
4.3.1 Membrane resistance measurement
4.3.2 Optimum HRT run
4.3.3 Shock loading run
4.3.4 Long run A and B
4.4 Conceptual idea for application of MBR system in
wastewater treatment and reuse at gas station

26
26
27
31
31
32
35
37

Conclusions and Recommendations

5.1 Conclusions
5.2 Recommendations
References
Appendix A: Experimental results
Appendix B: Membrane resistance measurement data
Appendix C: Photographs of experimental works

43
43
44
46
49
56
68

41

List of Figures
Figure

Title

2.1
2.2
2.3
2.4
2.5

Process flow diagram of car wash process (Awas, 1997)

Oil/water emulsion conventional treatment systems
Different configurations of MBR process
Membrane fouling
Schematic diagram of dynamic porous PAC layer in cross flow
membrane filtration (Pirbazari et al., 1996)
Relative contributions of COD and BOD from the oil, glucose and
emulsifier of a typical feed wastewater sample having oil
concentration of 150 mg/L
Overall experimental course
Membrane bioreactor setup
Laboratory scale MBR system to treat oily wastewater
Variation of equilibrium COD vs. different contact times (PAC dose =
100 mg/L; T = 25oC; agitation speed = 100 rpm)
Experimental data plotted according to Freundlich isotherm
Experimental data plotted according to Langmuir isotherm
Variation of COD removal efficiency vs. HRT
Variation of O&G removal efficiency vs. HRT
Comparison of COD removal efficiency between AS process and
BAC process (PAC = 500 mg/L)
Comparison of COD removal efficiency between AS process and
BAC process (PAC = 500 mg/L)
Resistance of the membrane before used and after chemical cleaning
Variation of COD of the influent and effluent during Optimum HRT
run 33
Variation of O&G in the reactor and in the effluent during Optimum
HRT run
O&G mass balance of Optimum HRT run
Variation of transmembrane pressure and MLSS during Optimum
HRT run
Variation of COD of the influent and effluent of Shock loading run
Variation of O&G in the reactor and in the effluent during Shock
loading run
Variation of COD of the influent and effluent of Long run A and B
Variation of O&G in the reactor and in the effluent during Long run
A and B
Biofilm development on carbon surface after 14 days of Long run B
BAC sludge after 14 days of Long run B (x580)
Variation of transmembrane pressure and MLSS during Long run A
and B
Conceptual diagram for a wastewater treatment and reuse system
using MBR process at gas station

3.1

3.2
3.3
3.4
4.1
4.2
4.3
4.4
4.5
4.6
4.7
4.8
4.9
4.10
4.11
4.12
4.13
4.14
4.15
4.16
4.17
4.18
4.19
4.20

Page

vi

4
6
9
10
11

17
18
21
22
26
27
27
29
29
30
30
32

33
34
35
36
36
37
38
39
39
40
42

List of Tables
Table

Title

2.1

Characteristics of wastewater from various gas stations in Bangkok,

Thailand (Limpananon and Yodsang, 1997)
Composition of lubricant oil
Comparison of operation parameters between industrial-scale applied
ultrafiltration system treating oil-contaminated wastewater from
machine factoring and the membrane bioreactor system (Scholz and
Fuchs, 2000)
Composition of the feed wastewater
The major properties of the PAC
Experimental conditions for equilibrium adsorption time test
Characteristics of the membrane module
Operational condition of the MBR experiments
Analytical methods
Average results of the batch experiments
Membrane resistances of the new membrane and the membrane after
chemical cleaning
Membrane resistances after each step of chemical cleaning course
after Long run B
Oil loading of Optimum HRT run
Oil loading of Shock loading run
Comparison of EPS content in the sludge of Long Run A and Long
Run B
Various components of membrane resistance contributing to
membrane clogging
Results of equilibrium adsorption time test
Results and calculation of adsorption isotherm test
Results of the batch experiments
Experimental results of Optimum HRT run
Experimental results of Shock loading run
Experimental results of Long run A
Experimental results of Long run B

2.2
2.3

3.1
3.2
3.3
3.4
3.5
3.6
4.1
4.2
4.3
4.4
4.5
4.6
4.7
A.1
A.2
A.3
A.4
A.5
A.6
A.7

Page

vii

4
5

12
16
17
19
20
23
24
28
31
32
34
37
40
41
50
50
51
52
53
54
55

List of Abbreviations
AC
API
AS
BAC
BOD
COD
CPI
DAF
Eff.
EPS
GAC
HRT
Inf.
MBR
MLSS
O&G
PAC
PAH
PPI
Rc
Rf
Rm
Rt
SBR
SRT
T
TMP

Activated Carbon
American Petroleum Institute
Activated Sludge
Biological Activated Carbon
Biochemical Oxygen Demand [mg/L]
Chemical Oxygen Demand [mg/L]
Corrugated Plate Interceptors
Dissolved Air Floatation
Effluent
Extracellular Polymeric Substance
Granular Activated Carbon
Hydraulic Retention Time [h]
Influent
Membrane Bioreactor
Mixed Liquor Suspended Solid [mg/L]
Oil and Grease concentration [mg/L]
Powdered Activated Carbon
Polyaromatic Hydrocarbon
Parallel Plate Interceptors
Cake layer resistance [m-1]
Fouling resistance [m-1]
Intrinsic membrane resistance [m-1]
Total membrane resistance [m-1]
Sequencing Batch Reactor
Solid Retention Time [day]
Temperature [oC]
Transmembrane Pressure [mmHg, kPa]

viii

Chapter 1
Introduction
1.1

General

Oil contaminated wastewater has been recognized as one of the most concerned
pollution sources. This kind of wastewater comes from variety of sources such as crude oil
production, oil refinery, petrochemical industry, metal processing, compressor
condensates, lubricant and cooling agents, car washing. The oily wastewater is considered
as hazardous industrial wastewater because it contains toxic substances such as phenols,
petroleum hydrocarbons, polyaromatic hydrocarbons which are inhibitory to plant and
animal growth and also are mutagenic and carcinogenic to human being.
Physical treatment of oily wastewater such as API gravity separator, dissolved air
floatation (DAF), ultrafiltration etc. does not remove the pollutants completely but just
transfer them to a more concentrated waste (Schols and Fuchs, 2000). Moreover, the
physical treatment cannot remove soluble fraction of the wastewater (Seo, 1997). Currently
conventional biological treatment techniques are mostly incapable of complete elimination
of hydrocarbon in stable emulsion. Removal efficiency of the conventional biological
processes is also low due to inhibitive effects of toxic substances and hydrophobic
characteristics of oil components (Schols and Fuchs, 2000). Therefore, there is a need to
develop a more efficient treatment technique based on biological process to treat oily
contaminated wastewater.
Membrane bioreactor (MBR) process is a novel technology in wastewater treatment
in recent years. It is a modification of conventional activated sludge process in which
solid/liquid separation is accomplished by membrane filtration instead of using a
secondary sedimentation tank. One of the advantages of MBR process is that it can be
operated at very high sludge retention time (SRT) in comparison with conventional
activated sludge process. This will create favorable conditions for the growth of slowgrowing microorganisms which can degrade recalcitrant and toxic compounds such as
petroleum hydrocarbons (Fuchs and Braun, 2001). Other advantages include stability
against shock loading, low rate sludge production, compact size and high effluent quality
which is attractive for water reuse.
However, membrane fouling which leads to high-energy consumption and high
cleaning chemical requirement has limited the application of the MBR process due to high
operation cost. Researches have been conducted to find out various causes relating to the
membrane fouling phenomenon. The presence of extracellular polymeric substances
(EPSs) and the characteristics of the polarization cake layer such as porosity and particle
size are among the factors affecting the membrane clogging process.
Recent efforts have been made to modify the MBR process to make it widely
applicable in wastewater treatment and reclamation in term of high removal efficiency and
reduction of membrane fouling. Among the modifications is the addition of filter aid into
the mixed liquor to control the membrane fouling by increasing the porosity of the cake
layer. Some researchers have proposed the addition of iron oxide particles (Chang et al.,
1998) and powdered activated carbon (PAC) (Pirbazari et al., 1996; Kim et al., 1998).
Among the filter aids, PAC has gained special interests because it also develops biological

activated carbon (BAC) process which is expected enhancing biodegradation and

producing less EPSs (Kim et al., 1998).
The concept of biological activated carbon (BAC) process has been applied in
water treatment as well as wastewater treatment. In the BAC process, activated carbon
either in powdered form (PAC) or in granular form (GAC) is added into the mixed liquor.
The removal of contaminants is achieved by a combination of biodegradation and
adsorption. The use of PAC in MBR process has been shown to enhance the
biodegradation and also maintain a high permeate flux for a long duration (Pirbazari et al.,
1996).
This study focuses on the development of a MBR system to treat the oily
wastewater from gas station effectively to meet the effluent standards for car wash
wastewater and to meet the requirements for water reuse. Effect of PAC addition into the
reactor to the performance of the system is also investigated.
1.2

Objectives of the study

1. to investigate the oil adsorption isotherm of powdered activated carbon.
2. to investigate the biodegradation of oily wastewater in the activated sludge process
and biological activated carbon (BAC) process.
3. to evaluate the performance of a MBR system to treat oily wastewater in term of
membrane fouling, removal efficiency and process stability.
4. to investigate the effect of PAC addition on the performance of the MBR system in
term of membrane fouling and removal efficiency.

1.3

Scopes of the study

1. Synthetic wastewater containing lubricant oil, surfactant and nutrient salts,
representing for oily carwash wastewater, was used in this study as feed
wastewater.
2. Mixed bacterial culture acclimated to oily wastewater was used in the biological
process.
3. Batch experiments were used to determine the adsorption isotherm and
biodegradation of the feed wastewater in the AS and BAC processes.
4. Laboratory scale submerged MBR with hollow fiber membrane module was used
to evaluate the performance of MBR system to treat oily wastewater.
5. Effluent quality and removal efficiency were mainly addressed in term of COD and
O&G concentration.

Chapter 2
Literature Review
2.1

Introduction

Oily wastewater is one of the most concerned pollution sources due to its toxic and
refractory characteristics. This kind of wastewater originates from a variety of sources such
as crude oil production, oil refinery, petrochemical industry, metal processing, compressor
condensates, lubricant and cooling agents, floor washing and car washing. Basically, the
oil in the oily wastewater can be classified into three fractions: free oil, oil/water emulsion
and soluble components. The oily wastewater is normally accompanied with emulsifier
which is used in oil cleaning processes. While the free oil can be removed mostly by
gravity oil separator, the other components of the oily wastewater cannot be removed
simply by gravity separation. In this study, car wash wastewater from gas station will be
studied as a representative for oily wastewater.
2.1.1

Sources of car wash wastewater

Typical car washing operation consists of four consecutive steps as shown in Figure
2.1. Each stage in the process is simply described as follows (Panpanit, 2001):

Stage (1) Dust cleaning: high-pressure water is injected on the car body and engine to
wash away dirty particles. The wastewater in this stage contains a high concentration
of sludge, clay and free oil. In addition, the mechanical force from the high pressure of
the water breaks the oil into oil/water emulsion.

Stage (2) Foaming: The emulsifier solution is sprayed on the car body. The wastewater
in this stage consists mainly of emulsifier at high concentration. Later the wastewater
from this stage is combined with oily wastewater from stage 1 and then the
stabilization of oil/water emulsion takes place.

Stage (3) Presoak: This stage is to remove the emulsifier from the car body by
spraying with fresh water. The wastewater generated in this stage mostly contains low
emulsifier concentration because it is diluted by fresh water.

Stage (4) Spot free rinse and dryer: The objective of this stage is to polish the car
color. High quality water is sprayed on the car body, which is later dried by hot air.
The fresh water contains high impurity such as hardness and organic are avoided in
this stage because it can create an unpolished appearance problems such as spot on the
cars surface color.

Characteristics of wastewater from various gas stations in Bangkok, Thailand are

presented in Table 2.1.
2.1.2

Characteristics of oil/water emulsion

Oil/water emulsion is oil dispersed in water phase. The emulsion is stabilized at the
presence of emulsifier. Generally, an emulsifier consists of a molecule with hydrophilic
and hydrophobic ends. The emulsifier plays the role of a bridging agent which helps to
lower the interfacial tension of the oil, resulting in very small oil droplet size (Althers,

1998). The oil droplet size plays an important role in the stability of the oil/water emulsion.
The oil/water emulsion formed at the presence of emulsifier may have as small oil droplet
as 5 m, resulting in rising velocity of these oil droplets is negligible to the Brownian
movement. Therefore, the emulsion cannot be removed by gravity force.
Fresh water
Emulsifier

Dirty
car

Dust
cleaning

Foaming

Fresh water

Presoak

Fresh water
(high quality)

Rinse
water

Dryer
(high quality)

Clean
car

Oily wastewater
Treated
wastewater

Free oil

API separator
Sludge

Figure 2.1

Process flow diagram of car wash process (Awas, 1997)

Table 2.1 Characteristics of wastewater from various gas stations in Bangkok, Thailand
(Limpananon and Yodsang, 1997)
Gas station
Caltex, Bangkaen
PTT, Bangkaen
Shell, Bangkaen
PTT, Vipavadee
Shell, Kaseat
Caltex, Nakhornpathum
Shell, Nakhornpathum
Esso, Nakhornpathum
PTT, Nonthaburi
Shell, Nonthaburi
Esso, Nonthaburi
Range
Average

O&G
(mg/L)
31.6
25.9
21.5
280.5
63.6
57.0
23.3
161.2
7.8
14.4
16.1
7.8 280.5
63.9

BOD
(mg/L)
42
39
23
180
200
500
10
1220
11
28
21
10 1220
206.72

Suspended solid
(mg/L)
113
86
92
346
246
4724
310
952
696
121
682
86 4724
760

pH
7.60
7.02
7.85
7.51
7.06
6.44
7.05
6.32
7.16
7.24
6.69
6.32 7.85
7.08

The formation of oil/water emulsion increases the bioavailability of oil components

to biodegradation due to the increased solubility and the greater oil-water interface.
Volkering et al. (1995) reported the effects of dissolution process to the increased
biodegradation rates of naphthalene and phenanthrene when surfactants were added. Some
researchers have also confirmed evidences that the greater the oil-water interface, the faster
the rate of decomposition by bacteria (Reisfeld et al., 1972; Oberbremer et al., 1990;
Rosenberg, 1993).

2.1.3

Pollution of oil/water emulsion

Lubricant oil and emulsifier are the main polluting components in carwash
wastewater. Physical properties of lubricant oil are very low volatility and less water
solubility. The lubricant oil is not volatile under normal environmental conditions. Table
2.2 shows the composition of a type of lubricant oil (Scholz and Fuchs, 2001). The
lubricant oil contains mainly aliphatic compounds such as paraffin and cycloparaffins,
aromatics and some amounts of olefins approximately C25 C40. (Cole, 1994; James and
Speight, 1991). The composition of the lubricant oil makes it highly stable to chemical and
biological oxidation. The lubricant oil also contains polyaromatic hydrocarbons (PAHs)
such as naphthalene, phenanthrene, anthracene etc. which are toxic substances and some
are listed as priority pollutants by US EPA. Due to their lipophilic behavior and low water
solubility, PAHs are often dissolved in the dispersed phase of oil/water emulsion or in
hydrophobic organic materials (Kornmuller and Wiesmann, 1999). These compounds are
thought to contribute to the toxic and inhibitive effects in biological processes for oily
wastewater treatment.
Table 2.2 Composition of lubricant oil
Compounds
n- and iso alkanes
Monocyclic alkane
Aromats

Content (%)
50
30 40
5 10

Emulsifier, which sometimes is called surfactant, is one of the major constituents in

carwash detergent. Emulsifier is also found in wastewater from oil industry, rising baths
from metal processing, compressor condensates (Scholz and Fuchs, 2000). Environmental
problems associated with emulsifier discharge are objectionable foaming and low
biodegradability of some types of emulsifiers. Their biodegradability depends greatly upon
chemical structure (Sawyer et al., 1994). There are two main types of emulsifiers used in
industries for cleaning purposes: anionic and nonionic emulsifiers. About 90% of the
industrial wastewater streams contains nonionic emulsifiers (Althers, 1998). The nonionic
surfactants formed from polymers of ethylene oxide appear susceptible to biological
degradation (Sawyer et al., 1994).
2.1.4

Oily wastewater treatment system

Treatment methods for oily wastewater can be classified into three categories
namely, primary or gravity treatment units, secondary processes and tertiary processes
(Figure 2.2). The primary treatment of oily wastewater is usually conducted by the API
separator which treats the free oil effectively by gravity force. Modifications of the API
separator include the use of parallel plate interceptors (PPI) or corrugated plate interceptors
(CPI). These modifications are to improve the removal efficiency and reduce the space
requirement of API separator. However, the API separator and its modifications have no
effect on the soluble fraction of the oil and on the oil/water emulsion. Because the densities
of the oil/water emulsion and water are approximate, the oil/water emulsion cannot be
removed by simple gravity separation. Therefore, a variety of secondary and tertiary
treatment methods have been applied to treat the soluble fraction and the oil/water
emulsion of the oily wastewater.

Primary

API
Separator

Secondary

Tertiary

Dissolved Air
Flotation
Adsorption

Oily
wastewater

Corrugate Plate
Interceptors

Membrane
Filtration

Treated
wastewater

Coalescence
Parallel Plate
Interceptors

Ozonation

High Rate
Filtration

Figure 2.2 Oil/water emulsion conventional treatment systems

-6-

Among the physical-chemical processes, dissolved air flotation (DAF) is the one of
the most common processes used to treat the oily wastewater after gravity separation. The
DAF process includes two different stages: (a) the chemical stage, which consists of
emulsion breaking and creation of solid aggregates (coagulation and flocculation) by
chemical addition, (b) the physical stage, which separates the aggregates from the liquid
phase using air bubbles released under pressure. This process has been reported to achieve
oil removal of 80% to 90% (ASTM, 1969; Donal, 1987 and Meyers, 1984). Galil and Wolf
(2001) also reported the removal efficiency of dissolved organic mater at 40% of the DAF
process.
Coalescence, filtration and adsorption are the other alternatives for oily wastewater
treatment. Coalescence method, which create the microdroplet coalesce to form large
droplet size to be easily separated by decantation (Liem and Woods, 1974), is normally
suitable for oil emulsion with low concentration of emulsion. Filtration process can be
carried out by various types of filter media ranging from coarse granular to fine filtration
such as sand, anthrasilt and diatomaceous earth. It has been reported that the influent oil
concentrations of 130 mg/L to 500 mg/L can be reduced to the range of 12 mg/L to 77
mg/L by filtration system (Panpanit, 2001). Campos et al. (2002) used microfiltration as
pretreatment of oilfield wastewater before biological process. The removals of 35%, 25%,
92% and 35% were reported for COD, TOC, O&G and phenols respectively. Adsorption
process is normally used as tertiary treatment to remove trace amount of oil and emulsifier.
Among the adsorbents used are silica base material, organic polymer, bentonite, activated
carbon etc.
Most of the physical-chemical treatment methods for oily wastewater require
intensive washing and replacement of filtration or adsorption materials that lead to
difficulty in operation and increase in treatment cost. Moreover, the common disadvantage
of all physical-chemical treatment methods is that they do not remove the oil completely
but just transfer them to a more concentrated waste. Therefore, waste disposal is always
problematic for physical-chemical treatment of oily wastewater because the oily waste is
considered as hazardous waste.
Biological processes have also been applied in oily wastewater treatment. These
processes are mainly to remove soluble organic matters remaining after physico-chemical
treatment. Biological treatment is only effective for highly diluted oily wastewater since oil
components are adsorbed on microorganism faster than they can be metabolized.
Subsequently the adsorbed oil tends to damage sludge settling characteristics and cause
system failure (Rhee et al., 1987). Zilverentant (1997) studied the treatment of oily
wastewater from road and rail car cleaning using SBR process indicating that COD
removal in range of 80 90 % and oil removal of less than 100 mg/L can be achieved.
2.2

Application of MBR process in wastewater treatment

2.2.1

MBR process

Membrane bioreactor (MBR) process is a novel technology in wastewater treatment

in recent years. Investigation and innovations to develop MBR process in wastewater
treatment have been conducted intensively during the last decade. To meet the
requirements of water reuse and stricter effluent standards in the future, application of
MBR process has become an attractive alternative in comparison with other conventional

treatment techniques due to its wide range of applicability and performance characteristics
(Visvanathan et al., 2000). There are 500 commercial MBRs in operation worldwide, with
many more proposed or currently under construction (Stephenson et al., 2000).
Generally, MBR process is a modification of conventional activated sludge process
in which solid/liquid separation is accomplished by membrane filtration unit instead of
using a secondary sedimentation tank. MBR systems can be categorized as two different
configurations by the allocation of membrane modules (Figure 2.3).
The first configuration is the externally pressurized cross-flow MBR in which the
membrane module is installed separately from the aeration tank. The mixed liquor is
pumped to the membrane module where it is filtrated by cross-flow filtration through the
membrane. The excess flow is circulated to the aeration tank.
The second configuration is the submerged MBR in which membrane module is
submerged inside the bioreactor and the permeate is suctioned directly by dead-end
filtration. The submerged MBR is superior to an externally pressurized cross-flow MBR in
regard to power consumption and the simplicity of the installation due to the absence of
recirculation pump (Yamamoto et al., 1989).
2.2.2

Advantages of MBR process

MBR process has been proved to have many advantages in comparison with
conventional biological processes. The main advantages are high quality of treated water,
small size of treatment unit, less sludge production and flexibility of operation
(Visvanathan et al., 2000).

Treated water quality: In conventional activated sludge process, effluent quality

strongly depends on the settling of sludge in sedimentation tank. In MBR process,
solid/liquid separation is conducted by membrane filtration. Therefore, the final
effluent does not contain suspended matter, this enables the direct discharge of the
final effluent into the surface water and the reuse of the effluent for cooling, toilet
flushing, lawn watering, or with further polishing, as process water.

Flexibility in operation: Solid retention time (SRT) can be controlled completely

independent from hydraulic retention time (HRT). Therefore, the system can be run at
very long SRT providing favorable conditions for the growth of slow-growing
microorganisms which are able to degrade biorefractory compounds.

Compact plant size: Because the MBR process is independent upon sludge settling
quality, high biomass concentration can be maintained up to 30 g/L in the system
(Yamamoto et al., 1989). Therefore, the system can stand for high volumetric loading
rate resulting in the reduced size of the bioreactor. In addition, secondary settling tank,
sludge thickener or post treatment for further BOD and SS removal are not necessary
in MBR process, thus the plant becomes more compact.

Low rate sludge production: Studies on MBR show that the sludge production rate is
very low. Excess sludge from MBR process is much lower than conventional activated
sludge process. Low F/M ratio and longer sludge age in the reactor may be the reason
for this low sludge production rate.

Influent

Bioreactor

Membrane
module
Air
Circulation
pump
Air diffuser
Effluent

(a) externally pressurized cross flow MBR

Effluent

Bioreactor

Membrane
module
Influent
Air
Air diffuser
(b) submerged MBR
Figure 2.3 Different configurations of MBR process

2.2.3

Membrane fouling

Despite the advantages of the MBR process, the present cost of treatment by MBR
is unfortunately higher than that of the conventional treatment. One of the major reasons
for this higher cost of treatment is attributable to membrane fouling. Membrane fouling
causes the increase in filtration resistance resulting in the decline in permeate flux.
Membrane fouling can result from the formation of a polarization cake layer and
the plugging of membrane pores (Figure 2.4).
Membrane

Membrane
Cake layer

Pore clogging

Permeate flux

Permeate flux

Clean membrane

Membrane fouling

Figure 2.4 Membrane fouling

Effects of membrane fouling on the decline of permeate flux can be explained
using the resistance-in-series model According to this model, the relationship between
permeate flux and transmembrane pressure (TMP) is described in by Equation 2.1.
P
J =

Eq. 2.1

. Rt
Where:
J : permeate flux (m3/m2.s)
P : transmembrane pressure (Pa)
: viscosity of the permeate (Pa.s)
Rt : total resistance for filtration (1/m)
Rt = Rm + Rc + Rf

Eq. 2.2

Rm : intrinsic membrane resistance

Rc: cake layer resistance
Rf: fouling resistance due to irreversible and pore plugging
Intensive researches have been conducted to understand the mechanisms and causes
of membrane fouling. Current trends of controlling membrane fouling are focused on (1)
controlling the production of extracelular polymeric substances (EPSs) in the bioreactor;
(2) reducing the cake layer resistance.

10

Extracelular polymeric substances (EPSs) are the substances excreted by

microorganism. These compounds comprises of protein, polysaccharide, nucleic acid and
lipid. EPSs in microbial flocs have been reported as a major foulant in the membrane
bioreactor system (Chang et al., 1996; Nagaoka et al., 1996) as they occupy the pores of
the membrane. Among different approaches to control of EPS production have been
investigated is control of nutrient composition in the reactor and development attached
growth for MBR system (Kim et al., 1998).
Characteristics of the cake layer play an important role in membrane fouling.
Effects of cake layer characteristics can be described by the Carman-Kozeny equation as
follows (Liew et al., 1995):
dp2 . 3
Ph =
Eq. 2.3
180 (1- )
where Ph : hydraulic permeability through the cake layer
dp : particle diameter
: porosity of the cake layer
Based on this model, one can derive that the greater the particle size and porosity,
the higher permeability. Many attempts have been conducted to improve the permeability
of the cake layer by the addition of filter aids such as metal-based coagulants (Chang and
Benjamin, 1996), PAC (Pirbazari et al., 1996) into the reactor. These filter aids are
expected to form a dynamic cake layer on the membrane surface. The permeability of the
dynamic cake layer is thought to be higher due to larger particle size and porosity.
Schematic diagram of the dynamic cake layer is illustrated in Figure 2.5. The porous layer
also plays as a filter layer to retain soluble organic compounds preventing them to contact
and plug in the membrane pores. Dan (2002) reported a different approach as developing a
yeast culture for MBR system. Due to larger size of yeast cells in comparison with bacteria
cells, the yeast cells play as a porous layer and therefore permeate flux can be enhanced.
Tangential Flow
Soluble organic compound

Biofilm
Dynamic porous cake layer

Carbon particle
Membrane
Permeate Flux

Figure 2.5 Schematic diagram of dynamic porous PAC layer in cross flow membrane
filtration (Pirbazari et al., 1996)
2.2.4

Application of MBR process in oily wastewater treatment

Some researchers have investigated the feasibility of using MBR process to treat
oily wastewater (Scholz and Fuchs, 2000; Seo et al., 1997; Fuchs and Braun, 2001).
Removal of fuel oil, lubricant oil, surfactant, residual oil-originated organic matters as well
as polyaromatic compounds by the MBR process was studied.

11

Scholz and Fuchs (2000) investigated the application of MBR process to treat oily
wastewater. External membrane module configuration was used. Synthetic wastewater
containing either fuel oil or lubricant oil and a surfactant was used in the study. Influent
concentration was in range of 500 1000 mg/L in term of hydrocarbon. Biomass
concentration in the system was maintained up to 48 g/L. Removal efficiency of 99.9% for
fuel oil as well as lubricant oil could be achieved at the hydraulic retention time of 13.3 h.
The maximum biodegradation of fuel oil could be observed at 0.82 g hydrocarbons/(g
MLVSS.day) with the average values ranging from 0.26 0.54. TOC and COD removal
efficiencies were also reported at 94 96 % for fuel oil and 97 98 % for lubricant oil.
The removal efficiency of surfactant was in range of 92.9 99.3 %. The permeate quality
was as high as the effluent can be reused in industrial process. The results when compared
with those from plain membrane filtration showed clearly that the implementation of a
biological stage enhanced permeate quality due to degradation of pollutants (Table 2.3).
However, membrane fouling and decline of permeate flux over operating time were not
reported.
Table 2.3 Comparison of operation parameters between industrial-scale applied
ultrafiltration system treating oil-contaminated wastewater from machine
factoring and the membrane bioreactor system (Scholz and Fuchs, 2000)
Parameter
COD (mg/L)
Oil (mg/L)
COD removal efficiency (%)
Oil removal efficiency (%)

Membrane bioreactor
129 131
0.036 - 0.35
97
99.9

Membrane application
373
1
85.6
99.2

Seo et al. (1997) investigated the treatment of residual organic matters from oily
wastewater from an automobile engine manufacturing plant by MBR process. The system
was run at HRT of 3.67 day, TMP of 1.0 kg/cm2, SRT of 300 day. Removal efficiency of
COD was greater than 95%. Removal of oil substances was 76.1% resulting in average
effluent concentration of 4.4 mg/L as n-Hexane extract. MLSS concentration increased
gradually to more than 2000 mg/L that was twice the initial concentration. Membrane was
cleaned when the flux decreased to about 2 L/m2/hr. after 7 days.
Fuchs and Braun (2001) studied the degradation of phenanthrene in a membrane
bioreactor. Synthetic wastewater containing phenanthrene in suspension form as sole
carbon source was fed at concentration up to 1900 ppm. Mixed culture of bacteria was
adapted with phenanthrene before the continuous run of 160 days. The effluent was
completely free of phenanthrene and the system was proved very stable against shock
loading. However, about 5 % of phenanthrene was not mineralized completely, indicated
by TOC values of the effluent ranging from 40 70 ppm. The metabolites from the
biodegradation of phenanthrene were not biodegraded further under biodegradability test.
No membrane fouling phenomenon was reported. Sorption of phenanthrene onto biomass
and membrane were not investigated.
2.3

Biological activated carbon process

2.3.1

Activated carbon adsorption

Activated carbon has been used for a long time in water and wastewater treatment.
Adsorption capacity of activated carbon is of special interest due to its large surface area.
12

The surface properties of activated carbon depend upon both the initial material used to
produce the carbon and the exact production procedure (Metcalf and Eddy, 1991).
Generally, granular carbon from bituminous coal has small pore size, large surface area
and the highest bulk density. Lignite carbon has the largest pore size, least surface area and
the lowest bulk density (Eckenfelder, 2000).
The ability of activated carbon to adsorb pollutants is a function of both the
characteristics and concentration of the pollutants and the temperature. Generally, the
amount of material adsorbed is determined as a function of concentration at a constant
temperature, and the resulting function is called an adsorption isotherm. The most common
adsorption isotherm equations used in water and wastewater treatment are Freundlich
isotherm and Langmuir isotherm.
Freundlich isotherm:
x
1/n
= K f . Ce
Where:

Eq. 2.4

m
x/m : amount adsorbate adsorbed per unit of carbon
Ce : equilibrium concentration of adsorbate in solution after adsorption
Kf, n : empirical constants
Langmuir isotherm:
x
ab. Ce
=
m
1 + bCe

Where:

Eq. 2.5

x/m : amount adsorbate adsorbed per unit of carbon

Ce : equilibrium concentration of adsorbate in solution after adsorption
a, b : empirical constants

Activated carbon can be classified into two types: powdered activated carbon
(PAC) which has a diameter of less than 200 mesh and granular activated carbon (GAC)
which has a diameter greater than 0.1 mm. GAC is usually used in fixed bed column while
PAC is added to the effluent from secondary biological treatment to serve as a polishing
process. Another application of PAC is direct addition of PAC to aeration basin of the
activated sludge process.
2.3.2

Biological activated carbon process

Rice and Robinson (1982) used the term Biological Activated Carbon (BAC) for
the water and wastewater treatment system in which aerobic microbial activity is
deliberately promoted in an activated carbon adsorber system. Both types of activated
carbon, PAC and GAC, can be used in the BAC process. In this study, the term BAC
process is referred to the process in which PAC is added directly to the bioreactor.
Many researchers have suggested that a synergy exists between activated carbon
and microorganism. Therefore, the BAC process could remove organic compounds more
efficiently than what would be expected from either biodegradation or adsorption alone.

13

The addition of PAC has served several process advantages including:

(1) system stability during shock loads,
(2) reduction of refractory pollutants,
(3) color and ammonia removal and
(4) improved settleability (Metcalf and Eddy, 1991).
The dosage of PAC and the mixed-liquor-PAC-suspended-solids concentration are
related to the sludge age as follows:
Xi c
Eq. 2.6
Xp =
Where :

Xp : equilibrium PAC MLSS content, mg/L

Xi : PAC dosage, mg/L
c : solid retention time, d
: hydraulic retention time, d

Carbon dosage ranges typically from 20 to 200 mg/L. With higher sludge ages, the
organic removal per unit of carbon is enhanced, thereby improving the process efficiency.
Reasons cited for this phenomenon include (Eckenfelder, 2000):
(1) additional biodegradation due to decreased biological toxicity or inhibition via
activated carbon,
(2) degradation of normally nondegradable substances due to increased exposure
time to the biomass through adsorption on the carbon,
(3) replacement of low-molecule-weight compounds with high-molecule-weight
compounds, resulting in improved adsorption efficiency and lower toxicity.
Pirbazari et al. (1996) explained the removal of contaminants in BAC process was
a combination of biodegradation and adsorption. Biodegradation of organics occurred both
in suspended form in the liquid form and attached form at the biofilm developed on the
carbon particles. The major factor for achieving high organic removal was conceivably the
retention time of enzymes capable of degrading the xenobiotic compounds. The extended
contact time between the microbial biota and organic solutes enhanced the biodegradation
and/or mineralization of the contaminants via microbial enzyme attack.
2.3.3

MBR process coupled with BAC process

The combination of BAC process and MBR process has gained special attention
from researchers because the PAC addition in this hybrid system would play the two roles
simultaneously: enhancement of pollutant removal and reduction of membrane fouling.
Seo et al. (1997) investigated the sorption characteristics of biological powdered
activated carbon (BPAC) in a hybrid membrane process that was accomplished by
introducing PAC into a MBR with external cross flow microfiltration. The system was
used for reclamation of secondary sewage effluent. PAC dose used in the system was 0.5
g/L. The results showed that a removal of 66% was achieved for refractory organic
materials. The sorption capacity of the BPAC was almost four times higher than that of
fresh PAC. The removal efficiency tends to increase when increasing PAC concentration.
No information about membrane fouling was reported in this study.

14

Pirbazari et al. (1996) studied the treatment of landfill leachate using a hybrid
technology known as the ultrafiltration-biologically active carbon (UF-BAC) process. The
system consisted of a bioreactor and a cross-flow ultrafiltrtion unit. The wastewater was
fed continuously into the reactor along with PAC slurry. The contents of slurry were
continuously pumped through the filtration unit. This configuration was similar to the
externally pressurized cross-flow MBR configuration. The process removal efficiencies
were in range of 95 - 98% in term of COD and exceeded 97% for specific organic
pollutants. The process compared well with the powdered activated carbon treatment
(PACT) process in terms of organic removal and produced higher quality effluent in terms
of suspended solids (100% removal). The study demonstrated that addition of 1% PAC
mitigated the permeate flux deterioration. Without PAC addition, the permeate flux
reduced to zero within the first hour of process operation. The mechanism for mitigation of
the permeate flux deterioration was explained by the formation of a PAC particular layer
on the membrane surface. This permeable PAC particular layer would filter out microbial
cells and colloids, preventing them reaching the membrane surface to cause a biofilm on
the membrane surface (Figure 2.5).
Kim et al. (1998) conducted a study to compare ultrafiltration characteristics of
activated sludge and biological activated carbon (BAC) sludge. The activated sludge
reactor was fed with synthetic wastewater using glucose as carbon source. The BAC sludge
was prepared by adding PAC to activated sludge reactor for one month. The biomass
suspended solids of the two systems were maintained equal at 3000 mg/L. The PAC dose
varied in range of 0.5 1.8 mg/L. The two kinds of sludge were then experimented
ultrafiltration characteristics using a batch stirred cell unit at constant transmembrane
pressure of 1 bar and stirring speed of 200 rpm. The results showed that the addition of
PAC increase the permeate flux in spite of the increase of suspended solid and reduced floc
size. This finding was explained by the fact that BAC sludge have lower compressibility
and higher porosity than normal activated sludge and BAC sludge have lower content of
EPSs inside the floc than activated sludge. The authors also confirmed the PAC addition as
a mere filter aid resulting in flux decline.
It is noted that membrane filtration experiment of the above studies were conducted
as crow-flow ultrafiltration. No study of flux enhancement effect of PAC addition in
submerged MBR and microfiltration has been found in the literature so far. Because the
mechanisms of the formation of dynamic cake layer in the two cases would be quite
different, effect of PAC addition in submerged MBR to membrane fouling is still
questionable.

15

Chapter 3
Methodology
3.1

Materials and microorganisms

3.1.1

Feed wastewater

In this study, synthetic wastewater was used as feed wastewater. Lubricant oil was
used to represent the oil fraction in the oily synthetic wastewater. Data from a survey for
various gas stations in Thailand (Table 2.1) showed that O&G concentration and BOD of
carwash wastewater were in range of 7.8 280.5 mg/L and 10 1220 mg/L respectively.
The oil concentration in this study was varied in range of 150 - 600 mg/L. Glucose was
supplemented to the feed wastewater to simulate the carbon source other than the oil in the
real wastewater. BOD contributed by glucose in the feed wastewater was maintained at
100 mg/L throughout all the experiments.
Table 3.1 Composition of the feed wastewater
Component
Concentration(1) (mg/L)
Oil
150(2)
Emulsifier
13.6(3)
Glucose
98.74(4)
K2HPO4
880
KH2PO4
440
NH4Cl
105
150
MgSO4.7H2O
ZnSO4.7H2O
5
FeSO4
5
MnSO4
5
CaCl2
20
(NH4)6Mo24.4H2O
0.02
CuSO4
0.02
CoCl2
0.02
(1)
Concentration of mineral salts was adjusted proportionally to COD of the feed
wastewater.
(2)
Oil concentration was varied in range of 150 600 mg/L.
(3)
Emulsifier concentration was varied proportional to oil concentration.
(4)
Glucose concentration was maintained constant at all experiments, providing a BOD
value of approximate 100 mg/L.
The oil fraction, provided in form of oil/water emulsion, was prepared by adding
1.0 g of oil and 100 mL of emulsifier solution (0.1% volume) to tap water to make one liter
of the stock oil/water emulsion solution. The mixture was blended by the Heidolph Stirrer
RZR1 (Germany) at the speed of 1500 rpm for 4 hours. Commercial lubricant Performa
SAE 20W-50, manufactured by Petroleum Authority of Thailand (PTT), was used in the
study. The emulsifier used was Ter 10 12A, a non-ionic emulsifier, which is principally the
main component of commercial car wash detergent. The stock oil/water emulsion was then
diluted to desired oil concentration and was added glucose and nutrient salts to ensure
favorable conditions for microorganism growth. Typical composition of the feed
wastewater is presented in Table 3.1.

16

Relative contributions of COD and BOD5 (20oC) from the oil, glucose and
emulsifier of a typical feed wastewater sample having oil concentration of 150 mg/L are
shown in Figure 3.1.

From oil (150 mg/L)

COD = 422 mg/L
BOD = 144 mg/L

Feed wastewater
COD = 552.6 mg/L
BOD = 261 mg/L

From glucose (98.74 mg/L)

COD = 102 mg/L
BOD = 97 mg/L

From emulsifier (13.6 mg/L)

COD = 28.6 mg/L
BOD = 20 mg/L
Figure 3.1 Relative contributions of COD and BOD from the oil, glucose and emulsifier of
a typical feed wastewater sample having oil concentration of 150 mg/L
3.1.2

Powdered activated carbon

The activated carbon used in this study was untreated powdered activated carbon
(PAC) supplied by Sigma Chemical Company. Major properties of the PAC are presented
in Table 3.2. Nominal size distribution of the PAC was in range of 100 400 mesh that is
equivalent to 37 150 m. The PAC was boiled and washed several times with distilled
water to remove impurity and then dried at 105oC and kept in desiccator before used.
Table 3.2 The major properties of the PAC
Parameter
Surface area
Mesh size
Methylene blue adsorption
Iodine number
pH
Ash content
Source: SIGMA Chemical Co., CAS # : 64365-11-3
3.1.3

Value
750 m2/g
100 400 mesh
10 15 g/100g
800 mg/g
9 - 11
6%

Microorganisms

Activated sludge collected at aeration tank of a wastewater treatment plant was

used as microorganism seeding. The sludge was acclimatized to the oily wastewater at oil
concentration of 150 mg/L in a batch reactor with fill-and-draw process for two months.
3.2

Overall experimental course

The experimental works can be divided into three main parts: PAC adsorption
isotherm experiment, batch experiment and MBR experiment. Overall experimental course
is outlined in Figure 3.2

17

PAC Adsorption
Isotherm Experiment

Batch Experiment

BAC Process
Run

AS Process Run

MBR Experiment

Optimum HRT
run

Shock loading
run

Long run A

Long run B
(with PAC addition)

Figure 3.2 Overall experimental course

18

3.3

Adsorption isotherm experiments

This experiment was to determine the adsorptability of the PAC on the oil fraction
of the feed wastewater. The experiment was conducted at the temperature of 25 0.2oC
using a series of 500-mL flasks containing 250 mL of sample. The flasks were agitated by
a rotatory shaker at 100 rpm. The adsorptability was measured in term of COD. First, the
equilibrium time experiment was carried out to determine the time needed for the
adsorption process reaching the equilibrium state. In this experiment, initial adsorbate
concentration and PAC dose were maintained constant while agitation time was varied.
The equilibrium time (4h) was used as agitation time in the adsorption isotherm
experiment which was conducted at different initial adsorbate concentrations and PAC
doses. The experimental conditions are presented in Table 3.3.
Table 3.3 Experimental conditions for equilibrium adsorption time test

Equilibrium time experiment

Adsorption isotherm experiment
3.4

Initial COD
(mg/L)
343
124; 240

PAC dosage
(mg/L)
100
20, 50, 100, 200

Contact time
(h)
1, 2, 3, 5, 8, 12
4

Batch experiments

These experiments were conducted to determine preliminary parameters of the

biodegradation of the oily wastewater through activated sludge process (AS) and biological
activated carbon (BAC) process.
The batch reactors were operated at sequencing batch reactor (SBR) mode in which
each cycle went through the four main steps: fill, react (aeration), settle and draw. Twoliter-glass-bottles were used as model reactors. There were four reactors: one was run as
activated process (AS) and to the remaining reactors PAC was added at different doses of
100, 300 and 500 mg/L.
The reactors were mixed and aerated by compressed air through stone air diffusers
to maintain suitable mixing and to supply sufficient dissolved oxygen for microorganism
growth (DO = 2 - 4 mg/L). The pH of the reactors was controlled within the range of 6.2
8.0 by adding NaOH when needed. The reactors were aerated at different periods of time
to achieve various HRTs. Calculation of HRT is followed Equation 3-1 (Grady et al,
1999).
.V
HRT =

Eq. 3.1

Q
Where:
V: reactor volume (2 L)
Q : volume of effluent withdrawn per cycle = volume of influent filled per cycle =1L
: aeration time per cycle (h)
The reactors were then let to settle for 2 hours. After the settling step, one liter of
the supernatant from each reactor was decanted for COD and O&G analyses. Each reactor
was then filled with one liter of the feed wastewater and aerated to start the next cycle.

19

The reactors were run at five different HRTs of 3, 6, 10, 13 and 16 hours. Each
HRT run lasted for four days. The feed wastewater used in the batch experiments had the
oil concentration of 150 mg/L. The reactors were operated without sludge wastage except
for sampling purpose.
3.5

Membrane bioreactor experiments

3.5.1

Membrane bioreactor set-up

Laboratory scale membrane bioreactor was used in this study. Schematic diagram
of the experimental set-up for the membrane bioreactor experiments is presented in Figure
3.3. Photograph of the lab-scale reactor is presented in Figure 3.4. The reactor was made of
transparent acrylic pipe having diameter of 100 mm. The working volume of the reactor is
6 L. A U-shaped hollow fiber microfiltration membrane was immersed in the reactor. The
membrane was manufactured by Sterapore Company (Japan) having a pore size of 0.1
m Characteristics of the membrane module are given in Table 3.4.
Table 3.4 Characteristics of the membrane module
Characteristic
polyethylene
hollow fiber
0.1 m
0.42 m2

Membrane material
Membrane type
Pore size
Surface area

The influent was fed at the bottom of the reactor from the level control tank. This
tank operated based on an automatic valve that controlled the flow-in by a floating buoy.
This set-up allowed the feed wastewater flow into the reactor at the same flow rate as the
influent being withdrawn. The effluent was withdrawn through the membrane module by a
roller pump. Flow rate of the permeate was adjusted by a pump speed controller. The
reactor was continuously aerated by compressed air through stone diffusers placed at the
bottom of the reactor.
The reactor was operated with periodic air backwashing. The alternative operation
of filtration and air backwashing was controlled by an intermittent controller (timer) and
solenoid valves. Each operational cycle consisted of 25 minutes of filtration followed by 3
minutes of air backwashing at air pressure of 300 kPa and 1 minute for releasing the
pressure in the system before starting next cycle.
3.5.2

Experimental conditions

The MBR experiments were carried out through four runs named as Optimum HRT
Run, Shock Loading Run, Long Run A and Long Run B. Operating conditions of the four
runs are presented in Table 3.5.
(1). Optimum HRT Run: The aim of this run was to determine appropriate HRT
for the MBR system. The oil concentration of the feed wastewater in this run was 150
mg/L. Based on the results from the batch experiments, four HRT values of 8, 6, 4 and 2 h
were experimented.

20

Timer
Hg manometer

Air
backwash

F
Air pressure
Regulator

Solenoid
valve

Pump

Feed tank

Level control
tank

Effluent
tank

Membrane
module
Influent
Compressed Air
Air diffuser

Figure 3.3 Membrane bioreactor setup

(2) Shock Loading Run: In this run, stability as well as capability of the treatment
system against shock loading was experimented. The system was run at the HRT = 4h as
selected from the previous run with increasing oil loading. The oil concentration in the
feed wastewater was increased stepwise from 300 mg/L to 600 mg/L with an increment of
150 mg/L.
(3) Long Run A: This run was to investigate the membrane clogging course under
long term basis. The reactor was run at HRT = 4 h and oil concentration of 300 mg/L. This
run was ceased when there was a sharp increase in transmembrane pressure.
(4) Long Run B: In this run, PAC was added to the reactor at dose of 2 g/L to
develop BAC sludge in the MBR reactor. The run was to evaluate the effect of the PAC
addition on the performance of the MBR reactor in terms of reduction of membrane
clogging rate and permeate quality improvement. This run was conducted at the same
operational conditions as the Long Run A., i.e. at HRT = 4 h and oil concentration of 300
mg/L. This run was ceased when there was a sharp increase in transmembrane pressure.
This made the comparison between the two runs possible.

21

Figure 3.4 Laboratory scale MBR system to treat oily wastewater

There was no sludge wastage except being sampled 10ml daily during Optimum
HRT run and Shock Loading Run because the operational conditions changed in a fairly
short time. The solid retention time (SRT) was maintained at 50 days through the Long
Run A and B by wasting 120 mL of the mixed liquor daily. Calculation of the SRT is as
follows:
Vr . X
Vr
SRT = =
Eq. 3.2
Qw.Xw + Qe . Xe

Qw

Where :
Vr : reactor volume = 6 L
X : MLSS in the reactor
Qw : wastage sludge flow rate = 0.12 L per day
Xw : MLSS in the wastage sludge flow (X = Xw)
Qe : Effluent flow rate
Xe : MLSS in the effluent = 0
For Long Run B, virgin PAC was supplemented to the reactor daily to compensate
the PAC being withdrawn with the sludge.

22

The pH of the reactor was maintained in range of 6.2 to 8 by adding NaOH when
needed. DO was adjusted in range of 2 4 mg/L. After each run, the membrane underwent
chemical cleaning to restore its permeability.
Table 3.5 Operational condition of the MBR experiments
Run

Optimum
HRT Run

Influent oil
concentration
(mg/L)
150
150
150
150

HRT
(h)
8
6
4
2

SRT
(day)

PAC dose
in reactor
(g/L)

600

Shock
Loading Run

300
450
600

4
4
4

600

Long Run A

300

50

Long Run B

300

50

3.5.3

Parameters to be
measured
Influent COD,
effluent COD and
O&G, reactor O&G,
MLSS, TMP
Influent COD,
effluent COD and
O&G, reactor O&G,
MLSS, TMP
Influent COD,
effluent COD and
O&G, reactor O&G,
MLSS, TMP, EPS,
Rm, Rc, Rf
Influent COD,
effluent COD and
O&G, reactor O&G,
MLSS, TMP, EPS,
Rm, Rc, Rf

Measured parameters in the MBR experiments

COD of the influent was analyzed to monitor the strength of the prepared feed
wastewater. COD and O&G of the permeate were determined to evaluate the effluent
quality. MLSS analysis was performed to check the microorganism growth. O&G
concentration of the mixed liquor was also determined to inspect the accumulation of the
oil in the reactor if any. Variation of transmembrane pressure was recorded to monitor
membrane-clogging process.
For Long Run A and B, content of extracellular polymeric substances (EPS) of the
activated sludge was additionally determined to inspect the relationship between EPS and
membrane clogging process if any. Various components of membrane resistance
contributing to membrane clogging were also measured as described in details in the next
section.
3.5.4

Membrane cleaning

The membrane after each run was taken out of the reactor for cleaning. The
membrane was first flushed with tap water to remove the cake layer attaching on the
membrane surface. Next, the membrane was soaked in NaOH 2% solution for 12 hours.
The membrane was then washed with tap water and soaked in HNO3 1% solution for 4
hours. The membrane subsequently washed with tap water again and was measured
membrane resistance before used in the next run.
23

3.5.5

Membrane resistance measurement

Membrane resistance was measured based on the resistance-in-series model (Choo

and Lee, 1996) according Equation 2.1 and 2.2.
Applying this model, membrane resistance was measured by filtrating with pure
water at different filtration fluxes and recording the corresponding transmembrane
pressures. Membrane resistance was derived from the slope of the linear curve of P
versus J as described by the following equation:
P = Rt. . J + Po

Eq. 3.3

Where:
Po is the initial pressure to overcome the membrane set-up system resistance
For further understanding of various components of membrane resistances causing
the membrane clogging, detailed membrane resistance measurements after Long Run A
and B were conducted in accordance with the procedure suggested by Kim et al. (1998).
The total resistance (Rt) was measured right after the run with the membrane still in its
clogging condition. Rm+ Rf was obtained by measuring the resistance of the membrane
after being washed with tap water to remove the cake layer. The membrane resistance at
the beginning of the run (after chemical cleaning) was considered as Rm. Value of Rc was
derived from Rt, Rm and Rf using Equation 2.2.
3.6

Analytical methods

The analyses of COD, BOD, O&G and MLSS were followed the procedures
recommended by Standard Methods (APHA et al., 1995). List of these methods is
presented in Table 3.6.
Table 3.6 Analytical methods
Parameters
COD
Oil and grease
Total suspended solid
(MLSS)

Principle
Closed reflux titrimetric method
n-Hexane extraction
Partition-Gravimetric method

Code
Standard methods, 5220 C

Dried at 103 105oC

Standard methods, 2540 D

Standard methods, 5520 C

For determination of the oil concentration in the reactor, 100 mL of the mixed liquor
sample was filled in a one-liter extraction funnel and was let for settling in 30 minutes. The
settled sludge was withdrawn from the bottom of the funnel. The supernatant was analysed
for O&G by Partition-Gravimetric method.
Thermal extraction method was used to extract EPS (Morgan et al., 1990). A
measured volume of sludge solid was concentrated by a centrifuge at 2000 rpm for 10
minutes. The sludge was then resuspended in distilled water before being heated at 80oC
for 1 h. The solution that contains the extracted EPS was harvested by centrifuging first at
2000 rpm for 10 minutes and then at 5000 rpm for 20 minutes to remove the sludge solids.
The extracted EPS solution was then analysed for total EPS and EPS composition
(carbohydrate and protein). Total EPS was determined by precipitated out from the

24

solution by adding three parts of solvent mixture of acetone and ethanol (3 vol: 1 vol) to
one part of the extracted EPS solution and then kept at 4oC overnight. The quantity of the
extracted EPS was determined as suspended solid using filtration method described in
Standard Method 2540 D. Contents of carbohydrate and protein in the extracted solution
were determined using spectrophotometric method at wave lengths of 480 nm and 570 nm
respectively.

25

Chapter 4
Results and Discussions
4.1

Adsorption isotherm of the PAC

Equilibrium adsorption time of PAC to the oil was determined by varying contact
times of the adsorption tests. The results are presented in Table A.1 and illustrated in
Figure 4.1. The results showed that the adsorption process reached the equilibrium status
somewhere between two and four hours. The COD values of the supernatant at the contact
time longer than two hours were changed slightly in range of 164 mg/L to190 mg/L.
Therefore, it is suitable to take 4 hours as the equilibrium time for the adsorption isotherm
experiments.
400
Equilibrium COD (mg/L)

350
300
250
200
150
100
50
0
0

10

12

14

Contact time (h)

Figure 4.1 Variation of equilibrium COD vs. different contact times

(PAC dose = 100 mg/L; T = 25oC; agitation speed = 100 rpm)
The adsorption isotherm was determined at initial COD of 124 mg/L and 240 mg/L
and at PAC doses ranging from 20 mg/L to 200 mg/L. The results were presented in Table
A.2. The experimental data were plotted in accordance with Freundlich and Langmuir
isotherm models (Figure 4.2 and 4.3). For Freundlich isotherm, the 1/n value of 0.22 was
within the magnitude of significance of reported isotherms. The reported 1/n values for
various priority pollutants are in range of 0.16 2 (Montgomery, 1985). Comparison of the
empirical values for Langmuir isotherm was impossible because of the lack of similar
work in the literature.
Based on the R-square values, the Langmuir isotherm was more appropriate model
for the adsorption of lubricant oil onto PAC. The R-square value for Langmuir isotherm
was 0.952, which is approaching 1, while that for Freundlich isotherm was only 0.689. It is
noted that lubricant oil mainly consists of long chain compounds which have large
molecule size. This would be the reason why the adsorption of lubricant oil onto PAC
follow the Langmuir isotherm model which is based on the assumption that the adsorbate
only can be adsorbed a monolayer onto the surface of the adsorption medium.

26

x/m (mg/g)

1000

x
--- = Kf Ce1/n
m
Kf = 225.84
1/n = 0.2244

x/m = 225.84Ce0.2244
R2 = 0.6892

100
10

100

1000

COD equilibrium, Ce (mg/L)

Figure 4.2

Experimental data plotted according to Freundlich isotherm

(T = 25oC, agitation speed = 100 rpm, contact time = 4 h)

0.35
0.30

Ce/(x/m) (g/L)

0.25
0.20
Ce

0.15
0.10
Ce/(x/m) = 0.0341 + 0.0012Ce

0.05

R2 = 0.952

------- = ---- + ---- Ce

(x/m)
ab
a
a = 833
b = 0.352

0.00
0

50

100

150

200

250

COD equilibrium, Ce (mg/L)

Figure 4.3
4.2

Experimental data plotted according to Langmuir isotherm

(T = 25oC; agitation speed = 100 rpm, contact time = 4 h)

Batch experiments

Batch experiments were conducted using four 2-liter reactors. Reactor 1 was purely
activated sludge process. In the reactors 1, 2 and 3, PAC was added at doses of 100, 300
and 500 mg/L respectively. The results are presented in Table A.3. Averaged values of the
experimental data is summarized in Table 4.1 and illustrated in Figure 4.4 and 4.5.
For AS process (Reactor 1), the removal efficiency of COD increased from 64% to
86% when HRT increased from 3h to 16h. Similarly, the removal efficiency of O&G
varied from 67% to 92% with HRT increasing from 3h to 16h. At HRT=13h, the removal
efficiencies of COD and O&G reached 80% and 90% respectively. At this HRT, the COD

27

of the effluent was 109 mg/L and that of O&G was 15 mg/L. The results revealed that
biodegradation of oily wastewater took place at significant level and treatment of oily
wastewater through biological process is possible.

MLSS
(mg/L)

CODeff.
(mg/L)

O&Geff.
(mg/L)

16

3220

78.4

12

86

92

13

2900

109

16

80

90

10

3140

126

24

77

84

3270

165

37

70

75

3310

197

50

64

67

Reactor 2
(PAC=100 mg/L)

16

3230

92.3

83

94

13

3050

113

19

80

87

10

3140

123

27

78

82

3240

172

39

68

74

3250

198

55

64

64

Reactor 3
(PAC=300 mg/L)

16

3390

87.6

11

84

93

13

3200

105

14

81

91

10

3220

126

26

77

83

3340

154

33

72

78

3410

176

48

68

68

16

3680

77.4

12

86

92

13

3460

111

15

80

90

10

3360

111

20

80

87

3530

142

34

74

78

3570

161

39

71

74

Reactor 1
(without PAC
addition)

HRT
(h)

Reactor 4
(PAC=500 mg/L)

Table 4.1 Average results of the batch experiments (Inf. COD = 550 mg/L; Inf.O&G =
150 mg/L)
COD removal O&G removal
(%)
(%)

Note: MLSS including PAC and biomass

There was no distinguished difference between the performance of BAC process
(Reactors 2, 3 and 4) and AS process at HRTs longer than 10h. At HRT = 13h, the COD
removal efficiency of BAC process was in range of 8081% in comparison with that of AS
process of 80%. The corresponding values for O&G were 8791% and 90%. The same
situation was observed at HRT = 16h. This would be due to the effect of biodegradation
process was predominant over the effect of adsorption process at long contact times. The
predominant effect of biodegradation could also be the reason why the performance of
Reactor 2, which had PAC dose of 100 mg/L, was not improved in comparison with AS
process at HRT of 10, 6 and 3h.

28

100
95
90
COD removal (%)

85
R1 (w ithout PAC addition)
80

R2 (PAC = 100 mg/L)

75

R3 (PAC = 300 mg/L)

70

R4 (PAC = 500 mg/L)

65
60
55
50
0

10

12

14

16

18

HRT (h)

Figure 4.4
Variation of COD removal efficiency vs. HRT
(Influent COD = 550 mg/L; Influent O&G = 150 mg/L)
100
95

O&G removal (%)

90
85
R1 (w ithout PAC addition)

80

R2 (PAC = 100 mg/L)

75

R3 (PAC = 300 mg/L)

70

R4 (PAC = 500 mg/L)

65
60
55
50
0

10

12

14

16

18

HRT (h)

Figure 4.5
Variation of O&G removal efficiency vs. HRT
(Influent COD = 550 mg/L; Influent O&G = 150 mg/L)
There was a tendency of effluent quality improvement of the BAC process with
increasing PAC dose. The removal efficiencies of COD and O&G of Reactor 3 (PAC =
300 mg/L) and Reactor 4 (PAC = 500 mg/L) were almost higher than those of Reactor 1.
The COD removal efficiency of Reactor 4 increased from 71% to 80 % when HRT
increased from 3h to 10h. The corresponding values for Reactor 3 and Reactor 1 were 68%
- 77% and 64% - 77%, respectively. Similar pattern could be found for O&G. The most
pronounced enhancement was observed at PAC dose = 500 mg/L and HRT = 3h (Figure
4.6 and 4.7). It was learned from the adsorption isotherm experiment that adsorption
process reach equilibrium at contact time longer than 2h. This would suggest that the
adsorption of PAC help to remove the oil from the supernatant and therefore improve the
performance of the BAC process at short HRTs.
29

197

200

161

R4 (PAC = 500 mg/L)

165

R1 (without PAC addition)

142

150
COD (mg/L)

126
111

109

111

100

78.4

77.4

50

0
3

10

13

16

HRT (h)

Figure 4.6

Comparison of COD removal efficiency between AS process

and BAC process (PAC = 500 mg/L)

60
50

O&G (mg/L)

R4 (PAC = 500 mg/L)

39

40

R1 (without PAC addition)

37
34
24
20

20

16

15

12

12

0
3

10

13

16

HRT (h)

Figure 4.7

Comparison of COD removal efficiency between AS process

and BAC process (PAC = 500 mg/L)

The results from the batch experiments suggested that the MBR experiments should
be conducted at HRTs shorter than 10h because the removal efficiency of MBR process is
expected higher than AS system. Another factor should be considered was the PAC/MLSS
ratio. For Reactor 4 (PAC = 500 mg/L), the averaging value of MLSS was about 3500
mg/L, therefore, the PAC/MLSS ratio was roughly 1/7. It is suggested that PAC should be
experimented at higher dose because MLSS in the MBR is much higher than that of AS
process.

30

4.3

MBR experiments

4.3.1

Membrane resistance measurement

Before used in the experiments, the membrane was measured membrane resistance.
Membrane resistance of the membrane after chemical cleaning were measured as described
in Section 3.5.4 before the next run. Detail data of membrane resistance measurements are
presented in Appendix B. Membrane resistances of the new membrane and the membrane
after undergoing chemical cleaning are given in Table 4.2 and illustrated in Figure 4.8.
Table 4.2 Membrane resistances of the new membrane and the membrane
after chemical cleaning
Membrane resistance
(1/m)
8.95x1011
8.73x1011
8.98x1011
8.60x1011
10.55x1011

New membrane
After Optimum HRT run
After Shock loading run
After Long run A
After Long run B

With an exception of the Long run B, the membrane resistances were almost
recovered to initial value of the new membrane. The membrane resistances after chemical
cleaning for Optimum HRT run, Shock loading run and Long run A were in range of
8.60x1011 - 8.98x1011 1/m, less than 3.9% different in comparison with the initial value
of the membrane. Therefore, these values could be considered as the same magnitude of
significant as the resistance of the new membrane of 8.95x1011 1/m, i.e. the membrane was
almost recovered to its original conditions after chemical cleaning. Visually, the cake layer
attaching on the membrane surface was removed mostly by flushing with tap water. When
the membrane was soaked in sodium hydroxide solution, the solution became turbid and
brownish yellow particles could be observed in the solution. This means that sodium
hydroxide solution took effect on removing the particles out of the pores of the membrane.
The acid nitric solution remained clear after membrane soaking time. This suggests that the
acid solution dissolved the substances attaching on the membrane and/or the foulants had
been removed mostly by the alkalis solution. However, the used membrane could not be
retrieved back to the pure white color of the new membrane. The used membrane became
slightly yellowish white.
For Long run B, the only run that PAC was added to the reactor, the membrane
resistance could not be retrieved back to the new membrane resistance by chemical
cleaning although additional cleaning was applied. In addition to the normal chemical
cleaning procedure, the membrane after Long run B was undergone an additional soaking
time of 12h in nitric acid solution in an attempt to recover its membrane resistance.
Membrane resistances after each step of chemical cleaning course after Long run B are
presented in Table 4.3. The data showed that with only the alkalis solution, the membrane
resistance (12.58x1011 1/m) was still 40.5% higher that of the new membrane. Acid
solution soaking significantly reduced the resistance to 10.55x1011 1/m, about 17.9%
higher than that of the new membrane. However, in spite of the long contact time for acid
solution soaking, the membrane could not be retrieved back to its initial membrane
resistance. This would suggest that the membrane pores in the case of Long run B be

31

plugged by submicron carbon particles in addition to the organic components and the
carbon particles be hard to be removed by NaOH and HNO3 solutions. This would be the
reason why the membrane resistance could not be recovered in the case of Long run B. In
future works, composition of the substances attaching on the membrane surface should be
determined somehow for better understanding of the cause of membrane fouling.

Membrane resistance (x1011 1/m)

12

+17.9%

10

-2.5%

+0.3%

-3.9%

8
6
4
2
0
New
membrane

Figure 4.8

After
Optimum
HRT run

After Shock After Long

loading run
run A

After Long
run B

Resistance of the membrane before used and after chemical cleaning

Table 4.3 Membrane resistances after each step of chemical cleaning course after Long
run B

After soaking in NaOH solution

After soaking time of 4h in HNO3 solution
After additional soaking time of 12h in HNO3 solution
4.3.2

Membrane resistance
(1/m)
12.58x1011
11.56x1011
10.55x1011

Optimum HRT run

The optimum HRT run was conducted to determine suitable HRT for the MBR
system to treat the oily wastewater. The run was carried out at four HRTs of 8, 6, 4 and 2h.
O&G concentration in the influent was maintained at 150 mg/L through out this run. The
experimental results are presented in Table A.4 and illustrated in Figure 4.9, 4.10, 4.11 and
4.12.
The MBR system produced excellent quality effluent at all experimented HRTs.
With the COD in the influent ranged from 495 607 mg/L, the effluent COD was in range
of 26.3 59.8 mg/L, providing the removal efficiency about 89.9% - 95.5%. In term of
O&G, the removal efficiency was 97.8% - 99.9%, with O&G concentration measured by
n-Hexane partition-gravimetric method was in range of 0.2 3.2 mg/L. Visually, the
effluent was very clear and oil free. The oil fraction contributing to the O&G concentration

32

of the effluent was the soluble fraction. It is noted that the removal efficiencies in terms of
COD and O&G were stable and not dependent upon the experimented HRTs of 8, 6, 4 and
2 h.

700

COD (mg/L)

600
500
400

HRT=8h

HRT=6h

HRT=4h

300

HRT=2h
Influent COD

200

Effluent COD

100
0
1

9 10 11 12 13 14 15 16

Time (day)

Figure 4.9

Variation of COD of the influent and effluent during Optimum HRT run

200

O&G (mg/L)

150
HRT=8h

HRT=6h

HRT=4h

HRT=2h

100
Influent O&G
Reactor O&G
Effluent O&G

50

0
1

10 11 12 13 14 15 16

Time (day)

Figure 4.10

Variation of O&G in the reactor and in the effluent

during Optimum HRT run

In comparison with the results from the Batch experiments at HRTs of 6 and 3 h,
the performance of the MBR system at HRT = 4h was much better. The effluent COD of
AS process at HRT of 6 and 3 h were 165 and 197 mg/L respectively, while that of the
MBR system was averagely 45.8 mg/L. This improved performance of the MBR would be
explained by the higher MLSS of the MBR system and the enhanced removal by
membrane separation. The MLSS values of the MBR system varied from 6040 mg/L to
8700 during the Optimum HRT run (Figure 4.12) while the MLSS of the AS process was

33

about 3000 mg/L. The biodegradation of the oil would also be enhanced by the membrane
separation which could concentrate the oil in the reactor and therefore provide better
contact condition between the oil and the microorganisms.
There was a pronounced increase in the reactor O&G concentration at HRT = 2h.
The reactor O&G concentration at HRT = 2h increased from 138 mg/L to 179 mg/L, which
was higher than the influent O&G of 150 mg/L (Figure 4.10). Therefore, it is necessary to
establish a mass balance to check whether the oil was significantly accumulated in the
reactor. Mass balance for the total oil inputted from the influent and the oil remaining in
the reactor was illustrated in Figure 4.11. The oil came out of the system through the
effluent was omitted because it was negligible. The data shows that the oil remaining in the
reactor did not increase in parallel with the increasing amount of oil fed into the reactor up
to 95.3g but remained at low level of 0.4 1.1g. This means that most of the oil was
degraded within the reactor. The increase of the O&G concentration in the reactor at HRT
= 2h was small (0.4g) in comparison with the increase in oil loading of 5.45g oil/day
(Table 4.4). However, this trend should be monitored at higher oil loading and at long-term
basis to verify the limit of the system
120
100

Total oil input from the influent

Oil remaining in the reactor

O&G (g)

80
60
40
20
0
0

Figure 4.11

8
10
Time (day)

12

14

16

O&G mass balance of Optimum HRT run

Table 4.4 Oil loading of Optimum HRT run

Operating time
(day)

Average HRT
(h)

14
58
9 11
12 16

7.94
6.03
4.04
2.00

Average O&G
loading
(g O&G/day)
2.72
3.58
5.35
10.80

Average O&G
remaining in reactor
(g O&G)
0.50
0.48
0.57
0.97

Figure 4.12 presents the variation of the transmembrane pressure during Optimum
HRT run. The TMP was rather stable in range of 9.6 kPa 10.7 kPa at HRT = 8h, 6h and
4h with a small increment when increasing the flow rate. However, when the system was
run at HRT = 2h, which equaled to the effluent flow rate of 3 L/h, the TMP increased
rapidly from 12.1 to 22.7 kPa and it was hard to control constant permeate flux. This

34

would be due to the formation of the polarization cake layer become so quickly at this
hydrodynamic condition, resulting in the sharp increase in TMP. However, because the
membrane had been operated for 11 days before operated at HRT = 2h, it would also be
possible that the membrane clogging resulted from the long time running. Therefore, it is
necessary to exam the membrane clogging process on a long term basis with the same
biological and hydrodynamic conditions. Because the effluent quality did not change with
various HRTs, HRT = 4h were a suitable selection for the next runs.
10000

20

TMP

9000

MLSS

8000

TMP (kPa)

7000
15

6000
5000

10

4000
3000

HRT=8h

HRT=6h

HRT=4h

HRT=2h

MLSS (mg/L)

25

2000
1000
0

9 10 11 12 13 14 15 16

Time (day)

Figure 4.12
4.3.3

Variation of transmembrane pressure and MLSS during Optimum HRT run

Shock loading run

The shock loading run was conducted at HRT = 4h at sudden increase of oil
loading from 300 mg/L to 600 mg/L to exam the stability of the MBR system against
shock loading. The results are presented in Table A.4 and illusted in Figure 4.11 and 4.12.
The MBR system showed good ability against shock loading. When the COD
influent varied from 1021 mg/L to 1835 mg/L and the influent O&G concentration
increased from 300 mg/L to 600 mg/L, the COD and O&G of the effluent did not change
significantly and still remained at low level (Figure 4.11 and 4.12). COD of the effluent
was in range of 11.2 mg/L to 54.1 mg/L and the O&G concentration was in range of 1.2
4.1 mg/L. This stability could be attributable to the membrane separation which retained
the oil in the reactor
It is noted that the first stage of the Shock loading run, when the influent O&G
concentration was 300 mg/L, had the same oil loading as the last stage of the Optimum
HRT run (O&G = 150 mg/L, HRT = 2h). The reactor O&G concentration in these two
stages was approximate to each other, 154 179 mg/L in comparison with 172 - 183 mg/L.
This means that the oil loading of 10g/day would be within the biodegradation limit of the
system.

35

2000
Influent COD

COD (mg/L)

1500

Effluent COD

1000

O &G = 300mg/L

500

O &G = 450mg/L

O &G=600 mg/L

0
1

Time (day)

Figure 4.13

Variation of COD of the influent and effluent during Shock loading run

The O&G concentration in the reactor increased quite quickly when the influent
changed to 450 mg/L and increased very sharply when the influent was 600 mg/L. The
average value of oil accumulating in the reactor was 4.3 g, about 20% of the daily input
from the influent of 20.9 g/day (Table 4.5). Whether the system has the ability to adapt this
high loading should be investigated in detail on long term basis.
1000
900
Influent O&G
Reactor O&G
Effluent O&G

800
O&G (mg/L)

700
600
500
400
300
200
100
0
1.0

2.0

3.0

4.0

5.0

6.0

7.0

Time (day)

Figure 4.14

Variation of O&G in the reactor and in the effluent

during Shock loading run

Because the Shock loading run was conducted in a rather short time, the parameters
of MLSS and TMP were less important. The MLSS increased from 7300 mg/L to 9100
mg/L when the organic loading increased from 10.6 g oil/day to 20.9 g oil/day. The
transmembrane pressure increased slightly from 9.3 kPa to 11.1 kPa.

36

Table 4.5 Oil loading of Shock loading run

Operating
time
(day)

Average
HRT
(h)

Average O&G
loading
(g O&G/day)

Average MLSS
(mg/L)

Average O&G
remaining in reactor
(g O&G)

13

4.1

10.6

8093

1.1

45

4.1

15.7

7574

1.6

67

4.1

20.9

8680

4.3

4.3.4

Long run A and B

The long run A and B were conducted to determine the membrane clogging course
on a long term basis for a given hydrodynamic and biological conditions (HRT = 4 h;
O&G = 300 m/L). PAC was added to the reactor at concentration of 2 g/L at the begging of
Long run B. The results are presented in Table A.6, A.7 and illustrated in Figure 4.15, 4.15
and 4.17.
PAC addtition
1200

COD (mg/L)

1000
800
Influent COD
600

Effluent COD

400

Long Run A

Long Run B

200
0
1

3 25
5 27
7 29
9 31
11 33
13 35
15
9 11 13 15 17 19 211 23
Time (day)

Figure 4.15

Variation of COD of the influent and effluent during Long run A and B

Over the time of both Long run A (20 days) and Long run B (16 days), the effluent
quality was stable at low level as expected from the results of previous runs (Figure 4.13
and 4.14). The effluent COD ranged from 29.3 - 85.9 mg/L for Long run A and 22.8
48.8 mg/L for Long run B. The range of O&G was 2.9 7.3 mg/L and 0.4 5.2 mg/L for
Long run A and B, respectively. The removal efficiencies of COD and O&G were 91.0
96.3% and 95.2 97.5%, respectively. The corresponding values for Long run B were 95.0
97.5% and 98.3 99.9%. It is noted that the effluent quality of Long run B was slightly
better than that of Long run A. This would be due to the effect of PAC addition as from
expected the results of the Batch experiments. However, the difference was not very
significant because the improvement by PAC addition was hidden by the enhanced effect
of membrane separation.

37

PAC addtition
400
Long Run A

350

Long Run B

O&G (mg/L)

300
Influent O&G
Reactor O&G
Effluent O&G

250
200
150
100
50
0
1

1 23
3 25
5 27
7 29
9 31
11 33
13 35
15
9 11 13 15 17 19 21
Time (day)

Figure 4.16

Variation of O&G in the reactor and in the effluent

during Long run A and B

It is interesting to look at the variation of the reactor O&G concentration (Figure

4.16). It is noted that the reactor O&G concentration of the first four days of Long run A
were significantly higher than that of the rest 16 days. In the first four days, the reactor
O&G concentration was in range of 225 380 mg/L. This would be due to the oil
accumulated from the Shock loading run. Whereas, during the rest of the run, the O&G
concentration in the reactor was in range 147 207 mg/L, which was at the same level as
the last stage of Optimum HRT run and the first stage of Shock loading run (same oil
loading of about 10 g oil per day). This revealed the MBR system had the ability to
assimilate the oil accumulated during shock loading when the loading backed to normal
level. The fact that the oil concentration in the reactor did not increase over 20 days of
operation showed that oil accumulation did not occur in the reactor.
For Long run B, the reactor O&G concentration was very low at the second day
after PAC was added to the reactor. This would result from the adsorption of the carbon.
The reactor O&G concentration still remained at low level of 98 108 mg/L from the
fourth day to the eighth day and then increased to the level of 159 182 mg/l. This would
be thought that the adsorption ability of the carbon was gradually decreased as the attached
growth developing on the carbon surface as confirmed by photograph of the BAC sludge
taken through microscope at the 14th day of Long run B (Figure 4.17). However, the
attached growth seemed not to be predominant in the reactor as most of the carbon
particles were trapped within bigger flocs (Figure 4.18). That would be the reason why
EPS concentration of the BAC sludge of Long run B showed little difference with the
activated sludge of Long run A (Table 4.6). Therefore, the enhancement in effluent quality
mentioned in previous paragraph would be attributable to adsorption effect.
As opposite to positive effects which was expected from the PAC addition to
reduce membrane fouling, the membrane clogging happened sooner in Long run B. The
transmembrane pressure increased sharply, i.e. the membrane started the clogging, after 13
days of operation in the case of Long run B. Whereas, the membrane in the case of Long
run A started the clogging after 18 days of operation. Because the hydrodynamic

38

conditions of the two runs were similar, i.e. same permeate flux, same turbulence in the
reactor, the reason for the difference should be attributable to the characteristics of the
suspension.

10 m

(a) Virgin carbon (x1100)

Figure 4.17

(b) Biofilm on carbon surface (x1100)

Biofilm development on carbon surface after 14 days of Long run B

10 m

Figure 4.18

BAC sludge after 14 days of Long run B (x580)

39

Table 4.6 Comparison of EPS content in the sludge of Long Run A and Long Run B
Sludge

EPS

AS taken at the 15th day

of Long Run A
BAC sludge taken at the 15th day
of Long Run B

Protein
Carbohydrate
mg/g MLSS

31

4.8

14

27

4.0

13

25

12000

20

10000
8000

15
6000
10
4000
5

Long Run A

Long Run B

MLSS (mg/L)

TMP (kPa)

PAC addtition

2000
0

1 23
3 25
5 27
7 29
9 31
11 33
13 35
15
1 3 5 7 9 11 13 15 17 19 21
Time (day)

Figure 4.19

Variation of transmembrane pressure and MLSS

during Long run A and B

In order to explain the difference between the two cases, it is necessary to

understand the clogging mechanism. It is noted that there was a stage that the TMP
remained very stable for both Long run A and B. As presented in Table 4.7, when the
membrane became clogged, the resistance of the cake layer was the highest component
contributing to the total resistance for both run A (39.1%) and run B (67.4%). Removal of
the cake layer could restore the membrane resistance significantly. The question is whether
the formation of the cake layer on the membrane surface happened gradually from the
beginning of the run and the cake layer became thicker and thicker with time or the
formation of the cake layer just became significant at a critical point when hydrodynamic
conditions became favorable for the formation of such a cake layer. If the former was the
case, the TMP should increase gradually from the beginning due to the increase from cake
layer resistance. This would not be true because the TMP did not increase from the start of
the run. Moreover, the MBR system was operated at intermittent air backwash which is
expected to remove the polarization cake layer at each filtration cycle. Therefore, it would
be thought that there was a point when air backwash became ineffective and the formation
of the polarization become very quickly resulting in a sharp increase in membrane
resistance. The possible cause of ineffective air backwash would be the pore plugging by
various organic and inorganic substances in the suspension which is called fouling. As long
as the pore spaces of the membrane available for the permeate flux (and also for air
backwash) were above a critical value, the TMP would not increase much and the air
backwash still remain effective. Below this critical value, the rapid formation of the
polarization cake layer would cause the membrane clogged quickly. In future works, more
40

thorough and frequent observation and measurement of both membrane fouling and cake
layer formation would give useful information for modeling the membrane clogging course
in a submerged MBR system operated with periodic air backwash.
Table 4.7 Various components of membrane resistance contributing to membrane
clogging

Run A
Run B

Rm
8.98x1011
(32.8%)
8.60x1011
(12.6%)

Membrane resistance (1/m)

Rc
Rf
11
10.69x10
7.68x1011
(39.1%)
(28.1%)
46.03x1011
13.67x1011
(67.4%)
(20.0%)

Rt
27.35x1011
(100.0%)
68.30x1011
(100.0%)

Based on the suggested membrane clogging mechanism, the worse performance of

Long run B in term of membrane clogging reduction could be explained by the fact that the
plugging of PAC particles into the membrane pores make the time at which air backwash
becomes ineffective came sooner in comparison with Long run A. It is noted that the initial
TMP of Long run B was higher than that of Long run A, 10.5 kPa in comparison with 9.2
kPa. The MLSS values of Long run A were in range of 8340 - 10020 mg/L while those of
Long run B were 9020 10660 mg/L. This slightly higher MLSS concentration would not
be the reason for the higher initial TMP of Long run B because the TMP was not greatly
dependent upon MLSS concentration. It is noted from Long run A that the MLSS
concentration varied from 8740 to 10020 mg/L but the TMP did not change. Therefore, the
increase in initial TMP of Long run B would be attributable to the PAC addition. The
virgin PAC directly added to the reactor would have a possibility to transfer to and be
trapped in the membrane pore before it could form BAC sludge. The PAC used in this
study had a nominal size range of 37 150 mg/L. Under the turbulence within the reactor,
PAC particles would be broken down to smaller size and get clogged into the pores of the
micromembrane. As discussed earlier in section 4.3.1, the clogged membrane after Long
run B was very difficult to retrieve back to its original condition by chemical cleaning.
This would be due to the carbon plugging in the membrane pores. Therefore, the
combination of PAC and microfiltration would not be suitable in term of permeate flux
enhancement. Future works on the coupling of PAC with membrane process should be
conducted with ultrafiltration.
4.4

Conceptual idea for application of MBR system in wastewater treatment and

reuse at gas station

From the results of this study, application of MBR process in wastewater treatment
and reuse at gas station would be possible. Wastewater streams at gas station basically
consists of domestic wastewater and wastewater from carwash activities. The carwash
wastewater has high content of oil and detergent resulting in very high COD value but
lacks of nutrients which are necessary for biological growth. Whereas, the domestic stream
is normally low strength and biodegradable. Moreover, the domestic wastewater normally
contains excess nutrients such as N, P and other micronutrients. Therefore, combined
treatment of these two streams in a MBR system would take advantage of excess nutrients
and biodegradable compounds in the domestic wastewater to enhance biodegradation of
the oily wastewater. Moreover, the high quality of the treated water from the MBR system
would make water reuse within carwash activities possible to reduce water cost. This
would be very interesting because carwash process requires large amount of water.
41

Schematic diagram of a suggested wastewater treatment and reuse system using MBR
process is presented n Figure 4.20.

Reused water
Emulsifier

Dirty
car

Dust
cleaning

Foaming

Dryer
Tap water

Tap water

Presoak

Rinse
water

Clean
car

Oily
wastewater

Domestic
wastewater

Settling tank

Figure 4.20

MBR system

Conceptual diagram for a wastewater treatment and reuse system using

MBR process at gas station

42

Chapter 5
Conclusions and Recommendations
5.1

Conclusions
1. The PAC used in this study showed an ability to adsorb the lubricant oil. The
equilibrium time for adsorption process was about 4h. The adsorption isotherm
of the PAC to the lubricant oil was determined following Langmuir isotherm
model.
2. There was a tendency of effluent quality improvement of the BAC process at
PAC dose = 50 mg/L and HRT = 3h in comparison to activated sludge process.
3. Application of MBR process to treat carwash oily wastewater provided
excellent quality effluent. With the influent COD ranging from 495 mg/L to
1835 mg/L, and the O&G concentration ranging from 150 mg/L to 600 mg/L,
the effluent COD still remained at low level of 11.2 mg/L to 85.9 mg/L, and the
effluent O&G concentration ranged from 0.2 7.3 mg/L.
4. The performance of the MBR process was much better than that of AS process
in treating oily wastewater. This could be explained by the higher MLSS of the
MBR system and the enhanced removal by membrane separation. The
biodegradation of the oil would also be enhanced by the membrane separation
which could concentrate the oil in the reactor and therefore provide better
contact condition between the oil and the microorganisms.
5. Visually, the treated water was very clear and oil free. The treated water meets
the industrial effluent standards of 120 mg/L for COD and 15 mg/L for O&G.
The treated water could be reused in carwash process.
6. The MBR system provided stable effluent quality against shock loading. The
system could stand for the COD loading of 10.5 g COD/L.day and oil loading
of 3.5 g oil/L.day without deteriorating the effluent quality. The MBR system
had the ability to assimilate the oil accumulated during shock loading when the
loading backed to normal level.
7. Long term run of the MBR system (without PAC addition) at COD loading of
6.0 g COD/L.day, oil loading of 1.8 g oil/L.day and permeate flux of 3.6 L/m2.h
showed no accumulation of oil in the reactor. The removal efficiency was 91.0
96.3% for COD and 95.2 97.5% for O&G. The system was operated for 18
days before the TMP increased sharply.
8. The addition of PAC at dose of 2 g/L into the reactor showed little
improvement in effluent quality. The reason would be due to the improvement
of PAC addition was hidden behind the enhanced removal by membrane
separation.
9. There was attached growth developing on the surface of the PAC but the
attached growth was not predominant in this reactor.

43

10. The addition of PAC at dose of 2 g/L into the submerged MBR system with
microfiltration made the membrane clogging happen more quickly. The hybrid
system was operated for 12 days before the TMP increased sharply in
comparison with 18 days in the case of the same system without PAC addition.
11. The membrane fouling in the cases of the MBR runs without PAC addition was
reversible as the membrane resistance was recovered back to the initial value of
the new membrane after being applied chemical cleaning. The membrane
resistance after the MBR run with PAC addition was not retrieved back to the
initial value of the new membrane but 18% higher although additional
treatment with chemicals was applied.
12. The resistance of the cake layer was the highest component contributing to the
total resistance of the clogged membrane, accounting for 39.1% in the case
without PAC addition and 67.4% in the case with PAC addition.
13. In both cases, there was a stage when the TMP remained very stable before a
sharp increase of TMP leading to the membrane clogging. This would be
explained by a hypothesis that there was a critical time when the blockage of
the membrane pores reached a level that made the air backwash ineffective, the
formation of the cake layer became intensive leading to membrane clogging.
14. Based on the above hypothesis, the negative effect of PAC addition to
microfiltration would be due to the plugging of PAC particles in the pores of
the membrane.
5.2

Recommendations
1. Based on the encouraging results of the performance of the MBR system to
treat oily wastewater, it is recommended that the treatability of MBR process
for the oilfield wastewater should be investigated. This approach would be very
interesting because the increasing environmental concern of discharging this
kind of wastewater into the natural receiving waters. The oilfield wastewater
contains various compounds originating from the crude oil such as aliphatic and
aromatic hydrocarbons, polyaromatic hydrocarbons, phenols that are
bioinhibitory and hard to be removed completely by physico-chemical process.
The usually high salinity of the oilfield wastewater and space limitation for
treatment facility on oil production installation also make the conventional
biological treatment troublesome. Therefore, the application of MBR process to
treat oilfield wastewater would be prospective because of its compact reactor
size and its ability to maintain very high solid retention time (SRT) which can
be taken as an advantage to develop slow-growing microorganisms that can
degrade biorefractory compounds and can stand for high salinity environment.
2. As the membrane clogging process and the possible accumulation of pollutants
in the BMR are long time processes, it is recommended that future researches
on MBR process should be designed on a long term run basis. Each operating
condition to be investigated should be conducted in an enough period of time so
that the membrane clogging course and other behaviors of the MBR process
such as pollutant accumulation, stability against shock loading etc. can be
observed clearly.
44

3. While many works have been done to model the membrane clogging course in
external MBR in which cross flow filtration is applied, the knowledge of
membrane clogging course in a submerged MBR is still limited. Due to the
turbulence caused by aeration, the mechanism of formation of cake layer near
the membrane surface in the submerged MBR would be totally different from
the case of cross flow filtration. It is recommended that future work should
focused on the modeling of the membrane clogging course in the submerged
MBR. An interrelating between membrane plugging process and cake layer
formation process would be good approach.
4. As doing a chemical cleaning for the clogged membrane, the substances
plugging into the membrane pores will be washed or dissolved in the cleaning
solution. It is suggested that composition and quantity of common foulants such
as EPS, protein, carbohydrate as well as other inorganic compounds in the used
cleaning solution should be determined somehow for better understanding of
the cause of membrane fouling.
5. Due to the characteristics of carwash activity, the flow rate of the carwash
wastewater stream might highly fluctuate during a week. The flow rate might be
very high at weekend and lower at weekdays. Therefore, it is recommended that
the shock loading should be additionally investigated in term of hydraulic
conditions besides the oil loading conditions as experimented in this study.

45

References
Althers, G. (1998). Put the Breaks on Wastewater Emulsions, Chemical Engineering, 102,
2 : 82-88.
APHA, AWWA, WPCF (1992). Standard methods for the Examination of Water and
Wastewater, 18th Edition, Washington DC: APHA.
ASTM, (1969). Manual on disposal of Refinery Wastes, American Petroleum Standard
Test Methods, Liquid Wastes, First Edition,USA.
Awas, C., (1997). Basic Information on Water Purification and Recycling System for Petro
Station and Workshop. Unpublished Report, AWAS GmbH Bayern Company, Germany
Campos, J.C., Borges, R.M.H., Oliveira Filho, A.M., Nobrega, R., Sant Anna Jr., G.L.
(2001). Oilfield wastewater treatment by combined microfiltration and biological
processes, Water Research, 36, 1 : 95-104.
Chang, I.S., Kim, J.S., Lee, C.H. (1996). Membrane Biofouling Characteristics in
Membrane Cooupled Activated Sludge System. In Proc. of ICOM 96 : 926-927.
Yokohama, Japan.
Chang, Y.J., Benjamin, M.M. (1996). Iron Oxide Adsorption and UF to remove NOM and
Control Fouling, J. American Water Works Association, 88, 12 : 74-78.
Cole, G.M., (1994). Assessment and Remediation of Petroleum Contaminated Sites, USA:
Lewis: ISBN 0-87371-824-0.
Dan, N.P., (2002). Biological Treatment of High Salinity Wastewater using Yeat and
Bacterial System, AIT Dissertation No. EV-02-1.
Donal, M. (1987). Formation and Stability of Water-in-Oil Emulsion. PhD Thesis,
University of Toronto, Ontario.
Eckenfelder, W.W.J. (2000). Industrial Water
Boston:USA:McGraw-Hill:ISBN 0-07-116275-5.

Pollution

Control.

3rd

Edition.

Fuchs, W., Braun, R., Degradation of Phenanthrene in a Membrane Bioreactor, Institute

for Agrobiotechnology Tulln (IFA), June 2001.
URL:http://www.boku.ac.at/iam/ifa/mbr.htm
Galil, N.I, Wolf, D. (2001). Removal of Hydrocarbons from Petroleum Wastewater by
Dissolved Air Flotation, Water Science and Technology, 43, 8 : 107-113.
Grady Jr., C.P.L., Daigger, G.T., Lim, H.C. (1999). Biological Wastewater Treatment. 2nd
Edition. New York:Basel:Hongkong: Marcel Dekker, Inc.: ISBN 0-8247-8919-9.
James, G., Speight, J. (1991). The Chemistry and Technology of Petroleum. New York,
USA, Marcel Dekler. ISBN 0-8247-8481-2.
Kim, J.S., Lee, C.H., Chun, H.D. (1998). Comparison of Ultrafiltration Characteristics
between Activated Sludge and BAC Sludge, Water Research, 32, 11 : 3443- 3451.

46

Kornmuller, A., Wiesmann, U. (1999). Continuous Ozonation pf Polycyclic Aromatic

Hydrocarbons in Oil/Water-Emulsions and Biodegradation of Oxidation, Water Science
and Technology, 40, 4-5 : 107-114.
Langlais, B., Reckhow, D.A., Brink, D.R. (1991). Ozone in Water Treatment: Application
and Engineering. USA:Lewis:2:ISBN 0-07-113908-7.
Liem, A.J.S., Woods, D.R. (1974). Review of Coalescence Phenomena Part: Industrial
Wastewater Treatment. AIChE Symposium Series: 70, 44 : 8-22.
Liew, M.K.H., Fane, A.G., Rogers, P.L. (1995). Hydraulic Resistance and Fouling of
Microfilters by Candida utilis in fermentation broth, Biotech. Bioeng., 48, 108-117
Limpananon, J., Yodsang, S. (1997). Study of Application of Bacteria on Oil Removal in
Gas Station. Unpublished Report, Petroleum Institute, Bangkok, Thailand
Matsui, Y., Colas, F., Yuasa, A. (2001). Removal of a Synthetic Organic Chemical by
PAC-UF System. II : Model Application, Water Research, 35, 2 : 464-470.
Meryers, J.L. (1984). Dissolved Air Flotation Effluent Treatment for Profit, SEPA
Wastewater Treatment Pty, Co. Ltd.
Metcalf and Eddy, (1991). Wastewater Engineering: Treatment Disposal Reuse. 3rd
Edition. New York : USA : McGraw-Hill : ISBN 0-07-100824-1.
Montgomery, J.M. (1985). Water Treatment: Principles and Design. New York :
Chichester : Brisbane : Toronto : Singapore : John Willey & Sons, Inc. : ISBN 0-47104384-2.
Nagaoka, H., Ueda, S., Miya, A. (1996). Influence of Bacterial Extracelullar Polymers on
Membrane Separation Activated Sludge Process, Water Science Technology, 34, 9 : 165172.
Oberbremer, A., Muller-Hurtig, R., Wagner, F., (1990). Effect of the Addition of Microbial
Surfactants on Hydrocarbon Degradation in a Soil Population in a Stirred Reactor, Applied
Microbial Biotechnology, 332 : 485-489.
Panpanit, S., (2001). Oily Wastewater Treatment by Coupling Membrane Filtration and
Ozonation, AIT Dissertation No. EV-01-2.
Pirbazari, M., Ravindran, V., Badriyha, B.N., Kim, S.H. (1996). Hydrid Membrane
Filtration Process for Leachate Treatment, Water Research, 30, 11 : 2691-2706.
Reisfeld, A., Rosenberg, E., Gutnick, D., (1972). Microbial Degradation of Crude Oil:
Factors Affecting the Dispersion in Sea Water by Mixed and pure Culture, Applied
Microbiology, 24 : 636-638.
Rhee, C.H., Martyn, P.C., Kremer, J.G. (1987). Removal of Oil and Grease in the
Hydrocarbon Processing Indsutry. The proceedings of the 42nd Purdue University
Industrial Waste Conference, 143-150.

47

Rice, R.G., Robinson, C.M. (1982). Biological Activated Carbon Enhanced Aerobic
Biological Activity in GAC Systems, Ann Arbor Science Publishers.
Rosenberg, E., (1993). Exploiting Microbial growth on Hydrcarbon New Markets, Trends
in Biotechnology, 11 : 419-423.
Sawyer, C.N., McCarty, P.L., Parkin, G.F. (1994). Chemistry for Environmental
Engineering. New York:USA:McGraw-Hill:ISBN 0-07-113908-7.
Scholz, W., Fuchs, W. (2000). Treatment of Oil Contaminated Wastewater in a Membrane
Bioreactor, Water Research, 34, 14 : 3621-3629.
Seo, G.T., Ohgaki, S., Suzuki, Y., (1997). Sorption Characteristics of Biological Powdered
Activated Carbon in BPAC-MF (Biological Powdered Activated Carbon Microfiltration
System for Refractory Organic Removal, Water Research, 35, 7 : 163 170.
Stephenson T, Judd S., Jefferson B, Brindle K. (2000). Membrane Bioreactor for
Wastewater treatment, IWA Publishing.
Vinitnatharat, S., (1999). A Biological Activated carbon Sequence Batch Reactor for the
Removal of Phenols, AIT Dissertation No. EV-99-7.
Visvanathan, C., Ben Aim, R., Parameshwaran (2000). Membrane Separation Bioreactors
for Wastewater Treatment, Environmental Science and Technology, 30, 1 :1-48.
Volkering, F., Breure, A.M., Andel, J.G., Rulkens, W.H. (1995). Influent of Nonionic
Surfactants on Bioavailability and Biodegradation of Polycyclic Aromatic Hydrocarbons,
Applied and Environmental Microbiology, 61, 5 : 1699-1705.
Yamamoto, K., Hiasa, M., Manhmood, T., Matsuo, T. (1989). Direcr Solid-Liquid
Separation Using Hollow Fiber Membrane in an Activated Sludge Aeration Tank. Water
Science and Technology, 21 : 43-55.

48

Appendix A
Experimental results

49

Table A.1 Results of equilibrium adsorption time test

Contact time (h)

12

Equilibrium COD (mg/L)

343

248

171

190

183

164

175

Table A.2 Results and calculation of adsorption isotherm test (T = 25oC; agitation speed =
100 rpm, contact time = 4 h)

mg/L
20.0

mg/L
124

mg/L
108

Change in
COD
(x)
mg/L
15

50.4

124

93

31

614

0.151

101.2

124

62

62

612

0.101

200.8

124

31

93

463

0.067

20.4

240

225

15

759

0.296

50.4

240

201

39

768

0.262

103.6

240

170

70

673

0.253

203.2

240

124

116

572

0.217

PAC dose
(m)

Initial COD Equibrilium COD

(Ce)
(Co)

50

q = x/m

Ce/q

mg/g
774

g/L
0.140

Table A.3 Results of the batch experiments (Influent COD = 550 mg/L; Influent O&G =
150 mg/L)
HRT
Date

Reactor 1
(without PAC addition)

Reactor 2
(PAC = 100 mg/L)

Reactor 3
(PAC = 300 mg/L)

Reactor 4
(PAC = 500 mg/L)

(h)

MLSS CODeff. O&Geff. MLSS CODeff. O&Geff. MLSS CODeff. O&Geff. MLSS CODeff. O&Geff.

3/14

16

3520

3670

3840

4180

3/15

16

3/16

16

3310

81.6

3280

93.6

3529

103

3830

76.1

3/17

16

78.4

103

92.2

80.1

3/18

16

3220

76.3

13

3250

87.4

3370

80.6

11

3610

75.8

12

3/19

16

3140

77.1

11

3160

85.1

10

3260

74.7

10

3590

77.6

Average

3220

78.4

12

3230

92.3

3390

87.6

11

3680

77.4

12

3/20

13

113

119

103

121

3/21

13

2960

105

3060

111

3120

113

3530

111

3/22

13

98.1

15

115

19

102

17

102

18

3/23

13

2840

120

17

3040

105

3280

102

11

3380

110

11

Average

2900

109

16

3050

113

19

3200

105

14

3460

111

15

117

121

102

3/24

10

123

3/25

10

3130

131

3130

125

3170

119

3290

119

3/26

10

127

26

128

29

137

24

110

24

3/27

10

3150

124

22

3150

121

24

3270

127

28

3430

114

16

Average

3140

126

24

3140

123

27

3220

126

26

3360

111

20

3/28

168

182

160

137

3/29

3250

160

3160

176

3310

150

3570

149

3/30

178

41

156

153

34

138

34

3/31

3290

154

33

3320

172

39

3360

151

31

3480

145

33

Average

3270

165

37

3240

172

39

3340

154

33

3530

142

34

4/1

179

206

182

154

4/2

3370

204

3210

187

3390

185

3560

172

4/3

187

50

219

58

172

52

160

42

4/4

3250

219

3280

179

51

3430

165

44

3580

158

36

Average

3310

197

50

3250

198

55

3410

176

48

3570

161

39

Note: MLSS including PAC and biomass

(*) Not analyzed

51

Table A.4

Experimental results of Optimum HRT run (Influent O&G = 150 mg/L)

Date

Operating
Day

HRT
(h)

25-Apr

8.03

72.0

9.6

0.747

26-Apr

7.95

72.5

9.7

27-Apr

7.73

72.0

28-Apr

8.05

29-Apr

30-Apr

TPM
(mm Hg)
kPa

Flow rate MLSS

(L/h)
(mg/L)

52

Inf. COD
(mg/L)

Eff. COD
(mg/L)

Eff. O&G
(mg/L)

Reactor O&G
(mg/L)

8160

577

-(*)

69

0.755

7560

551

40.8

57

9.6

0.776

6500

595

59.8

63

72.0

9.6

0.745

6100

495

36.9

72

6.04

75.0

10.0

0.993

6040

547

37.5

0.2
-

80

5.98

75.0

10.0

1.003

6350

600

33.8

72

1-May
2-May

5.98

75.0

10.0

1.003

6120

597

30.1

84

6.10

75.0

10.0

0.983

6240

585

26.3

1.6

83

3-May

4.08

80.0

10.7

1.469

6320

570

33.8

103

4-May

10

4.06

80.0

10.7

1.479

6520

548

52.5

93

5-May

11

3.97

80.0

10.7

1.510

6680

607

38.3

1.4

87

6-May

12

1.98

91.0

12.1

3.031

7140

47.3

138

7-May

13

1.98

104.5

13.9

3.031

8500

502

36.2

154

8-May

14

2.00

105.5

14.1

3.000

535

37.5

173

9-May

15

2.01

120.0

16.0

2.990

8300

495

40.0

3.2

179

10-May
16
Not analyzed

2.04

170.5

22.7

2.948

8700

45.7

164

(*)

52

Table A.5

Experimental results of Shock loading run

Date

Operating
Day

HRT
(h)

11-May

4.08

70.0

12-May

4.11

13-May

14-May

TPM
(mm Hg)
kPa

Flow rate
(L/h)

MLSS
(mg/L)

Inf. COD
(mg/L)

Inf. O&G
(mg/L)

Eff. COD
(mg/L)

9.3

1.469

7300

1101

300

11.2

-(*)

183

69.0

9.2

1.459

9020

1024

300

22.3

172

4.03

71.0

9.5

1.490

7960

1021

300

32.2

1.2

184

4.11

70.0

9.3

1.459

7400

1309

450

35.6

245

15-May

4.14

81.5

10.9

1.448

7740

1363

450

42.6

4.1

287

16-May

4.17

83.0

11.1

1.438

8260

1791

600

39.4

471

17-May
7
Not analyzed

4.11

83.0

11.1

1.459

9100

1835

600

54.1

3.5

946

(*)

53
53

Eff. O&G Reactor O&G

(mg/L)
(mg/L)

Table A.6
Date

Experimental results of Long run A (Influent O&G = 300 mg/L)

Operating
Day

HRT
(h)

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

4.08
3.92
3.94
3.87
3.79
3.82
4.03
3.97
3.89
3.89
3.87
3.87
4.00
3.97
3.63
3.97
3.92
3.95
4.06
4.14

20-May
21-May
22-May
23-May
24-May
25-May
26-May
27-May
28-May
29-May
54

30-May
31-May
1-Jun
2-Jun
3-Jun
4-Jun
5-Jun
6-Jun
7-Jun
8-Jun
(*)
Not analyzed

TPM
(mm Hg) kPa
69
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
71
88
96
115

9.2
9.3
9.3
9.3
9.3
9.3
9.3
9.3
9.3
9.3
9.3
9.3
9.3
9.3
9.3
9.3
9.5
11.7
12.8
15.3

Flow rate
(L/h)

MLSS
(mg/L)

Inf. COD
(mg/L)

Eff. COD
(mg/L)

Eff. O&G
(mg/L)

Reactor O&G
(mg/L)

1.469
1.531
1.521
1.552
1.583
1.572
1.490
1.510
1.541
1.541
1.552
1.552
1.500
1.510
1.655
1.510
1.531
1.520
1.479
1.448

9480
8740
9980
10020
9820
9700

1056
947
1093
955
907
945
1071
939
944
973
-

85.9
84.9
45.9
35.8
43.0
75.4
76.5
62.9
39.3
54.4
-

-(*)
5.1
3.7
2.9
3.2
2.9
5.3
3.5
7.3
5.3
-

380
342
225
207
180
183
174
147
161
175
-

9020
8800
9320
8340
-

54

Table A.7

Experimental results of Long run B (Influent O&G = 300 mg/L)

TPM

Operating
Day

HRT
(h)

(mm Hg)

kPa

9-Jun

3.87

79

10.5

1.552

10-Jun

3.87

79

10.5

11-Jun

3.87

79

12-Jun

3.97

13-Jun

14-Jun

Inf. COD
(mg/L)

Eff. COD
(mg/L)

Eff. O&G
(mg/L)

Reactor O&G
(mg/L)

-(*)

1.552

10660

901

22.8

0.5

50

10.5

1.552

80

10.7

1.510

9680

1096

41.6

2.5

98

3.94

79

10.5

1.521

3.77

79

10.5

1.593

10280

975

48.8

0.4

104

15-Jun
16-Jun

3.94

79

10.5

1.521

3.87

79

10.5

1.551

9220

945

45.0

4.1

108

17-Jun

3.87

79

10.5

1.552

18-Jun

10

3.87

80

10.7

1.552

10100

946

30.5

3.1

174

19-Jun

11

3.82

79

10.5

1.572

20-Jun

12

3.82

80

10.7

1.572

9120

976

30.1

3.2

165

21-Jun

13

3.94

93

12.4

1.521

22-Jun

14

4.08

105

14.0

1.469

9020

900

37.5

1.0

159

23-Jun

15

4.11

115

15.3

1.459

24-Jun
16
Not analyzed

4.13

186

24.8

1.453

9500

1027

42.8

5.2

182

Date

Flow rate MLSS

(L/h)
(mg/L)

55

(*)

55

Appendix B
Membrane resistance measurement data

56

Membrane surface area

Dynamic viscosity

0.42m2
7.98 x 10-07 (kN.s)/m2

Membrane resistance of new membrane

TMP
mm Hg
117
107
98
85
77

Flow rate Filtration flux

mL/min.
L /(m2.h)
190
27.1
145
20.7
109
15.5
34
4.8
8
1.2

kPa
15.6
14.3
13.1
11.3
10.3

8.95x1011 1/m

Membrane resistance

18
16

TMP (kPa)

14
12
10
y = 0.1985x + 10.154
R2 = 0.9946

8
6
4
2
0
0

10

15

20
2

Filtration flux (L/(m .h)

57

25

30

Membrane resistance of the membrane after Optium HRT run being cleaned
with chemicals

TMP

Flowrate
mL/min.
185
160
130
90
31

kPa
10.7
9.7
9.1
8.1
6.3

mm Hg
80
73
68
61
47

Filtration flux
L /(m2.h)
26.4
22.8
18.6
12.8
4.5

8.73x1011 1/m

Membrane resistance

12

TMP (kPa)

10
8
6

y = 0.1936x + 5.4763
R2 = 0.994

4
2
0
0

10

15

20

Filtration flux (L/(m 2.h)

58

25

30

Membrane resistance of the membrane after Shock loading run being cleaned
with chemicals

TMP
mm Hg
86
77
68
61
52

Flowrate
mL/min.
182
152
109
67
29

kPa
11.5
10.3
9.1
8.1
6.9

Filtration flux
L /(m2.h)
26.0
21.8
15.5
9.5
4.1

8.98x1011 1/m

Membrane resistance

14
12
TMP (kPa)

10
8
6
y = 0.199x + 6.113

R = 0.9918

2
0
0

10

15

20
2

Filtration flux (L/(m .h)

59

25

30

Total membrane resistance of the clogged membrane after Long run A

TMP
mm Hg
86
98
105
114
128

Flowrate
mL/min.
21
33
45
51
85

kPa
11.5
13.1
14.0
15.2
17.1

27.35x1011 1/m

Membrane resistance

TMP (kPa)

Filtration flux
L /(m2.h)
3.0
4.8
6.4
7.3
12.1

20
18
16
14
12
10
8
6
4
2
0

y = 0.6063x + 10.093
R2 = 0.9555

10
2

Filtration flux (L/(m .h)

60

12

14

Membrane resistance of the membrane after Long run A being washed

with tap water
TMP
mm Hg
52
60
70
81
90

Flowrate
mL/min.
25
45
71
97
121

kPa
6.9
8.0
9.3
10.8
12.0

Membrane resistance

Filtration flux
L /(m2.h)
3.6
6.4
10.2
13.8
17.3

16.66x1011 1/m

14
12
TMP (kPa)

10
8
y = 0.3692x + 5.6258
R2 = 0.9996

6
4
2
0
0

10
Filtration flux (L/(m 2.h)

61

15

20

Membrane resistance of the membrane after Long run A being cleaned

with chemicals

TMP
mm Hg
61
68
79
86
90

kPa
8.1
9.1
10.5
11.5
12.0

Flow rate
mL/min.
53
74
138
173
187

Filtration flux
L /(m2.h)
7.6
10.6
19.7
24.7
26.7

8.60x1011 1/m

Membrane resistance

14
12
TMP (kPa)

10
8
y = 0.1907x + 6.8314
R2 = 0.9918

6
4
2
0
0

10

15

20
2

Filtration flux (L/(m .h)

62

25

30

Total membrane resistance of the clogged membrane after Long run B

TMP
mm Hg
60
79
103
90
123

kPa
8.0
10.5
13.7
12.0
16.4

Membrane resistance

Flowrate
mL/min.
15
27
43
34
53

Filtration flux
L /(m2.h)
2.1
3.9
6.2
4.9
7.6

68.30x1011 1/m

18
16

TMP (kPa)

14
12
10
8

y = 1.5139x + 4.6693
R2 = 0.9949

6
4
2
0
0.0

2.0

4.0
Filtration flux (L/(m 2 .h)

63

6.0

8.0

Membrane resistance of the membrane being washed with tap water

after Long run B
TMP
mm Hg
106
98
90
79
69

kPa
14.1
13.1
12.0
10.5
9.2

Membrane resistance

Flowrate
mL/min.
107
93
76
56
37

Filtration flux
L /(m2.h)
15.2
13.2
10.9
8.1
5.3

22.27x1011 1/m

16
14

TMP (kPa)

12
10
8

y = 0.4936x + 6.5864
R2 = 0.9996

6
4
2
0
0.0

5.0

10.0
Filtration flux (L/(m 2 .h)

64

15.0

20.0

Membrane resistance of the membrane after Long run B being cleaned with
NaOH solution
TMP
mm Hg
86
78
70
62
54

kPa
11.5
10.4
9.3
8.3
7.2

Membrane resistance

Flowrate
mL/min.
144
130
100
75
40

Filtration flux
L /(m2.h)
20.6
18.6
14.3
10.7
5.8

12.58 x1011 1/m

14
12
TMP (kPa)

10
8
6

y = 0.2788x + 5.4324
R2 = 0.9843

4
2
0
0.0

5.0

10.0

15.0

Filtration flux (L/(m 2 .h)

65

20.0

25.0

Membrane resistance of the membrane after Long run B being cleaned with
NaOH solution and HNO3 solution (4h)
TMP
mm Hg
83
76
70
62
53

kPa
11.1
10.1
9.3
8.3
7.1

Membrane resistance

Flowrate
mL/min.
147
122
95
69
39

Filtration flux
L /(m2.h)
21.1
17.4
13.6
9.8
5.6

11.56 x1011 1/m

12

TMP (kPa)

10
8
y = 0.2562x + 5.7156
R2 = 0.9975

6
4
2
0
0.0

5.0

10.0

15.0

Filtration flux (L/(m 2 .h)

66

20.0

25.0

Membrane resistance of the membrane after Long run B being cleaned with
NaOH solution, HNO3 solution (4h) and additional 12h HNO3 solution soaking
TMP
mm Hg
82
77
70
62
55

kPa
10.9
10.3
9.3
8.3
7.3

Flowrate
mL/min.
144
122
98
66
34

Filtration flux
L /(m2.h)
20.5
17.4
14.0
9.4
4.9

10.55x1011 1/m

Membrane resistance

12

TMP (kPa)

10
8
y = 0.2339x + 6.124
R2 = 0.9981

6
4
2
0
0

10

15

Filtration flux (L/(m 2.h)

67

20

25

Appendix C
Photographs of experimental works

68

Oil/water emulsion droplet (x530)

Virgin PAC used in the experiments (x530)

Ruler with increment of 10 m (x530)

69

BAC sludge from Batch experiment (x530)

Activated sludge from Long run A (x530)

BAC sludge from Long run B (x530)

70

MBR system Long Run A

MBR system Long Run B

71

Clogged membrane
after Long Run A

Clogged membrane
after Long Run B

After washed with tap

water (Long Run A)

After cleaned with

chemicals (Long Run A)

Membrane soaked in
After washed with tap After cleaned with
water (Long Run B)
chemicals (Long Run B) nitric acid solution

72

Af
ch

OILY WASTEWATER TREATMENT

BY MEMBRANE BIOREACTOR PROCESS COUPLED WITH
BIOLOGICAL ACTIVATED CARBON PROCESS
By Mr. Phan Thanh Tri

Examination Committee: Prof. C. Visvanathan (Chairperson)

Dr. Josef Trankler
Dr. Preeda Parkpian

PTT

1/30

Carwash Wastewater
Reused
Tap
water
water

Dirty
car

Dust
cleaning

Emulsifier

Foaming

Biodegradable
Low strength
Surplus nutrients

Domestic
wastewater

PTT

Tap
water

Presoak

Tap water

Dryer
(hot air)

Rinse
water

Clean
car
Oil + emulsifier
Birefractory
Lack of nutrients

Oily
wastewater

Settling
tank

MBR
system

2/30

Membrane Bioreactor Process

Conventional Activated Sludge Process
Influent

Aeration
Tank

Sedimentation
Tank

Effluent

Advantages:
Compact size
High effluent quality
High SRT degrade biorefractory compounds
Slow rate sludge production
Drawback: Membrane fouling high operation
cost due to increase in energy consumption and
cleaning chemicals
Effluent

Excess sludge

Bioreactor

Influent
Aeration
Tank
Membrane
module
Effluent

Membran
e module

External cross flow MBR

Influent

Submerged MBR
PTT

Air
Air diffuser

3/30

Membrane Fouling and Membrane Resistance

p
J = ------ Rt

J : permeate flux (m3/m2.s)

P : transmembrane pressure (Pa)
: viscosity of the permeate (Pa.s)
Rt : total resistance for filtration (1/m)

Rt = Rm + Rc + Rf
Rm : intrinsic membrane resistance
Rc: cake layer resistance
Rf: fouling resistance due to fouling and pore plugging
Membrane
Cake layer

Filtration

New membrane

Rt = R m
PTT

Fouling or pore
plugging
Washed with
tap water

Membrane clogging

Rt = R m + R c + R f

Irreversible fouling
Cleaned with
chemicals

Rt = R m + R f

Rt = Rm
4/30

BAC Process
Adsorption

Suspended Growth

Aeration tank
Activated
Carbon

Pollutant

Biofilm

PTT

Attached Growth

Microbial
Suspension
5/30

Literature Review
MBR Process in Oily Wastewater Treatment
Characteristics of
wastewater
Fuel oil and
lubricant oil +
surfactant

Operation
conditions
- HRT = 13.3h
- MLSS = 48 g/L

Influent
concentration
- 500-1000 mg/L as
hydrocarbons
- Oil : Surfactant =
100 : 7

Membrane
fouling

Reference

- 99.9% for fuel oil or

- Membrane
lubricant oil
fouling: not
- 94 - 98 % for COD
reported
- 93-99 % for emulsifier

Scholz and
Fuchs (2000)

Removal efficiency

- 780-1960 mg/L
- HRT = 3.67 day
Soluble fraction of
COD
- 95.3 % for COD
- MLSS > 2 g/L
oily wastewater
- 18.4 mg/L of oil as - 76.1 % for oil
- SRT = 300 days
n-Hexane extracts
Phenanthrene
(toxic component - MLSS = 5 g/L
in oil)

PTT

- Membrane
Seo et al.
washing
(1997)
every 7 days

- Membrane
- Phenanthrene
- 25 - 400 ppm/day
fouling: not
concentration < 0.1ppm
reported

Fuchs and
Braun (2001)

6/30

Literature Review
BAC-MBR Process in Wastewater Treatment

Pirbazari et al. (1996) studied the treatment of landfill leachate using the
ultrafiltration-biologically active carbon (UF-BAC) process.

Influent COD = 3,000 mg/L

COD removal efficiency = 95-98%

PTT

Addition of 1% PAC was proved to mitigate the permeate flux decline

significantly.
Possible mechanisms for enhancement of biodegradation and mitigation of
permeate flux decline are discussed.

Kim et al. (1998) conducted a study to compare ultrafiltration characteristics of

activated sludge and biological activated carbon (BAC) sludge.

The two kinds of sludge were then experimented ultrafiltration

characteristics using a batch stirred cell unit.

The results showed that the addition of PAC increases the permeate flux in
spite of the increase of suspended solid and reduced floc size.

This finding was explained by the fact that BAC sludge has lower
compressibility and higher porosity than normal activated sludge and BAC
sludge has lower content of EPSs inside the floc than activated sludge
7/30

Objectives
to investigate the oil adsorption isotherm of powdered
activated carbon.

to preliminarily determine the biodegradation of oily

wastewater in activated process and BAC process.

to evaluate the performance of a MBR system to treat oily

wastewater in term of membrane fouling, removal
efficiency and process stability.

to investigate the effect of PAC addition on the

performance of the MBR system.

PTT

8/30

Methodology

Overall Experimental Course

Adsorption isotherm experiment
Batch experiment

Activated sludge process

Biological activated carbon process

MBR experiment
Optimum HRT run
Shock loading run
Long run A
Long run B
(with PAC addition)
PTT

9/30

Methodology:

PTT

Materials and Microorganisms

Feed wastewater : synthetic wastewater

Lubricant oil
: 150 600 mg/L

Emulsifier : 13.6 54.4 mg/L

Glucose BOD = 100 mg/L

Mineral salts nutrients

Microorganisms:

Activated sludge from domestic wastewater treatment plan

Acclimated to oily wastewater for two months

Activated carbon

PAC supplied by Sigma Chemical Co.

Nominal size : 37 150 m

10/30

Methodology:

250 mL sample in 500-mL flasks agitated at 100 rpm

Adsorption isotherm experiment: to determine suitable isotherm

model for adsorption of lubricant oil onto PAC

Temperature: 25oC
Adsortability expressed in term of COD
Equilibrium time experiment: to determine suitable contact time for
adsorption reach equilibrium.

Equilibriumtime
time
Equilibrium
experiment
experiment
Adsorptionisotherm
isotherm
Adsorption
experiment
experiment

PTT

Adsorption Isotherm Experiment

InitialCOD
COD
Initial
(mg/L)
(mg/L)

PACdose
dose
PAC
(mg/L)
(mg/L)

Contacttime
time
Contact
(h)
(h)

343
343

100
100

1,2,
2,3,
3,5,
5,8,
8,12
12
1,

124,240
240
124,

20,50,
50,100,
100,200
200
20,

44

11/30

Methodology:

Batch experiment

To determine preliminary parameters of the biodegradation of oily

wastewater by AS process and BAC process

2 L reactors run at SBR mode: Fill, Aerate, Settle (2 h), Draw

Influent : O&G = 150 mg/L; COD = 550 mg/L

Reactor 1

Reactor 2

Reactor 3

Reactor 4

(No PAC)

(PAC = 100 mg/L)

(PAC = 300 mg/L)

(PAC = 500 mg/L)

.V
HRT = ----------Q

PTT

V : reactor volume (2 L)
Q : volume of effluent withdrawn per cycle
= volume of influent filled per cycle =1L
: aeration time per cycle (h)
HRT = 16, 13, 10, 6 and 3

Analysed parameters: MLSS, COD and O&G for effluent.

12/30

Methodology:

MBR Experiment
Timer
Air
backwash
F
Air pressure
Regulator

Hg manometer
P

Solenoid
valve

Pump

Feed tank

Membrane
module

Submerged MBR
Reactor volume: 6L

Level control
tank

Effluent
tank

Membrane module: hollow fiber,

microfiltration, pore size 0.1m,
surface area 0.42 m2.
Intermittent air backwash for 3
minutes every 25 minutes of
filtration

Sampling point

Influent
Compressed Air

PTT

Air diffuser

13/30

Methodology:

MBR Experiment
Experimental conditions

Run
Run

OptimumHRT
HRT
Optimum
Run
Run

ShockLoading
Loading
Shock
Run
Run

LongRun
RunAA
Long

LongRun
RunBB
Long

Influentoil
oil
Influent
concentration
concentration
(mg/L)
(mg/L)
150
150
150
150
150
150
150
150
300
300
450
450
600
600
300
300

300
300

HRT
HRT
(h)
(h)
88
66
44
22
44
44

SRT
SRT
(day)
(day)

PACdose
doseinin
PAC
Parametersto
tobe
bemeasured
measured
reactor
Parameters
reactor
(g/L)
(g/L)

indefinite
indefinite

00

Inf.COD,
COD,eff.
eff.COD
CODand
andO&G,
O&G,
Inf.
reactorO&G,
O&G,MLSS,
MLSS,TMP
TMP
reactor

indefinite
indefinite

00

Inf.COD,
COD,eff.
eff.COD
CODand
andO&G,
O&G,
Inf.
reactorO&G,
O&G,MLSS,
MLSS,TMP
TMP
reactor

00

Inf.COD,
COD,eff.
eff.COD
CODand
andO&G,
O&G,
Inf.
reactorO&G,
O&G,MLSS,
MLSS,TMP,
TMP,
reactor
EPS,RRm, ,RR,c,RRf
EPS,
m
c
f

22

Inf.COD,
COD,eff.
eff.COD
CODand
andO&G,
O&G,
Inf.
reactorO&G,
O&G,MLSS,
MLSS,TMP,
TMP,
reactor
EPS,RRm, ,RR,c,RRf
EPS,
m
c
f

44
44

44

50
50

50
50

Membrane was cleaned with chemicals after each run

PTT

14/30

Results and Discussions

Adsorption Isotherm Experiment

Equilibrium time experiment

Equilibrium COD (mg/L)

400
350
300
250
200
150
100
50
0
0

10

12

14

Contact time (h)

PTT

Equilibrium time : 4 h

15/30

Results and Discussions

Adsorption Isotherm Experiment
Freundlich Isotherm

Langmuir Isotherm

0.35

1000

Ce/(x/m) = 0.0341 + 0.0012Ce

Ce/(x/m) (g/L)

x/m (mg/g)

0.30

1/n

x/m = Kf Ce
x/m =

Kf = 225.84
1/n = 0.2244

0.2244
225.84C e

R2 = 0.6892

R = 0.9520

0.25
0.20

Ce

0.15

------- = ---- + ---- Ce

(x/m) ab
a
a = 833; b = 0.352

0.10
0.05
0.00

100

10

100
COD equilibrium, Ce (mg/L)

PTT

1000

50

100
150
200
COD equilibrium, C e (mg/L)

250

Based on R-squared values, Langmuir isotherm more appropriate

Oil long chain compounds large molecule size monolayer
adsorption (Langmuir isotherm)

16/30

Results and Discussions

Batch Experiments
100

100

Variation of COD removal vs. HRT

90

90

85

85

80
75
70
65
R1 (without PAC addition)

60

PTT

80
75
70
65
60

55

55

50

50
2

10
HRT (h)

12

14

Variation of O&G removal vs. HRT

95

O&G removal (%)

COD removal (%)

95

16

R1 (without PAC addition)

10
HRT (h)

12

14

16

COD removal efficiency increased from 64% to 86% when HRT increased
from 3h to 16h

At HRT=13h, the removal efficiencies of COD and O&G reached 80% and
90% respectively

biodegradation of oily wastewater took place at significant level

MBR experiments should be conducted at HRT < 10 h
17/30

Results and Discussions

Batch Experiments
100

100

Variation of COD removal vs. HRT

95

90

85
80
75
70
R1 (without PAC addition)
R2 (PAC = 100 mg/L)
R3 (PAC = 300 mg/L)
R4 (PAC = 500 mg/L)

65
60
55

O&G removal (%)

COD removal (%)

90

85
80
75
70

R1 (without PAC addition)

65
60

R2 (PAC = 100 mg/L)

R3 (PAC = 300 mg/L)

55

R4 (PAC = 500 mg/L)

50

50
2

PTT

Variation of O&G removal vs. HRT

95

10
HRT (h)

12

14

16

10
HRT (h)

12

14

16

There was no distinguished difference between the performance of BAC

process (Reactors 2, 3 and 4) and AS process at HRTs longer than 10h

biodegradation was predominant over the effect of adsorption at long

contact times

There was a tendency of effluent quality improvement of the BAC

process with increasing PAC dose
18/30

Results and Discussions

161

60
50

R4 (PAC = 500 mg/L)

165
142

150
COD (mg/L)

Comparison of effluent O&G of AS process

and BAC process (PAC = 500 mg/L)

Comparison of effluent COD of AS process

and BAC process (PAC = 500 mg/L)
197

R1 (without PAC addition)

126
111

109 111

100

78.4 77.4

O&G (mg/L)

200

Batch Experiments

40

39

37

R4 (PAC = 500 mg/L)

R1 (without PAC addition)
34
24

20

20

16 15

12 12

13

16

50

0
3

PTT

10
HRT (h)

13

16

10
HRT (h)

The most pronounced enhancement was observed at PAC dose = 500 mg/L
and HRT = 3h

the adsorption of PAC helped to remove the oil from the supernatant and
therefore improve the performance of the BAC process at short HRTs

PAC dose in MBR experiments should be higher because MLSS in MBR is

much higher
19/30

Results and Discussions

MBR Experiments Optimum HRT run

COD (mg/L)

700

Excellent effluent quality:

600

COD: 26.3 59.8 mg/L

500

O&G: 0.2 3.2 mg/L

Visually, clear and oil free

400

HRT=8h

HRT=6h

HRT=4h

300

HRT=2h

Influent COD
Effluent COD

200
100

MBR performance better batch experiment

due to higher MLSS (6040 8700 mg/L)

and the enhanced removal by membrane
separation

0
1

9 10 11 12 13 14 15 16

200

There was a pronounced increase

in the reactor O&G concentration
at HRT = 2h :
Reactor O&G = 138 179mg/l >
influent O&G of 150 mg/L

should check for oil accumulation

in the reactor

O&G (mg/L)

Time (day)

150
HRT=8h

HRT=6h

HRT=4h

HRT=2h

100
Influent O&G
Reactor O&G
Effluent O&G

50
0
1

9 10 11 12 13 14 15 16

Time (day)

PTT

20/30

Results and Discussions

MBR Experiments Optimum HRT run
120
100

Oil remaining in the reactor

80
O&G (g)

Operating Average Average O&G

time
HRT
loading
(day)
(h)
(g O&G/day)

Total oil input from the influent

14
58
9 11
12 16

60
40
20
0
0

8
10
Time (day)

12

14

16

TMP (kPa)

HRT=8h

HRT=6h

HRT=4h

0.50
0.48
0.57
0.97

Oil fed into reactor up to 95.3g

Oil remaining in reactor: 0.4 1.1g

At HRT = 2h, reactor O&G increased 0.4 g vs.

increase in oil loading of 5.45 g/day

most of the oil degraded within reactor

HRT=2h

15
10
5

TMP: stable in range of 9.6 kPa 10.7 kPa at

HRT = 8, 6 & 4h.

HRT = 2h, TMP increased rapidly from 12.1 to

22.7 kPa membrane clogging.

HRT = 4h was selected for next runs

0
1

Time (day)

PTT

2.72
3.58
5.35
10.8

25
20

7.94
6.03
4.04
2.00

Average O&G
remaining in
reactor
(g O&G)

10 11 12 13 14 15 16

21/30

Results and Discussions

MBR Experiments Shock loading run

MBR system showed good stability against

shock loading:

Inf. COD = 1021 - 1835 mg/L

Eff. COD = 11.2 - 54.1 mg/L

Inf. O&G = 300 - 600 mg/L

COD (mg/L)

2000
Influent COD
Effluent COD

1500
1000
500

Eff. COD = 1.2 4.1 mg/L

0

Reactor O&G increased quickly to 946 mg/L

when inf. O&G = 450 mg/L - 600 mg/L

possibility of oil accumulation in the reactor

capacity of the system at high loading should
be investigated in long term basis

O&G (mg/L)

1000
900
800
700
600
500
400
300
200
100
0

Influent O&G
Reactor O&G
Effluent O&G

Time (day)

PTT

22/30

Results and Discussions

MBR Experiments Long run
PAC addtition

PAC addtition

1200

800
Influent COD
Effluent COD

600
400

Long Run A

Long Run B

200
0

PTT

O&G (mg/L)

COD (mg/L)

1000

400
350
300
250
200
150
100
50
0

Long Run A

Long Run B
Influent O&G
Reactor O&G
Effluent O&G

1 3 5 7 9 11 13 15 17 19 21
31 33
1 23
3 25
5 27
7 29
9 11
13 35
15

1 3 5 7 9 11 13 15 17 19 21
31 33
1 23
3 25
5 27
7 29
9 11
13 35
15

Time (day)

Time (day)

Effluent was stable at low level over long run

Eff. quality of Run B was slightly better than Run A :
Run A: COD = 29.3 85.9 mg/L; O&G = 2.9 7.3 mg/L
Run B: COD = 22.8 48.8 mg/L; O&G = 0.4 5.2 mg/L
The difference was not significant because the improvement was hidden behind the
enhanced removal of MBR process
Reactor O&G of the first 4 days of Run A were significantly higher than the rest 16 days
degradation of oil accumulated in Shock loading run
Reactor O&G of the first 8 days of Run B were at low level of 50 108 mg/L then
increased to 165 182 mg/l adsorption effect decreased gradually as attached growth
23/30
developed

Results and Discussions

MBR Experiments Long run
Biofilm
Activated sludge

There was biofilm attached on

carbon surface

10 m

But the attached growth would

not predominant in this reactor
because most of PAC particles
were trapped in bigger flocs

Carbon particles

PTT

24/30

Results and Discussions

MBR Experiments Long run
PAC addtition
25

TMP (kPa)

20

Long Run A

Long Run B

15
10
5
0
1 23
3 25
5 27
7 29
9 11
15
1 3 5 7 9 11 13 15 17 19 21
31 13
33 35
Time (day)

PTT

Membrane clogging happened sooner in Run B (13 days vs. 18 days of Run A)

Initial TMP of Run B was higher than that of Run A (10.5 kPa vs. 9.2 kPa)

There was a stage that the TMP remained very stable for both Run A and B before
the TMP increased sharply
25/30

Results and Discussions

MBR Experiments Long run
80
70

Membrane resistance (x 10

11

1/m)

Cake layer resistance was

the highest contribution to
total membrane resistance
of the clogged membrane

The formation of the cake

layer occured gradually
from the beginning ?
Pressure

60

Fouling resistance Rf
Cake layer resistance Rc
Intrinsic membrane resistance Rm

13.7 (20.0%)

50
40
46.0 (47.4%)

30
20

7.7 (28.1%)
10.7 (39.1%)

10
8.9 (32.8%)

8.6 (12.6%)

Run A

Run B

RtRt

Rc

Time

PTT

26/30

Results and Discussions

MBR Experiments Long run

Cake layer
TMP

Effective air
backwash

Membrane

Fouling and
pore plugging

Effective air
backwash

Ineffective air
backwash

Time

PTT

27/30

Results and Discussions

MBR Experiments Long run

Membrane resistance (x1011 1/m)

12

+17.9%

10

-2.5%

+0.3%

Resistance of the clogged

membrane recovered back to
initial value after chemical
cleaning except Run B

Fouling after Run B was

partial irreversible
carbon plugging

-3.9%

8
6
4
2
0
New
membrane

PTT

Membrane clogging of Run B

plugging of PAC particles into
the membrane pores
air backwash becomes ineffective sooner

After
Optimum
HRT run

After Shock After Long

loading run
run A

After Long
run B

28/30

Conclusions

PTT

The adsorption isotherm of the PAC to the lubricant oil was determined
following Langmuir isotherm model.

There was a tendency of effluent quality improvement of the BAC process run
at SBR mode for oily wastewater treatment when increasing PAC dose.

Application of MBR process for oily wastewater treatment provided excellent

effluent quality which is suitable for water reuse at gas station.

MBR system provided stable high quality effluent against high oil loading.

Combination of MBR process and BAC process for oily wastewater treatment
showed little improvement in effluent quality because the improvement was
hidden behind the enhanced removal of MBR process. Attached growth was not
predominant in the combined system.

The hybrid system caused membrane clogging more quickly due to the plugging
of PAC particles into the pores of the membrane.

Cake layer resistance was found the highest contribution to total resistance of
the clogged membrane. It is suggested that during operation there was a
critical point when the blockage of the membrane pores reached a level that
made the air backwash ineffective, the formation of the cake layer became
intensive and lead to membrane clogging

29/30

Recommendations

Application of MBR process for other sources of oily wastewater such as oilfield
wastewater should be investigated.

As the membrane clogging process and the possible accumulation of pollutants

in the MBR are long time processes, it is recommended that future researches
on MBR process should be designed on a long term run basis.

Future work should focused on the modeling of the membrane clogging course
in the submerged MBR. An interrelation between membrane plugging and
fouling process and cake layer formation process would be a good approach.

Composition and quantity of common foulants such as EPS, protein,

carbohydrate as well as other inorganic compounds in the used cleaning
solution should be determined somehow for better understanding of the cause
of membrane fouling.

PTT

30/30