Separation and Purification Technology 52 (2007) 470–477

A submerged nanofiltration membrane bioreactor for domestic wastewater

treatment: the performance of cellulose acetate nanofiltration
membranes for long-term operation
Jae-Hoon Choi a,∗ , Kensuke Fukushi b , Kazuo Yamamoto b
a Department of Urban Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-8656, Japan
b Environmental Science Center, The University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-0033, Japan

Received 5 April 2006; received in revised form 26 May 2006; accepted 26 May 2006

Abstract
A submerged nanofiltration membrane bioreactor (NF MBR) using cellulose acetate membranes was operated for 240 days to examine the
performance of the NF membrane in domestic wastewater treatment. For the first 130 days, dissolved organic carbon (DOC) concentration in the
permeates ranged from 0.5 to 2.0 mg/L. The rejection rates of monovalent and divalent ions by the NF membranes varied between 40 and 60%
and between 70 and 90%, respectively, for the initial 80 days. The permeate flux increased gradually with decreasing transmembrane pressure
(TMP) during the operation. The results of MW distribution and fractionation of dissolved organic matter in the waters demonstrated the increase
in membrane pore size and decrease in membrane hydrophobicity over operating time. From the results, the degradation of each water-quality
parameter over operation time might be attributed to the qualitative deterioration of the NF membrane caused by the hydrolysis of cellulose acetate,
which leads to an increase in pore size and porosity, and decrease in surface charge and hydrophobicity of cellulose acetate membranes.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Advanced wastewater treatment; Cellulose acetate membrane; Hydrolysis; Nanofiltration; Submerged membrane bioreactor

1. Introduction Frequent occurrence of organic contaminants in natural waters,

The membrane bioreactor (MBR) process, an effective and
efficient membrane application for advanced wastewater treat-
ment, usually combines biological wastewater treatment with
microfiltration (MF) or ultrafiltration (UF) process to treat
wastewater biologically and to separate biomass physically from
mixed liquor in an integrated step. The MBR has demonstrated
its superiority in improving effluent quality over the past 30
years, and has been extended to advanced wastewater treatment
due to stringent wastewater effluent regulations and the con-
tinuous development of membrane technology [1]. Municipal,
agricultural and industrial wastewater effluents continue to be
discharged into water sources, and moreover, the amount of
organic pollutants from the effluents has gradually increased.
∗ Corresponding author. Present address: Division of Environmental Science
and Engineering, National University of Singapore, Block EA #07-23, 9 Engi-
neering Drive 1, Singapore 117576. Tel.: +65 6874 5265; fax: +65 6874 5266.
E-mail addresses: jaehoonchoi2@hanmail.net (J.-H. Choi),
fukushi@esc.u-tokyo.ac.jp (K. Fukushi), yamamoto@esc.u-tokyo.ac.jp
(K. Yamamoto).
especially drinking water sources, raises concern over the poten-
tial for these pollutants to affect human health through chronic
exposure [2–4]. Therefore, more advanced wastewater treatment
processes, which have low-environmental load technology, are
required to reduce or minimize the contaminants released into
the water environment.
The nanofiltration (NF) process has potential here, because
a NF membrane can typically reject organic matters with
molecular weight (MW) greater than approximately 200 Da [5].
Although the MBR using UF membranes showed a high removal
efficiency of particle and organic matter, indicating that the efflu-
ent COD ranged from 10 to 20 mg/L [6–8], the system will not
be adequate to remove known and unknown dissolved organic
matter with several hundreds of MW, due to the relatively coarse
pore size distribution of the UF membranes.
To date, application of NF membranes to wastewater treat-
ment has been generally limited to the area of additional
advanced treatment of wastewater effluent already treated by
a conventional activated sludge process [9,10]. Our previous
studies demonstrated that the adoption of NF membrane in a
submerged MBR (NF MBR) was feasible because the system

1383-5866/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2006.05.027
 J.-H. Choi et al. / Separation and Purification Technology 52 (2007) 470–477
could provide extra-clean permeate and reasonable water pro-
ductivity [11,12]. In addition, the submerged NF MBR using
cellulose acetate membranes showed treatment performance,
especially permeate productivity, that was better than that of the
MBR using polyamide NF membranes in domestic wastewater
treatment [13]. However, the NF MBR using cellulose acetate
membranes was unsatisfactory because the permeate quality
deteriorated over operating time in long-term operation. In order
for the submerged NF MBR to be feasible in wastewater treat-
ment, the MBR system has to achieve sustainable membrane
performance for long-term operation.
The objective of this work was to observe the membrane
performance of the submerged NF MBR using cellulose acetate
membranes, and to examine the causes of deterioration of perme-
ate quality in the submerged NF MBR. Therefore, MW distribu-
tion and hydrophilic/hydrophobic fractions of dissolved organic
matter (DOM), as well as organic matter and salt rejection, were
measured.
2. Materials and methods
2.1. NF membrane
A NF hollow-fiber membrane module (HA3110, Toyobo,
Japan), which has a surface area of 12.1 m2 of cellulose acetate
materials, was adopted for this study. The commercial mem-
brane module manufactured for a cross-flow filtration system
was modified for adaptation to the submerged MBR system.
The pressure vessel was removed and the original roll-up shape
was converted to a U shape. Table 1 summarizes properties of
the NF membrane module. In this study, the cellulose acetate
NF membrane module was adopted due to the compactness of
a hollow-fiber membrane module and to practical limitations.
However, the membrane has potential for qualitative deterio-
ration in wastewater as a result of hydrolysis and biological
degradation of the cellulose acetate [14–17]. The relationship
between the change of permeate qualities and hydrolysis will be
discussed later in this work; however, biological degradation will
not be addressed because the effect of biological degradation on
the performance of cellulose acetate membranes is controversial
[16,17].
Table 1
Properties of the cellulose acetate NF membrane module
Item NF membrane
Membrane configuration U-shaped hollow-fiber
Outer and inner diameter (␮m) 177 and 86, respectively
Number of hollow-fiber/module 81,000
Membrane fiber length (mm) 270
Salt rejectiona (%) 94
Pure water permeabilityb (L/m2 h kPa) 0.0028
a The information on salt rejection was obtained from the membrane manu-
facturer (test conditions; (1) pressure-driven mode, (2) target: 500 mg/L NaCl
solution, (3) operating pressure: 0.98 MPa, (4) temperature: 25 ◦ C, (5) recovery
ratio: 30%).
b Mean value of three NF membranes (operating temperature: 25 ◦ C).
471
Table 2
Characteristics of influent domestic wastewater
Parameter Range (mean value)
Total organic carbon (TOC, mg/L) 35.3–91.2 (62.5)
Suspended solids (SS, mg/L) 40–180 (82.9)
pH 7.27–7.85 (7.61)
Conductivity (mS/m) 33.8–206.0 (122.0)
Dissolved oxygen (mg/L) 6.07–7.59 (6.61)
Total nitrogen (T-N)a (mg N/L) 7.2–31.9 (25.3)
Total phosphorus (T-P) (mg P/L) 2.27–31.1 (6.53)
Temperature (◦ C) 16.0–22.5 (18.6)
Volumetric loadingb (kg TOC/m3 day) 0.018–0.039 (0.030)
(day 1–day 161)
0.045–0.061 (0.052)
(day 162–day 240)
a The data represent the concentrations of dissolved T-N.
b The data were calculated without consideration for the volume of tap water
(approximately 3.15 L/day) used for periodic membrane flushing.
2.2. Experimental setup and operating conditions
Three NF membrane modules were immersed in a bioreactor
with an effective volume of 36.3 L. Periodic membrane flushing
using tap water – meaning not backwashing (inside-to-out), but
merely the washing of the outside of the membrane fibers in the
bioreactor – was performed to control concentration polarization
at the surface of the NF membranes and to remove anaerobic
conditions from the inside of each membrane module. NF#2
and NF#3 membranes were flushed, at the rate of approximately
450 mL/trial, three and four times a day, respectively.
Characteristics of the influent domestic wastewater are given
in Table 2. Since the feed wastewater was provided from a munic-
ipal sewage treatment plant located at the landfill site of Tokyo
Bay, Japan, the influent included a considerable amount of chlo-
ride ion (254.2 ± 147.0 mg/L) due to the effect of seawater.
Initial permeate flux and hydraulic retention time (HRT) were
initially set to approximately 0.021 L/m2 h and 2.0 days, respec-
tively, and after day 160, converted to 0.029 L/m2 h and 1.5 days
due to the increase in permeate flux. The membrane filtration was
operated intermittently, meaning a cyclic mode of a 5 min run
and 5 min pause.
Seed-activated sludge was collected from the pilot-scale
anoxic-aerobic wastewater treatment works at a mixed-liquor
suspended solids (MLSS) concentration of approximately
3600 mg/L. Daily withdrawal of mixed liquor was conducted
from the reactor in order to maintain the predetermined SRT
and to control an excessive increase of organic matter and salt
concentrations in the bioreactor. The SRT of 40 days was main-
tained from reactor startup to day 38, and thereafter, the SRT
was prolonged to 80 days. Chemical cleaning of the membrane
module was not carried out during the operation.
2.3. Sampling and pretreatment
To measure water-quality parameters such as total organic
carbon (TOC) and total phosphorus (T-P) in the influent wastew-
ater, samples were pretreated with high-frequency sound waves
(40 W) for 3 min. Supernatant was obtained by centrifuging the
472 J.-H. Choi et al. / Separation and Purification Technology 52 (2007) 470–477
mixed liquor from the bioreactor for 5 min at 3000 × g with a
centrifuge (H-3R, Kokusan, Japan), followed by filtering with
a 0.45 ␮m cellulose acetate membrane filter (DISMIC, Toyobo,
Japan). Permeate was taken 3 h after a flush of the membrane
to reduce the influence of flushing. To measure the dissolved
organic carbon (DOC) in the waters of the NF MBR, samples
were filtered using the 0.45 ␮m membrane filter.
2.4. Analytical methods
The TOC and DOC of the influent wastewater and super-
natant were measured using a TOC-500 analyzer (Shimadzu,
Japan) with an auto-sampler. The TOC and DOC of perme-
ates from the NF MBR were analyzed using a TOC-5000A
analyzer (Shimadzu, Japan) and the non-purgeable organic car-
bon (NPOC) method. The concentrations of anions and cations
were analyzed using an ion chromatographic analyzer (IC7000,
Yokogawa, Japan) and an inductively-coupled plasma-atomic
emission spectrophotometer (Optima 3000DV, Perkin-Elmer,
USA), respectively.
Molecular weight cutoff (MWCO) of the NF membrane
was determined using single non-charged organic solutes. In
this measurement, a U-shaped hollow-fiber membrane module
(surface area: 0.2 m2 ) and a pressure vessel (DV-20-ST, Advan-
tec, Japan) were used. Size-exclusion chromatography (SEC)
was used to determine the MW distribution of DOM in the
waters from the NF MBR. The measurement was carried out by
high-performance liquid chromatography (LC 10A, Shimadzu,
Japan) using a protein KW 802.5 column (Column No. 12022,
Shodex, Japan) at pH 7.00 ± 0.05. To calibrate the equipment,
MW standards of various sodium polystyrene sulfonates (PSS)
were used. Detailed methodology of the SEC measurement is
given elsewhere [18]. To fractionate the DOM in the waters
from the NF MBR, macroporous resins (XAD-8 and XAD-4)
were adopted. The organic matter in the waters consisted of
hydrophobic (XAD-8 sorbable), transphilic (XAD-4 sorbable),
and hydrophilic (neither XAD-8 nor XAD-4 sorbable) fractions.
The detailed measurement protocol is given elsewhere [19].
3. Results and discussion
As mentioned above, the membrane flushing was employed to
control the concentration polarization at the membrane surface
and to improve the water flow inside the membrane modules. The
NF#1 membrane without periodic flushing showed unexpected
performance in terms of organic matter and salt rejections, espe-
cially during the early stage of the operation (permeate DOC:
average 8 mg/L; Cl− rejection: below 10%), and after day 160,
the permeate DOC was restored to the same level as that of NF#2
and NF#3. This might be explained by the buildup of an anaer-
obic condition inside the NF#1 membrane module, which could
be formed by the configuration of the NF membrane. The results
and discussion on the performance of the NF#1 membrane have
thus been excluded from this paper. On the contrary, the NF#2
and NF#3 membranes showed expected performances, suggest-
ing that the periodic flushing was efficient to prevent anaerobic
condition from occurring. However, the flushing did not achieve
Fig. 1. Evolution of TOC and DOC concentrations in the waters from the NF
MBR.
the primary purpose to moderate the concentration polarization
and high initial suction pressure. Since the performance differ-
ences between the NF#2 and NF#3 membranes provoked by
different flushing conditions were effectively negligible as well,
the averaged data of the NF membranes were shown in this paper.
3.1. Removal of organic matter
Fig. 1 represents the evolution of the averaged DOC concen-
trations in the permeates from the NF#2 and NF#3 membranes.
The DOC concentrations were in the range of 0.5–2.0 mg/L for
the first 130 days, suggesting that the NF membranes could
produce very good-quality permeate for a long-term operation.
After day 130, the DOC values were gradually increased and
reached approximately 3.0 mg/L. In addition, the average total
nitrogen and total phosphorus in the permeates during the oper-
ation were 20.56 ± 4.14 and 3.08 ± 1.49 mg/L, respectively.
To measure the potential of the fresh NF membrane in terms
of organic-matter rejection, MWCO analysis was carried out
(Table 3). The non-charged organic solutes were used as the
target materials because their rejection is primarily governed by
the sieving exclusion of the NF membrane. The MWCO result
indicates that the NF membrane used is not a tight membrane,
and the NF MBR can produce a better-quality permeate when a
tighter NF membrane is employed.
The submerged MBR system removes organic matter through
two functional units, the bioreactor (biodegradation) and the
Table 3
Molecular weight cutoff (MWCO) of the fresh NF membrane
Organic solute MW (Da) Rejection (%)
Ethanol 46.07 0.10
Glucose 180.16 5.45
Sucrose 342.34 10.25
Raffinose 504.42 13.73
␣-Cyclodextrin 972.85 16.95
Test conditions; (1) suction mode, (2) membrane surface: 0.21 m2 , (3) pressure:
70 ± 5 kPa, (4) temperature: 20.0 ± 1.0 ◦ C, (5) pH: 6.0 ± 0.5, (6) feed concen-
tration: 10 mgC/L.
 J.-H. Choi et al. / Separation and Purification Technology 52 (2007) 470–477
Fig. 2. Contributions of biological treatment and membrane filtration to the
removal of organic matter.
membrane module (membrane separation). To evaluate the
achievement of organic removal by both units in the NF
MBR, overall removal efficiency (ROverall ), removal efficiency
by bioreactor (RReactor ), and removal efficiency by membrane
(RMembrane (= ROverall − RReactor )) were calculated (Fig. 2). The
ROverall of the NF membranes (NF#2 and NF#3) averaged
97.3%. 80.1% of the removal efficiency was removed by the
bioreactor and the residual of 17.2% was rejected by the mem-
brane filtration. While 20–30% of the influent TOC was removed
by the membrane filtration for the first 130 days, less than 10%
of the influent TOC was removed for the last 110 days.
To investigate further the performance of organic rejection
by the membrane filtration, the removal efficiency by the NF
membrane was recalculated using the following equation:
100 × [Supernatant DOC − Permeate DOC]
rMembrane =
Supernatant DOC
From Fig. 2, it was determined that the rejection efficiency
for the first 130 days was over 80%, indicating that the NF
membrane module played a significant role in organic removal
irrespective of a variety of supernatant concentrations.
To examine why the permeate DOC increased gradually over
operating time, the permeate TOC (the concentration of organic
carbon before filtering with a 0.45 ␮m membrane filter; data not
shown) was measured at irregular time intervals. As a conse-
quence, the difference between TOC and DOC in the permeate
was effectively negligible, meaning that there was no mechanical
damage to the membrane modules. The poor-quality of the NF
MBR permeate could thus be attributed to the deterioration of
the cellulose acetate membranes resulting from increase in pore
size and porosity, and the decrease of hydrophobicity caused by
the hydrolysis of cellulose acetate, which will be discussed in
the next sections [20].
3.2. Rejection of salt
Salt rejection is an important factor in evaluating the elec-
trostatic repulsion property of the NF membrane. For charged
NF membranes, the performance of ion separation is controlled
473
Fig. 3. (a) Salts (Cl− , Na+ , SO2 − and Ca2+ ) rejection (salt rejection = 100 ×
[supernatant − permeate]/[supernatant]) and (b) evolution of salts concentration
in the supernatant.
primarily by the Donnan exclusion effect, which increases
with membrane charge [21,22]. Throughout the operation,
the rejection of cationic and anionic ions was measured to
observe changes in the electrical property of the NF membrane
(Fig. 3(a)). For the initial 80 days, the rejection rates of mono-
valent and divalent ions by the NF membranes ranged from
40 to 60% and from 70 to 90%, respectively. Similar to the
removal efficiency of the organic matter, the rejection rates here
decreased gradually after day 80. In addition, the evolution of
the ion concentration in the supernatant is shown in Fig. 3(b).
Since ions are retained by the NF membrane, there is a possi-
bility of their accumulation in the bioreactor. However, the salts
were mostly passed at the late stage of the operation. The result
clearly showed that salts were not accumulated in the bioreac-
tor, resulting from the decrease of salt rejection by the cellulose
acetate NF membrane.
The decrease in salt rejection by the NF membrane over
operating time might be explained by the increase in pore
size and the decrease in the surface charge of the NF mem-
brane caused by the hydrolysis of cellulose acetate materials
in wastewater [20]. Generally, cellulose acetate membranes
undergo hydrolytic decomposition. This is manifested by the
substitution of hydroxyl groups for acetyl groups, which dras-
tically degrades reverse osmosis (RO) and NF membrane per-
474 J.-H. Choi et al. / Separation and Purification Technology 52 (2007) 470–477

formance [15]. The mechanism by which ions are rejected by

the cellulose acetate NF membrane is primarily governed by
parameters such as steric hindrance and electrostatic interac-
tion between membrane and ion. The steric hindrance depends
on the stability of the formed complex between the cation and
the ligand. For simple electrolytes, the rejection depends on the
electrical interactions, which are controlled by the surface charge
developed on the membrane material. With the increase of the
extent of hydrolysis (desalting of polymer matrix) of the cel-
lulose acetate, the permeation rate increases and salt rejection
inversely decreases [20,23]. Vos et al. reported that the salt rejec-
tion of a cellulose acetate membrane drops from more than 95%
to less than 80% when exposed to a pH of 8.3 in feed solution
for 135 days [14]. Although there was no direct evidence, such
as decrease of membrane surface charge, relevant to the hydrol-
Fig. 4. Evolution of relative flux (J/J0 , J0 : initial flux, J: flux), transmembrane
ysis of cellulose acetate membranes, the decline in salt rejection pressure (TMP), and permeability in the NF MBR.
suggests that the quality of the NF membrane used in this work
was degraded by the hydrolysis.
and permeability were observed (Fig. 4). The averaged relative
flux of NF#2 and NF#3 membranes was maintained at the con-
3.3. Changes of permeate flux and transmembrane pressure stant level of 1.0 or less (the permeability: 0.0006 L/m2 h kPa),
whereas the averaged TMP of the NF membranes fluctuated
To evaluate water productivity of the submerged NF MBR in within the range of 60–85 kPa for the first 80 days. High TMP in
actual domestic wastewater treatment, relative flux (the ratio of the early stage of the operation can be explained by the intrinsic
each flux (J) to initial flux (J0 )), transmembrane pressure (TMP), tightness and high salt rejection of the NF membrane. After 80

Fig. 5. MW distribution of supernatant and permeates on (a) day 30, (b) day 97, and (c) day 157.
 J.-H. Choi et al. / Separation and Purification Technology 52 (2007) 470–477 475

days, the relative flux of the NF membranes increased gradually

to approximately 1.2 (the permeability: 0.0017 L/m2 h kPa), and
finally the initial permeate flux was forced to increase from 0.021
to 0.029 L/m2 h in order to keep up a relative flux of 1.0 after
day 162. On the other hand, the TMP of the membranes con-
tinued to decrease to approximately 20 kPa irrespective of the
increase in the initial flux. In addition, the averaged permeability
(0.0035 L/m2 h kPa) of NF#2 and NF#3 membranes at day 228
was higher than the pure water permeability (0.0028 L/m2 h kPa)
of the fresh NF membranes.
The increase in permeate flux and decrease of TMP during the
operation might be attributable to the increase in pore size and
porosity, and decrease in surface charge of the NF membrane,
resulting from the hydrolysis of the cellulose acetate. The cellu-
lose acetate membrane is a porous membrane, and therefore the
water permeation is governed by a function of the pore radius
[24]. With the increase of the pore size or porosity resulting
from the extent of the desalting of the polymer, the permeation
rate increases. In addition, the decrease in salt rejection could
contribute to the increase in permeate flux since the net driving
force in the NF process increases with decreasing salt rejection
[25].

3.4. Further investigation into the performance change of

the NF membrane

To observe the change in pore size and hydrophobicity of

the NF membranes employed in this work, MW distribution and
fractionation of the DOM in the supernatant and permeate of the
NF MBR were observed.

3.4.1. Molecular weight distribution
The MW distributions of DOM in the supernatant and perme-
ates were measured using size-exclusion chromatography and
were expressed in terms of UV absorbance at a wavelength of
260 nm over elution time. Fig. 5 illustrates the chromatograms
for the waters from the NF MBR on days 30, 97 and 157. The
MW values calculated by the data from PSS standards were also
expressed in the chromatograms.
The MW distributions of the supernatant and permeates on
day 30 showed that the permeates of the NF#2 and NF#3 mem-
branes consisted of organic matter smaller than approximately
2700 Da, with the largest fraction being 747 Da (Fig. 5(a)).
This shows that the NF membranes did not completely reject
organic matter with MW smaller than 607 Da. Similar to the
result of the MWCO analysis, this unexpected finding indicates
that the NF membranes used in this study were not as tight as
expected.
To compare the change of MW over operation time, the MW
distributions on days 97 and 157 were also measured, and are
shown in Fig. 5(b and c), respectively. In comparison to the chro-
matogram on day 30, the MW distribution of permeates on day
97 had changed significantly, whereas the MW distribution curve
of permeates on day 157 corresponded approximately with that
of the supernatant. The largest MW fraction of organic matter in
permeates of the NF MBR increased from 747 Da on day 30 to
1189 Da on day 157. This could be explained by the fact that the
Fig. 6. Fractionation of dissolved organic matter in the waters from the NF MBR
using XAD-4 and XAD-8 resins; (a) supernatant and (b) permeate.
pore size of the NF membranes gradually increased over oper-
ation time as a result of the hydrolysis of the cellulose acetate.
In addition, the change of MW distribution of DOM over time
could be seen as evidence demonstrating the relation between
the increase in permeate DOC and the increase in pore size.
3.4.2. Fractionation of dissolved organic matter by XAD
resins
The fractional distribution by hydrophobicity/hydrophilicity
of DOC in the waters from the NF MBR during the operation
is illustrated in Fig. 6. The isolation procedure permits determi-
nation of hydrophobic (HPO), transphilic (TPI) and hydrophilic
(HPI) DOC fraction. The three isolated fractions of DOC exhib-
ited different characteristics in terms of molecular size, aro-
maticity and charge density. The HPO fraction was comprised
of the least polar and generally highest MW humic materi-
als, and the highest aromaticity of the DOC fractions. The TPI
fraction was of intermediate polarity and contained greater car-
boxyl acidity and lower MW organic matter. The HPI fraction
consisted of the most polar organic matter, and included the
most mobile and lowest MW compounds of the three fractions
[26,27].
476 J.-H. Choi et al. / Separation and Purification Technology 52 (2007) 470–477
From the averaged data of the NF#2 and NF#3 membranes on
days 68 and 114, the NF membranes rejected large amounts of
the HPO and TPI fractions in the supernatant, resulting in very
low DOC concentration in the permeate. On the other hand,
the NF membranes did not effectively reject the HPO and TPI
fractions as well as the HPI fraction on days 157 and 199. The
change of MW distribution in each permeate from the NF MBR
indicates the change in pore size distribution in the NF mem-
branes. The HPO and TPI fractions possessed MW larger than
the HPI fraction and a high negative charge due to deprotonated
carboxylic groups as well [26]. Therefore, it could be hypothe-
sized from the result that the increase in HPO and TPI fractions
during the operation was primarily attributed to the increase in
pore size and decrease in surface charge and hydrophobicity of
the membranes that resulted from the hydrolysis of the cellulose
acetate.
4. Conclusions
In this work, the submerged NF MBR using hollow-fiber
membrane modules produced very good water-quality and rea-
sonable water productivity. The following conclusions in terms
of the performance of cellulose acetate NF membranes in the
submerged NF MBR for long-term operation are supported by
the experimental results.
(1) The DOC concentration in the permeates from the NF
MBR using cellulose acetate membranes ranged from 0.5 to
2.0 mg/L for the first 130 days, and subsequently increased
to approximately 3.0 mg/L, indicating that the NF MBR
could produce very good-quality permeate for a long-term
operation.
(2) Each rejection rate of monovalent and divalent ions by the
NF membranes varied between 40 and 60% and between
70 and 90%, respectively, for the initial 80 days, whereas
the salt rejection decreased gradually thereafter. Through-
out the operation, relative flux increase was observed with
decreasing TMP as well.
(3) The MW distributions of DOM in the permeates from the
NF MBR showed that the pore size increased over operating
time. The fractionation of DOM in the waters using XAD
resins suggested that the hydrophobicity and charge of the
cellulose acetate NF membranes decreased over operating
time.
(4) The degradation of each water-quality parameter over oper-
ating time might be attributable to the change in the proper-
ties of the NF membrane resulting from the hydrolysis of the
cellulose acetate in wastewaters, suggesting that hydrolysis
leads to an increase in pore size and porosity, and a decrease
in hydrophobicity and charge, of the cellulose acetate mem-
branes.
Acknowledgement
The authors wish to acknowledge the NF membrane mod-
ules and technical support provided by TOYOBO Co. Ltd.,
Japan.
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