Journal of Water and Environment Technology, Vol.5, No.

2, 2007

Fouling characteristics of PVDF microfiltration membranes in a pilot-scale drinking

water production system after a coagulation/sedimentation using PSI (polysilicato-iron)
and PACl (polyaluminium chloride)

S. R. Chae◎ and Y. Watanabe○

Department of Environmental Engineering, Graduate School of Engineering,
Hokkaido University, Nishi 8, Kita 13, Sapporo 060-8628, Japan
(Tel: +81-11-706-6267, E-mail: srchae@eng.hokudai.ac.jp; yoshiw@eng.hokudai.ac.jp)

ABSTRACT

A pilot-scale microfiltration polyvinylidene fluoride (PVDF) membrane with multiple pore sizes
(0.1 ㎛ and 0.05 ㎛) was operated after a coagulation/sedimentation using a polysilicato iron (PSI) as
coagulant has been fabricated and operated. As a result, turbidity was removed completely and organic
matter, humic substances, and metals (Al, Fe) were removed very well by the experimental system.
Accordingly, it was concluded that a membrane with a dense skin was more effective for reducing
membrane fouling than a membrane with homogeneous structure although the nominal pore size of the
former (0.05 ㎛) was smaller than that of the latter (0.1 ㎛). It still remains to study the effects on
membrane fouling of the interaction between organic and oxidized inorganic matters (such as Fe and Mn)
which occure during pre-chlorination.

Keywords: microfiltration PVDF membrane; coagulation/sedimentation; PSI; pre-chlorination;

membrane fouling.

INTRODUCTION

Low-pressure membrane techniques such as microfiltration (MF) and ultrafiltration (UF) can remove
particulate and colloidal matters bigger than the pore size of the membrane and usually produce a filtrate
free of turbidity and bacteria. These have been widely used to produce drinking water from river, lake,
and underground water (Hagen, 1998; Ma et al., 1998; Yuasa, 1998; Bian et al., 1999; Klijn et al., 2000;
Kimura et al., 2004). However, those membranes are less effective in removing dissolved molecules such
as humic substances and inorganic matters. To mitigate membrane fouling, a hybrid membrane system
combined with processes such as coagulation/sedimentation, ozonation, and activated carbons has been
widely adopted.
Jang et al. (2002 and 2005) applied the jet mixed separator (JMS) (Watanabe et al., 1998) as a
coagulation/sedimentation unit for a polymerized polyacrylonitrile (PAN) UF membrane with a nominal
pore size of 0.01 ㎛. Use of the coagulation/sedimentation process with a polysilicato iron (PSI) as a
coagulant (Hasegawa et al., 1991) extended the UF membrane operation period by removing dissolved
organic carbon (DOC) effectively. Lee et al. (2004) reported that pre-ozonation reduced membrane
fouling of a PVDF membrane with a nominal pore size of 0.1 ㎛ by degrading organic material such as
humic substances. The increase of particle size by use of an ozone-induced destabilization reaction also
improved filtration efficiency of the membrane.
As based on literature, the effectiveness of membrane filtration depends on the raw water quality and
the operating conditions. Because this high permeability, high strength PVDF membrane was only
recently developed for drinking water production (Yeh and Wang, 2004; Kurihara et al., 2004). Therefore,
the feasibility of the new PVDF membrane processes should be evaluated by long-term tests using natural
raw water. Building upon previous work, this study was designed to challenge current problems in
drinking water production related to pollutant removal and membrane fouling, using a novel PVDF
membrane for filtration after pre-coagulation/sedimentation.

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 Journal of Water and Environment Technology, Vol.5, No.2, 2007

MATERIALS AND METHODS

Characteristics of raw water

For this study, Chitose River water in the Kamiebetsu Water Purification Plant (Ebetsu City, Japan)
was used as raw water. Although the water quality of Chitose River changed seasonally, it typically
contains relatively high turbidity, organic matter, and humic substances (Bian et al., 1999; Jang et al.,
2002).

Experimental set-up of a pilot-scale PVDF membrane filtration system

The pilot-scale membrane filtration system was composed of a coagulation/sedimentation (JMS and
sand filtration) process and filtration using PVDF membranes (TORAY Industries, Inc., Japan) having
multiple pore sizes. Details of the composition of this system are summarized in Table 1. Periodic
backwashing was conducted as follows: 30 minutes filtration; 30 seconds backwash with permeate; 1
minute backwash with pressurized air; 1 minute idle; 30 seconds fill. Under this condition, the overall
recovery rate was found to be 98%.

Table 1. Operation conditions of the pilot-scale membrane filtration system

System information Jang et al., 2002 and 2005 This study
- Influent Chitose River water Chitose River water
Temperature 21.9 7.4
Turbidity 20.3 13.1
pH 7.2 7.3
E260 (1/cm) 0.12 0.08
TOC (mg/l) 2.54
DOC (mg/l) 2.31 2.07
Total Al (ppb) 500 194
Total Mn (ppb) 100 171
Total Fe (ppb) 2,100 473
- Coagulation/sedimentation process JMS JMS
Hydraulic retention time 84 minute 84 minute
Coagulant polysilicato-iron, PSI polysilicato-iron, PSI
Dosage 12 mg/l as Fe 12 mg/l as Fe
pH 6.2 6.5
- Sand filtration Three layer sand filter
Linear velocity - 100 m/day
Backwashing every 48 hours
- Membrane filtration process PAN membrane PVDF membrane
Module type Hollow fiber Hollow fiber
Nominal pore size 0.01 ㎛ 0.1 ㎛ and 0.05 ㎛
Operation mode Pressurized type Pressurized type
Filtration mode Constant flow rate Constant flow rate
Surface area: 12 m2 7 m2
Permeate flux 0.9 - 1.5 m/day 2.5 m/day
Interval of physical cleaning 1 hour 30 minute
Chlorine dose (as Cl2) - 1 mg/l (in-line addition)

Analytical methods
Turbidity was analyzed using an integration ball type turbidity meter (SEP-PT-706D, Mistubishi
Chemical, Japan) after ultra-sonification for 10 seconds. To check temperature and pH, a portable pH
meter (HM-12P, TOA electronics Ltd., Japan) was used. Humic substances (E260) were measured by
UV/VIS spectrophotometer (U-2000, Hitachi, Japan) with a one cm cell. Total organic carbon (TOC) and
DOC were measure by a TOC meter (TOC-5000A, Shimadzu, Japan). Inorganic matter such as Al, Mn,
Fe were determined by an inductively coupled plasma atomic emission spectrophotometer (ICPS-7500,
Shimadzu, Japan). The chlorine dose was measured by the DPD method.

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 Journal of Water and Environment Technology, Vol.5, No.2, 2007

RESULTS AND DISCUSSIONS

As shown in Fig. 1, average concentrations of turbidity, TOC, and humic substances (E260) in raw
water were 13.4, 2.54 mg/l, and 0.08 cm-1, respectively. About 81% of TOC was composed of dissolved
matter. The PVDF membrane filtration system showed almost complete removal of turbidity, humic
substances, and inorganic matters (Al, Fe). Most of the turbidity (94.1%), humic substances (78.5%),
TOC (41.8%), and total Al (90.4%) were removed by the coagulation/sedimentation process (Fig. 1
(right)). However, total Fe (73.2%) that was mostly rejected by the SF. As a result, Al and Fe removal
efficiencies were greater than 95% and 99%, respectively, while Mn concentration in permeates exceeded
the drinking water standards of Japan (< 50 ppb). Specially, as shown in Fig. 2, Fe and Mn concentration
in the effluent of JMS increased as water temperature decreased. Therefore, it could be concluded that
those inorganic matters were oxidized by chlorine and caused severe membrane fouling. As based on
literature, Fe and Mn were found to cause membrane fouling in the treatment of drinking water (Xu et al.,
2004; Choo et al., 2005). Fig. 3 (left) shows variations of temperature and transmembrane pressure
(TMP) of the HFM (0.1 ㎛) and HFS (0.05 ㎛) membranes during the experimental period. It was
concluded that decrease of temperature adversly affected TMP, and that the HFS membrane was more
effective to reduce membrane fouling than the HFM membrane. On the other hand, it was found that Fe
and Mn were major foulants (Fig. 3 (right)).

0.20 30 5
Turbidity
0.18 E260
25 TOC 4
0.16 DOC
TOC and DOC (mg/l)

20
0.14
E260 (1/cm)

3
Turbidity

0.12 15

2
0.10
10
0.08
1
5
0.06

0.04 0 0
0 5 10 15 20 25 30 35 35 40 50
Time (day)

Fig. 1 Variations of raw water quality (left) and average removal efficiency of pollutant by each unit
process (right).

600 12
0.05 3.0 12
Al
Concentration of inorganics (ppb)

Turbidity 500 Fe 10
2.5 TOC 10 Mn
0.04
Turbidity (-) and TOC (ppm)

Temperature Si
Temperature (oC)

UV260 400 Ca 8
2.0 8
Temperature ( C)
o
E260 (1/cm)

0.03
300 6
1.5 6

0.02
1.0 4
200 4

0.01 100 2
0.5 2

0.00 0.0 0 0 0
Oct. Nov. Dec. Oct. Nov. Dec.
Year 2004 Year 2004
Fig. 2 Variation of the effluent quality of JMS during the experimental period.

1.6 20

TMP of 0.1μm membrane

1.4
TMP of 0.05μm membrane
Temperature
Water temperature (oC)

1.2 15
TMP@25 C (Bar)

1.0
o

0.8 10

0.6

0.4 5

0.2

0.0 0
0 5 10 15 20 25 30 35 40 45 50
Time (day)

Fig. 3 Variations of temperature and TMP (left) and inorganics extracted by HCl and oxalic acid (right).

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 Journal of Water and Environment Technology, Vol.5, No.2, 2007

CONCLUSIONS

In this study, the new pilot-scale PVDF membrane filtration system was fabricated and operated to
produce potable water from river water. As a result, turbidity was removed completely and organic matter,
humic substances, and inorganic matters (Al, Fe) were removed very well by the experimental system. In
addition, it was concluded that the HFS membrane (0.05 ㎛) was more effective to reduce membrane
fouling than the HFM membrane (0.1 ㎛) although the nominal pore size of the former was half of the
latter. However, Mn concentration in permeates exceeded the drinking water standards of Japan and
membrane fouling severed by increase of Fe and Mn concentration in the effluent of JMS.
In the next phase of experimentation, the coagulant will be changed from PSI to polyaluminium
chloride (PACl) and coagulant dose will be controlled and chlorine will be supplied during the
backwashing period instead of pre-chlorination to mitigate membrane fouling by Mn . Batch tests will
also be conducted to study the effects of organic and inorganic matters on membrane fouling .

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