Desalination 238 (2009) 183–191

Study on ultrafiltration for surface water by a polyvinylchloride

hollow fiber membrane
Xiaoyan Guoa, Zhenjia Zhangb, Lin Fanga, Liguo Sua
a
Tianjin Key Laboratory of Environmental Remediation and Pollution Control, College of Environmental Science
and Engineering, Nankai University, 23 Hongda Street, TEDA, Tianjin 300457, China
Tel./Fax: +86 (22) 6622 9535; email: guoxyan@nankai.edu.cn
b
College of Environmental Science and Engineering, Shanghai Jiaotong University,
800 Dongchuan Road, Shanghai 200240, China

Received 23 October 2005; Accepted 28 November 2007

Abstract
Low pressure membrane filtration processes are increasingly competing against conventional surface water
treatment plants. In comparison with conventional processes, UF technology has many advantages, but it is also
important that a kind of membrane is suitably selected and operated. In this paper, a pilot plant study on a
polyvinylchloride ultrafiltration (MWCO of 80 kD) hollow fiber membrane process was performed for the treatment
of surface water. The new membrane had an optimized pore size distribution over membrane thickness while
membrane material and fiber dimensions remained the same, the modification resulted in a much higher pure water
flux (160 l/(m2 h bar) at 20EC). The membrane system was operated in the dead-end filtration modes with different
constant permeate fluxes. The results showed that the permeate quality was stable, regardless of different surface
water for a long duration of filtration. The transmembrane pressure should be operated in less than 1 bar to avoid
irreversible fouling. Treating cold raw water below 5EC in constant pressure operation mode was better than in
constant permeate flux.

Keywords: Ultrafiltration; Hollow fiber membrane; Drinking water treatment; Surface water

1. Introduction
UF membranes are physical barriers which are
Today, ultrafiltration (UF) technology is able to efficiently remove suspended particles,
recognized by the water industry as a very attrac- turbidity, bacteria, colloids, algae, parasites and
tive process for producing drinking water [1]. viruses for clarification and disinfection purposes.
In comparison with conventional processes such
*Corresponding author. as coagulation, flocculation, sedimentation and/or

0011-9164/09/$– See front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2007.11.064
184 X. Guo et al. / Desalination 238 (2009) 183–191

flotation, rapid and slow sand filtration, UF tech- operating conditions to minimize fouling for UF
nology has many advantages such as (1) superior membrane to be run stably for a long time.
quality of treated water, (2) a much more compact
system, (3) easier control of operation and main-
tenance, (4) fewer chemicals, and (5) less pro- 2. Materials and methods
duction of sludge [1,2].
2.1. Feed water characteristics
Communities are increasingly looking to UF
as a safer treatment alternative. At present, UF Tianjin is a city lacking in drinking water;
full-scale applications are evenly spread over every year it is supplied by the Luan River in the
Europe and the US [3]. The US ultrafiltration summer and autumn and the Huang River in the
market was expected to reach US $727 million by winter and spring. So there were two types of
2007, according to an updated report available surface water under investigation in this study.
from Business Communications Co Inc (BCC). The first water originated from the Luan
Except for developed countries, in many areas of River. The water is pumped to a reservoir. It is
developing countries potable water production is characterized by high algae contents in the
potentially a very large market for UF mem- summer. This meant that turbidity ranged from
branes. Because one of the most critical problems 6–20 NTU.
in developing countries is the lack of drinking The second water originated from the Huang
water, people in these regions are supplied with River; the water has a high content of low mole-
surface water which contains a significant amount cular weight organic components. This resulted in
of microorganisms that can cause several diseases high KMnO4 consumption (about 6 mg/l CODMn).
[4]. And another characteristic was low temperature
It should be emphasized that due to the rapid in winter (below 5EC).
development of this fairly new technology, capi- The two types of surface water were used
tal and operational costs of UF membrane tech- separately in this study.
nology are still expected to decrease. So it is
attractive to develop a new UF membrane tech-
2.2. Membrane and membrane module
nology which is cheaper in capital and operation
costs. The hollow fiber UF membrane was made
This study deals with one new type of UF from PVC (a commercial product from Litree
hollow fiber membrane made from polyvinyl- Co., Hainan, China). It has an internal fiber dia-
chloride (PVC) used for drinking water treatment meter of 0.9 mm and outer fiber diameter of
of surface water, although the tubular UF mem- 1.4 mm; the given cut-off value is 80 kD, and the
branes made from PVC have been used for puri- average pore size is 4–6 nm. As shown in Fig. 1,
fication of bilge water and copper wire drawing its structure is doubly asymmetric, which means
emulsion by Karakulsi et al. [5,6]. The UF mem- that the hollow fiber has an inner and outer skin.
brane has many merits such as high permeability, This was the result of the phase inversion process
low cost etc., in comparison with other UF when spinning those fibers. One might presume
hollow fiber membranes such as polysulfone, that permeability would be decreased by two
cellulose acetate etc.. skins due to a higher flow resistance, but in fact
The objectives of this study were to: (1) evalu- the double asymmetric structure gave the fiber a
ate the UF performances in terms of permeability higher mechanical stability compared to a con-
and quality of treated water, and (2) select the ventional anisotropic hollow fiber membrane.
 X. Guo et al. / Desalination 238 (2009) 183–191 185

size to remove bigger suspended solids, about

1–5 mg/L coagulation agents of ferric chloride
are added in the pipe and stirred by centrifugal
pump, and then the water is filtrated by the bag-
style filter with 150 µ pore size to remove flocs.
The pretreated water enters the UF filtration unit.
The UF unit includes two membrane modules
which can be used separately or simultaneously.
The parameters such as pressure (0–2 bar), pH,
turbidity (0–100 NTU), conductivity, temperature
(0–30EC), the filtrate and retentate flows can be
real time measured by a data transmitter. The unit
enables the dead-end and cross-flow filtration
Fig. 1. SEM photograph of PVC hollow fiber UF mode to be carried out automatically. In this
membrane.
study, the dead-end filtration mode was used in
the filtration period of 20–40 min (flux decreased
A further advantage is that there is no risk of an about 5% of initial one), then hydraulic cleanings
in-pore clogging of the membrane when back- in the sequence of flushing, backwashing and
washing with higher pressures from the permeate flushing for about 10 s respectively were carried
side [7]. out. The flushed and backwashed water were
The membrane module is the LH-3-1060 returned to the feed tank. When the fouling of the
model, 250 mm diameter, 1500 mm module UF membrane was serious (the flux decreased
length. The total effective membrane area is about 10% of initial one), chemical cleanings
50 m2, permeability of pure water is 160 l/(m2 h with agents like NaClO, NaOH and HCl were
bar) (at 20EC), the pH range is 2–11, and maxi- used, and the duration was about 10–20 min,
mum resistant temperature is 40EC. Another respectively.
advantage of the PVC membrane is that it is more
resistant to free chlorine (100 ppm in continuous)
2.4. Methods of analysis
than polysulfone membranes (25 ppm in con-
tinuous) [4]. This is very important from the point Natural organic matter was characterized by
of view of cleaning when the membranes suffer CODMn, and the bacteria and coliform were
biofouling, which could happen when treating detected according to the Standard Methods for
surface water. the Examination of Water and Wastewater,
4th ed. (2004).
2.3. Pilot plant description
A schematic diagram of the pilot-scale hollow 3. Results and discussion
fiber UF system is shown in Fig. 2. The system
3.1. Performance characteristics of the UF
consists of three parts: the pretreatment unit, UF
membrane
filtration unit and cleaning unit. The pretreatment
unit is comprised of a Y-style filter, coagulation The raw water was pretreated with the Y-style
system and bag-style filter. The raw water firstly filter which pore size was 500 µ to remove
passes trough the Y-style filter with 500 µ pore suspended solids, and then was filtrated by UF
 186
X. Guo et al. / Desalination 238 (2009) 183–191
Fig. 2. Schematic diagram of pilot-scale hollow fiber UF system.
 X. Guo et al. / Desalination 238 (2009) 183–191 187

Table 1
Removal of bacteria and coliform by UF

Bacteria, cfu/ml Coliform, cfu/ml

Raw water Permeate Raw water Permeate

1600 2 120 0
2500 5 230 0
1800 1 790 0
1500 3 5400 0
450 1 50 0
620 0 920 0
1300 1 1800 0

Fig. 3. Removal of turbidity by the UF membrane. fore, an important advantage of the membrane
process towards the conventional filtration exists.

3.1.2. Removal of bacteria and coliform by the

UF membrane
The reductions of bacteria and coliform are
shown in Table 1. The experiments show excel-
lent results from the point of view of micro-
organism rejection, with values near 100%, and
with no difference with regard to feed water
characteristics. Thus, the tested membrane can be
successfully applied to water disinfection.

3.1.3. Removal of natural organic matter by

the UF membrane
Fig. 4. Removal of natural organic matter by the UF
membrane. As shown in Fig. 4, the raw water pretreated
by the Y-style filter was treated by the UF mem-
brane for the first 2000 m3; the raw water pre-
membrane. Samples of permeate and feed water treated by the Y-style filter in addition to coagu-
were collected for turbidity, bacteria and CODMn lation agents and a bag-style filter was filtrated by
analysis to determine the membrane retention. the UF membrane for another 8000 m3. The
Figs. 3 and 4 and Table 1 present the main char- removal results of natural organic matter by the
acteristics of the feed and the filtrate obtained. UF membrane with two different pretreatments
are presented in Fig. 4. There are no differences:
3.1.1. Removal of turbidity by UF membrane their removal rates reached about 20–40% in both
The turbidity of raw water and filtrate is cases. It is seen that the addition of coagulants is
shown in Fig.3. The absolute independence of the useless for improving the removal of natural
filtrate from the raw water can be seen. The organic matter by this PVC UF membrane.
filtrate was characterized by turbidity far below Fig. 5 presents the filtration characteristics of
0.1 NTU, whatever the raw water values. There- UF membrane for two different pretreatment
188 X. Guo et al. / Desalination 238 (2009) 183–191

Fig. 5. Filtration results for two different pretreatment Fig. 6. TMP over the volume of treated water (short
processes. period) for different constant permeate fluxes.

processes. The different results are observed as filtration of natural organic matter by UF is due
follows: (1) sharp increase from 0.7 to 1.0 bar to adsorption sequestration which is not easy to
due to a rapid build-up of a fouling layer for the clean and forms irreversible fouling. If coagu-
pretreatment without coagulation, (2) stable lation is combined with UF, the fine particles can
pressure until 6 m3 treated water due to water be aggregated to be sieved by UF membrane,
pretreated by using coagulation. which form concentration polarization that is
This can be explained as follows: there are considered as reversible fouling and easy to clean
two mechanisms commonly attributed to matter by physical methods when the filtration pro-
removal by UF—sieve retention and adsorption gresses [10]. This treatment combination can be
sequestration. In sieve retention the UF mem- considered for surface water containing high level
brane acts as a barrier for particle penetration. of organic, especially when UF membranes do
The particles are retained on the membrane not remove well dissolved organics and minimize
surface and form a cake that grows in thickness as membrane fouling potential.
the filtration progresses. The second mechanism
involves the entry and capture of the particles into 3.2. Operating characteristics of UF membrane
the membrane matrix. Colloidal stability theory
can be applied to the interaction between colloids 3.2.1. Comparisons of different constant per-
and the membrane matrix. Mechanisms that can meate fluxes
stabilize a colloidal suspension can similarly pre- The UF system was operated in the mode of
vent adhesion of colloids to the internal surfaces constant permeate flux due to stable volume of
of the membranes. The factors that can cause treated water for waterworks. In this study the
more interaction may increase the rejection. If the operating characteristics of two different constant
particles and the membrane are oppositely permeate fluxes operated during short and long
charged or if their zeta potentials are appropriate periods were compared.
the particles will adhere to the membrane matrix Fig. 6 shows the running characteristics of the
resulting in removal of the particles smaller than unit filtration cycle (short period) for two differ-
the pores of the membrane [8,9]. The direct ent constant permeate fluxes. It can be seen for
 X. Guo et al. / Desalination 238 (2009) 183–191 189

As shown in Fig. 7, during more than

3 months for 60 l/(m2 h) constant permeate flux,
the TMP is stable. The increase of TMP for each
cycle is due to concentration polarization which
is considered as reversible fouling [11], the initial
TMP of next cycle can be recovered by hydraulic
cleaning. Whereas for 100 l/(m2 h) constant per-
meate flux a gradual increase of TMP over
volume of treated water is observed, the initial
TMP of next cycle is higher than the former one,
which is attributed to irreversible fouling that
Fig. 7. TMP over the volume of treated water (long cannot be recovered by physical cleaning [12,13].
period) for different constant permeate fluxes. Even if using chemical cleaning, the initial pres-
sure of the next cycle is not the same as the initial
pressure of the beginning cycle. The higher the
60 l/(m2 h) constant permeate flux the increase of permeate flux, the higher the corresponding TMP.
the transmembrane pressure (TMP) is less than That means the higher the TMP, the more serious
0.05 bar, whereas for 100 l/(m2 h) constant per- the membrane fouling. The operation of higher
meate flux the TMP increases for 0.2 bar. So the constant permeate flux is less stable than the
operation mode of higher constant permeate flux lower one.
is easier to foul than the lower one.
Table 2 shows the different operation charac-
Fig. 7 shows the running characteristics of two
teristics of the above-described constant permeate
different constant permeate fluxes for a long time.
fluxes. It can be seen that the operation mode of
The unit filtration cycle is 30 min, and then the
the lower constant permeate flux is better than the
membrane is physically cleaned in the process of
higher one, not only the permeability is higher,
flushing (raw water is entered from the one end of
but also the energy consumption is lower.
the hollow fiber membrane module and go out
Because of that the higher the TMP the more
from the other end for 10 s), backwashing (per-
compact the UF membrane, resulting in easily
meate water is fed from the permeate side and go
fouling. Unfortunately this stands in contradiction
out from the feed water side for 10 s in pressure
to a high TMP to obtain a high permeate flux. In
1.2–1.4 bar) and next flushing (permeate water is
order to minimize the amount of irreversible
entered from the one end of the hollow fiber
fouling and keep a stable flux, the UF membrane
membrane module and go out from the other end
should be operated in a small TMP (#1 bar).
for 10 s) (all of the permeate water used for
physical cleaning is about 200 l per one physical
cleaning cycle). After 8 h (about 16 cycles of unit Table 2
filtration), chemical cleanings are performed in Operation characteristics of different constant permeate
the process which consists of a mixture of 30 ppm fluxes
NaClO and NaOH (pH 11) for 20 min and 0.5
HCl for another 10 min, and then the membrane Constant permeate flux (l/(m2 h)) 100 60
is rinsed with the permeate (the quantity is about
Average TMP (bar) 1.08 0.55
250 l per one chemical cleaning cycle). Accord-
Average permeability (l/(m2 h bar)) 92.6 110
ing to this way described above, the UF system
Average energy consumption (kWh/m3) 0.5 0.3
has been run for about 3 months.
190 X. Guo et al. / Desalination 238 (2009) 183–191

Fig. 9. Permeate flux over volume of treated water during

the process of temperature rising from near 0EC to 5EC.

When the temperature of raw water increases,

the operation mode of constant pressure of 1bar is
Fig. 8. TMP vs. temperature of raw water. selected, as shown in Fig. 9. It can be seen that
when the temperature of raw water increases from
3.2.2. Influences of temperature on operating near 0EC to 5EC, the permeate flux increases
characteristics from 32 to 38 l/(m2 h), or about 1.18 times,
according to the above formula; it can be deduced
The UF system runs in the constant permeate
that the resistance increases little. This means that
flux of 60 l/(m2 h) when the temperature of raw
the UF membrane is not easily fouled in this
water (Huang River) becomes colder; the changes
operation mode. So when the temperature of the
of the TMP are shown in Fig. 8. When the tem-
raw water is lower than 5EC, it is suitable to
perature decreases from 13EC to 5EC, the TMP
select the constant pressure operating mode.
changes little; when the temperature decreases
from 5EC to near 0EC, the increased TMP is 2.75
times higher than the one at 5EC. The viscosity of
4. Conclusions
raw water increases from 1.518 mPa s at 5EC to
1.781 mPa s at 0EC, or about 1.17 times. The pilot tests clearly indicate that the PVC
According to the formula UF membrane is a promising and effective tech-
P nology for drinking water production from
J surface water. The optimized operation (TMP
R #1 bar, filtration time 30 min) with a hydraulic
where J is the permeate flux, l /(m2 s); ΔP the cleaning (30 s) and a chemical cleaning (interval
TMP, Pa; η the viscosity, mPa s; and R resistance 8 h) ensures a quite steady flux [110 l/(m2 h bar)].
(m!1), R increases by 2.35 times. This means the Permeate quality is very high (turbidity 0.1 NTU
membrane is fouled. It can be explained that the etc.).
decrease of temperature makes the pore size of The operating strategy may be either to ope-
the membrane contract, resulting in the decline of rate the plant with a fixed TMP or with a constant
permeate flux if the TMP is constant. But now the permeate flux. With fixed TMP one accepts
system runs in a constant permeate flux, so the short-term variations in permeate flux due to
TMP becomes higher to make the membrane seasonal change in feed water quality and long-
more and more compact and the foulants on the term decay in membrane permeability, caused by
membrane surface are not easily cleaned to form, irreversible fouling. Opposed to this, applying a
thus causing irreversible fouling. fixed permeate flux needs the control of the TMP.
 X. Guo et al. / Desalination 238 (2009) 183–191 191

The short-term change in raw water quality and [3] J.-M. Laîné, D. Vial and P. Moulart, Status after 10
the long-term decay in membrane permeability years of operation—overview of UF technology
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Acknowledgements [10] V. Chen, A.G. Fane, S. Madaeni and I.G. Wenten,
Particle deposition during membrane filtration of
The authors would like to acknowledge colloids: transition between concentration polari-
Mr. He Wenjie and Mr. Han Hongda and the rest zation and cake formation, J. Membr. Sci., 125
of the people at the Jieyuan Waterworks of Tian- (1997) 109–122.
jin for their contribution to this work; and the [11] K.-H. Ahn, H.-Y. Cha, I.-T. Yeom and K.-G. Song,
Litree Company for its invaluable collaboration Applications of nanofiltration for recycling of paper
on their membrane modules. regeneration wastewater and characteristics of fil-
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[12] G.F. Crozes, J.G. Jacangelo, C. Anselme and J.M.
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