Desalination 221 (2008) 168173

Presented at the conference on Desalination and the Environment. Sponsored by the European Desalination Society
and Center for Research and Technology Hellas (CERTH), Sani Resort, Halkidiki, Greece, April 2225, 2007.
Water softening using a generic low cost
nano-filtration membrane
S.C. Low*, Cheng Liping, Lee Seng Hee
School of Mechanical and Aerospace Engineering, Nanyang Technological University,
50 Nanyang Ave, S 639798, Singapore
email: msclow@ultra-flo.com
Received 19 March 2007; accepted 30 April 2007
Abstract
In applications where the water hardness and TDS were marginally higher, the nano-filtration membrane came
in very handy due to its ability in reducing the permeate TDS at reasonable energy cost. In this work, a thin nano-
filtration membrane formed by M-phenylenediamine (MPD) and trimesoyl chloride (TMC) and coated on both
sides of a polyacrylonitrile (PAN) membrane. Interfacial polymerization method was used for the nano-film
formation. Tests showed that thick monomers solution and denser PAN structure would lead to a membrane of
better solutes rejection.
Keywords: Nanofiltration; Polyamide composite membrane; Water softening
1. Introduction
The water available on earth and suitable for
human consumption is very limited. The available
potable water is further reduced due to natural
and human contamination. With the growth of
world population, water shortage in the future
would be eminent if modern and cost effective
technologies are not in large scale applications.
Nano-filtration membrane could play a role by
reducing the hardness and TDS of the marginally
lower quality water and making it suitable for
consumption at reasonable cost.
It performs separation for substance up to
10 nm and applies to water demineralization, soft-
ening and colour removal.
2. Objective
This objective of this work was to cast and test
a generic nano-filtration membrane to address part
of the water availability issues due to the water
hardness [1]. In particular, apply nano-membrane
to hard water with excessive dissolved calcium. *Corresponding author.
doi:10.1016/j.desal.2007.04.064
0011-9164/08/$ See front matter 2008 Published by Elsevier B.V.
S.C. Low et al. / Desalination 221 (2008) 168173 169
3. Materials and methods
The materials used in casting the membrane
were polyacrylonitrile (PAN), N-dimethylfor-
mamide (DMF), M-phenylenediamine (MPD),
trimesoyl chloride (TMC), N-hexane, glycerol and
polyester non-woven fabrics with basis weight
of 83.88 g/m
2
.
This project involved casting of the PAN in
DMF solution [2] on the polyester non-woven
fabric before coating both sides with polyamide
to form a composite nano-filtration membrane.
The PAN membranes used in all experiments
were hydrophilic, thus required storage in wet
conditions when not in use.
The PAN membranes were formed by phase
inversion method which referred to the transfor-
mation of a polymeric casting solution from a
liquid state to a solid state. The membrane cast-
ing started with spreading the viscous PAN in
DMF solution over the non-woven fabric. It was
then immersed into a coagulation bath contain-
ing water as non-solvent. The DMF solvent in
the PAN solution evaporated leaving behind a
layer of porous PAN support structure which
consisted of many finger-like macro-voids. The
solvent, DMF, controlled the membrane poros-
ity during the phase inversion process. In this
application, PAN membranes were coated on
both sides of the non-woven fabric to provide
an extra layer of support strong enough for
backwashing.
A polyamide nano-filtration membrane was
cast on top of a PAN ultrafiltration membrane
which was porous and had distributed pores
in its surface. The nano-membrane was formed
by interfacial polymerization of M-phenylenedi-
amine (MPD) solution in water and trimesoyl
chloride (TMC) solution in N-hexane [3].
Various concentration of MPD and TMC form-
ing the polyamide layer are shown in Table 1.
The active circular area of the membranes used
in all experiments was 0.012868 m
2
.
4. The results
The performances of polyamide composite
nano-filtration membranes with different material
compositions were tested in a setup as shown in
Fig. 1.
Pump was used for controlling the feed flow
rate and feed pressure. However, the energy to
the pump caused the rise in fluid temperature
in continuous operation. Tap water of 25C and
150 ppm (TDS) was supplied continuously to
the feed tank and maintained its temperature at
30C. This setup could attain the feed pressure
of 4 bars through proper valve settings.
The permeate flux and % solutes rejection for
the nano-membranes having different material
composition are shown in Figs. 2 and 3. The trans-
membrane pressure (TMP) was kept at 3.5 bars.
Keeping the TMC concentration at constant,
the membranes with 3% MPD showed a higher
Table 1
Membrane material contents
PAN 15 wt% +
DMF
0.05 wt%
TMC
0.1 wt%
TMC
2 wt% MPD Membrane 1
and 2
Membrane 5
and 6
3 wt% MPD Membrane 3
and 4
Membrane 7
and 8
Return flow
Valve 1
Water
tank
Pump
Membrane
holder
Reject flow
Pressure guage
Valve 2
Permeate
Fig. 1. Setup of the experiment.
170 S.C. Low et al. / Desalination 221 (2008) 168173
solutes rejection and lower permeate flux com-
pared with the one with only 2% MPD. For mem-
branes having the same MPD concentration, the
one created from higher TMC concentration
rejected more solutes and lowered permeate flux
[4]. The membrane with a 3 wt% MPD and
0.1 wt% TMC was the best in terms of its solutes
removal ability. There was 33.56% of solutes was
removed from the tap water feed of TDS 150 ppm.
These results indicated that both the concentra-
tion of MPD and TMC affected the membrane
performance. A higher MPD solution inclined to
form a thicker membrane and the high concen-
tration of TMC enhanced interfacial reaction
and affected the membrane structures.
The results of the membranes backwashed
after 20 h of test are also presented in Figs. 2 and 3.
Generally, the membrane performances were
almost recovered with a slight drop in permeate
flux and increase in solutes rejection rate.
The surface textures of a PAN membrane
and two other nano-membranes are shown in
Figs. 46. One could sense visually that they are
Note : Source TDS = 150 ppm
10%
0%
10%
20%
30%
40%
50%
Time (h)
T
D
S

r
e
d
u
c
t
i
o
n

(
%
)
2% MPD .05% TMC 3% MPD .05% TMC
2% MPD .1% TMC 3% MPD .1% TMC
0 5 10 15 20 25
Fig. 2. Solute removal rate for membranes with different
composition.
Note : Source TDS = 150 ppm
0
0 5 10 15 20 25
1
2
3
4
5
Time (h)
P
e
r
m
e
a
t
e

f
l
u
x

(
G
F
D
)
2% MPD .05% TMC 3% MPD .05% TMC
2% MPD .1% TMC 3% MPD .1% TMC
Fig. 3. Permeate flux for membranes with different
composition.
Fig. 4. Surface of a PAN membrane.
Fig. 5. Surface of a nano-membrane (2% MPD & 0.05%
TMC).
S.C. Low et al. / Desalination 221 (2008) 168173 171
quite distinct. The dense surface texture exhibited
in Fig. 6 explained why that membrane had a
greater solutes rejection rate as shown in Fig. 2.
The pore size became smaller and more neatly
structured when the MPD and TMC contents
increased.
The nano-membrane inclined towards forming
a layer of smaller pores structure with the increase
in polyamide content. The increase in TMC con-
tent caused more cross-linking in the top layer
and that would form a dense membrane structure.
From the membrane cross-sectional view, the
MPD was observed to be pressed into the PAN
membrane pores forming a polyamide layer com-
prised of much smaller pores (Fig. 7).
Tests were conducted to investigate the quality
of PAN membrane substrate on the performance
of the composite nano-membrane. This was con-
ducted by modifying the PAN membrane by
additives. These additives transformed the PAN
fingers like pores into that of spongy and smaller
in scale. The same nano-membranes were then
cast on top of the modified PAN membranes.
The Fig. 8 showed results of the nano-cast on
the improved PAN base.
With a source feed having 900 ppm of CaCO
3
and trans-membrane pressure (TMP) of 2.5 bars,
the steady state permeate TDS changed from
550 ppm to 500 ppm for using a PAN support with
additive 1. The same was improved to 310 ppm
when using a PAN support with additive 2. The
permeate flux was also increased due to the
changes in the PAN support membrane. A good
quality PAN support for the nano-membrane
had positive effects on both solute rejection and
permeate flux (Fig. 9).
Fig. 6. Surface of a nano-membrane (2% MPD & 0.1%
TMC).
Fig. 7. X-section of a nano-membrane formed by
3% MPD and 0.1% TMC.
Solute rejection rate (%) vs time (h)
0
0 5 10 15 20 25
10
20
30
40
50
60
70
Time (h)
S
o
l
u
t
e

r
e
j
e
c
t
i
o
n

r
a
t
e

(
%
)
Generic With additive 1 With additive 2
Fig. 8. Solutes rejection of nano-membranes with
different PAN supports.
172 S.C. Low et al. / Desalination 221 (2008) 168173
After a 20 h of continuous use of membrane
with PAN support using additive 2, the permeate
of 310 ppm TDS was re-channeled back to the
same membrane, as input feed, to simulate a
2-pass process. The permeate TDS after the
second pass was reduced to only 190 ppm as
shown in Fig. 10.
Tests also conducted to assess the solutes
rejection rate for different levels of water hardness.
The results in Figs. 11 and 12 indicated that the
effects due to the increase in hardness, from 900
to 1200 ppm, on both the membrane solutes rejec-
tion rate and permeate flux were slight. There
was a slight increase in rejection rate and reduction
in permeate flux.
Water flux (GFD) vs time (h)
0
2
4
6
8
10
12
14
0 5 10 15 20 25
Time (h)
W
a
t
e
r

f
l
u
x

(
G
F
D
)
Generic With TA With TA and NaHCO
3
Fig. 9. Permeate flux for nano-membranes with different
PAN supports.
Permate (ppm) vs time (h)
in a 2 pass system
0
100
200
300
400
500
600
700
800
900
0 5 10 15 20 25
Time (h)
P
e
r
m
e
a
t
e

(
p
p
m
)
2 Pass
Fig. 10. CaCO
3
was reduced from 900 ppm to 190 ppm
though a 2-pass process.
Solute rejection rate (%) vs time (h)
for different feed concentration
0
10
20
30
40
50
60
70
80
0 5 10 15 20 25
Time (h)
S
o
l
u
t
e

r
e
j
e
c
t
i
o
n

r
a
t
e

(
%
)
900 ppm 1050 ppm 1200 ppm
Fig. 11. Solute rejection rate of the nano-membrane for
different feed hardness.
Water flux (GFD) vs time (h)
for different feed concentration
0
2
4
6
8
10
12
14
0 5 10 15 20 25
Time (h)
W
a
t
e
r

f
l
u
x

(
G
F
D
)
900 ppm 1050 ppm 1200 ppm
Fig. 12. Permeate flux of the nano-membrane for
different feed hardness.
Solute rejection rate (%) vs time (h)
for different trans-membrane pressures
0
10
20
30
40
50
60
70
80
0 5 10 15 20 25
Time (h)
S
o
l
u
t
e

r
e
j
e
c
t
i
o
n

r
a
t
e

(
%
)
1.5 bar 2.5 bar 3.5 bar
Fig. 13. Solutes rejection rate of the nano-membrane
under different TMP.
S.C. Low et al. / Desalination 221 (2008) 168173 173
The results in Figs. 13 and 14 showed that the
trans-membrane pressure would have no effect
on the solutes rejection rate but higher trans-
membrane pressure led to higher permeate flux.
5. Conclusions
The quality of the nano-filtration membrane
cast on both sides of a PAN ultra-filtration
membrane as base depended on the MPD and
TMC contents.
The quality of the PAN membrane as base
for the nano-cast contributed positively to both
solutes rejection rate and permeate flux.
Higher level of water hardness would not
change much of the nano-membrane solutes
rejection rate and the permeate flux.
Increase in TMP only led to higher permeate
flux but caused no change to the membrane
ability in solutes rejection.
The presented nano-filtration membrane could
reduce the water hardness from 900 ppm to
190 ppm through a 2-pass process with TMP
of 2.5 bars in each pass.
References
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Influence of the diamine structure on the nano-
filtration performance, surface morphology and
surface charge of the composite polyamide
membranes, J. Membr. Sci., Available online
31 January 2006.
[2] In-Chul Kim, Hyung-Gu Yun and Kew-Ho Lee,
Preparation of asymmetric polyacrylonitrile mem-
brane with small pore size by phase inversion and
post treatment process, J. Membr. Sci., 199 (2001)
7584.
[3] I. Juhn Roh, Influence of rupture strength of inter-
facially polymerized thin film structure on per-
formance of polyamide composite membrane,
J. Membr. Sci., 198 (2001) 6374.
[4] A.L. Ahmad, et al., Composite nanofiltration poly-
amide membrane: a study on the diamine ratio and
its performance evaluation, Ind. Eng. Chem. Res.,
43 (25) (2004) 80748082.
Water flux (GFD) vs time (h)
for different transmembrane pressures
0
2
4
6
8
10
12
14
16
0 5 10 15 20 25
Time (h)
W
a
t
e
r

f
l
u
x

(
G
F
D
)
1.5 bar 2.5 bar 3.5 bar
Fig. 14. Permeate flux of the nano-membrane under
different TMP.