DESALINATION

ELSEVIER Desalination 168 (2004) 215-221

www.elsevier.com/locate/desal

Development of a highly hydrophilic nanofiltration membrane

for desalination and water treatment

A . L . A h m a d a*, B . S . O o P , A . W a h a b M o h a m m a d b, J . P . C h o u d h u r y a
aSchool of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia,
Seri Ampangan, 14300 Nibong Tebal, Penang, Malaysia
Tel. +60 (4) 5937788 Ext. 6418; Fax +60 (4) 5941013; email: chlatiJ@eng.usm.my
bDepartment of Chemical and Process Engineering, Universiti Kebangsaan Malaysia,
43600 Bangi, Selangor, Malaysia

Received 16 February 2004; accepted 24 February 2004

Abstract

Thin film composite (TFC) co-polyamide membranes were modified by adding carboxyl group to the
polypiperazinamide backbone. The sodium chloride, sodium sulphate, magnesium chloride and magnesium sulphate
rejections were measured at various feed pressures for the modified and unmodified membranes. The pure water
permeability was improved as much as 20% for the modified membrane. Besides, the membrane rejection ability
towards divalent ions was excellent compared to the monovalent ions. The rejection of multivalent ions was more
than 96% at the operating pressure as low as 450 kPa. The modified membrane was more negatively charged
compared to the unmodified membrane. The membranes developed earl be used for pre-treatment in a desalination
plant as well as for hardness removal in water treatment process at a higher production rate.

Keywords: Nanofiltration; Hydrophilic; Carboxyl group; Desalination

1. Introduction of a nanofiltration membrane are typically much

A nanofiltration membrane is a type of pressure
driven membrane that could perform a preferential
separation for different fluids or ions. The pores
*Corresponding author.
larger than the membrane pores that are used in
reverse osmosis so it requires less energy to
perform the separation.
Higher flux and lower operating pressure of
nanofiltration makes the membrane feasible to be

Presented at the EuroMed 2004 conference on Desalination Strategies in South Mediterranean Countries: Cooperation
between Mediterranean Countries of Europe and the Southern Rim of the Mediterranean. Sponsored by the European
Desalination Society and Office National de l'Eau Potable, Marrakech, Morocco, 30 May-2 June, 2004.
0011-9164/04/$- See front matter © 2004 Elsevier B.V. All rights reserved
doi;10.1016/j.desa1.2004.07.001
216 A.L. Ahmad et al. / Desalination 168 (2004) 215-221
applied in both water and wastewater treatment
processes. Nowadays, nanofiltration has been
widely used in drinking water industry [1] and
wastewater treatment for removal of contaminants
such as pesticides [2], arsenic [3], soil leachate
[4] and dyes [5]. Recently, nanofiltration mem-
branes were also studied for the application in food
[6] and bio-process [7] purposes.
Interfacial polymerization (IP) technique is one
of the techniques used in preparing composite
nanofiltration membranes. The membranes
produced have high water permeation flux and
salt rejection. There are several advantages in
making a membrane using the IP process. The IP
film which forms the selectivelypermeable barrier
layer can be made quite thin - - less than 0.1 ~tm
[8]. The thin film composite (TFC) membranes
made by the IP process also offer good selectivity
and high permeability of water. Besides, IP tech-
nique allows the properties of the permselective
barrier layer to be optimized independently from
the supporting layer.
The common materials used to produce the
barrier layer include the aliphatic or aromatic
diamine [8-11 ], polysulfonamide [12], aromatic
diol and a combination of diol and amide [13]
while the common crosslinkers used are trimesoyl
chloride, isophthaloyl chloride and terephthaloyl
chloride. Piperazine and m-phenylenediamine,for
example, are the most popular primary and
secondary diamines used in the preparation of the
high rejection ultra thin reverse osmosis and
nanofiltration membranes. 3,5-diaminobenzoic
acid which is known to be more hydrophilic than
the conventional m-phenylenediamineis another
potential membrane material. Since a higher ratio
ofhydrophilicity to hydrophobicity in the polymer
resulted in an increase in water flux of membranes,
polymeric material with a hydrophilic group
would be of improved quality to be developed as
a membrane-grade polymer. Polyamides having
a pendant carboxylic group at their backbone are
expected to result in an improvement of the
product rate [ 14].
The objective of the current research is to
develop a highly hydrophilic membrane by
modifying the conventional polypiperazinamide
membrane. The modifiedmembranes were studied
and their performance was checked and compared
to that of the unmodified membrane in terms of
sodium chloride, sodium sulphate, magnesium
chloride and magnesium sulphate rejection.
2. Experimental
2.1. Materials
The polysulfone Udel P-1700 (Mn 17,000)
was supplied by Union Carbide Corporation.
Piperazine, 3,5-diaminobenzoic acid, n-hexane,
sodium chloride, sodium sulphate, magnesium
chloride and magnesium sulphate were supplied
by Merck, Germany. N-methylpyrrolidone and
trimesoyl chloride were purchased from Fluka and
polyvinylpyrrolidone from Sigma-Aldrich Co.
The tightly woven polyester, style 0715 Dacron
Fabric was supplied by Texlon Corporation
(USA).
2.2. Preparation o f polysulfone support layer
The polysulfone support was prepared by
dissolving 15% polysulfone (Udel P-1700) in N-
methylpyrrolidone with 18% polyvinylpyrro-
lidone as pore-former. The solution was cast onto
a tightly woven polyester fabric with a thickness
of 150 ktm. Then, the membrane was immersed
into the water bath and kept in the water bath for
at least 24 h until most of the solvent and water
soluble polymer were removed [ 15].
2. 3. Fabrication o f thinfilm composite membranes
The support layer which was taped on a glass
plate was immediately dipped into an aqueous
diamine solution for 5 min at ambient temperature.
For unmodified polypiperazinamide membrane,
the aqueous diamine solution consists of 2 wt%
piperazine only whereas for modified membrane,
 A.L. Ahmad et al. / Desalination 168 (2004) 215-221 217

the aqueous solution consists of 1.95 wt% Real rejection (Ro~) was calculated by the
piperazine and an extra of 0.05 wt% of 3,5- relation below [ 16]:
diaminobenzoic acid. After immersion in the
aqueous solution, the excess solution from the
impregnated membrane surface was removed (2)
using a rubber roller. The membranes were then
reacted with 0.1 w/v% trimesoyl chloride(TMC) To find the film layer concentration, the con-
in the n-hexane solution for 10 s. centration polarization equation was employed.
For a stirred cell configuration, the observed rejec-
2. 4. Membrane permeation characterization
tion was related to the real rejection by volume
Membrane permeation test was carried out flux, J (m.s -1) and mass transfer coefficient, k
using the Amicon 8200 stirred cell at five different (m.s-1) as follows [16]:
pressures: 150 kPa, 250 kPa, 350 kPa, 400 kPa
k ~.~kt(3}0'567 (3)
and 450 kPa. The membrane was cut to a diameter
of 5.5 cm (effective area of 28.27 cm 2) and then and
mounted at the bottom of the stirred cell. For each
operating pressure, fresh solution was used as a
feed. Bulk feed concentration was calculated k' = 0.23 D (4)
r
based on the average of initial and final feed
concentration. Nitrogen gas was used to pressurize
where k', co, r, v and D are mass transfer
the water flux through a membrane. The solution
coefficient (m.s-1), stirring speed (s-l), stirrer
was stirred at the speed of 350 rpm to reduce
radius (m), kinematic viscosity (mZ.s-~) and bulk
concentration polarization. The feed solutions
diffusivity (m2.s-1)
were pure water, 0.01 M sodium chloride, 0.01 M
The pure water permeability, PWP
sodium sulphate, 0.01 M magnesium chloride and
(L.h-l.m-2.bar-~)can be calculated from the relation:
0.01 M magnesium sulphate. All the above elec-
trolyte solutions were measured using a con- PWP=
ductivity meter (Hanna Instruments, Italy, Model
HI8633). volumeof permeate(1) (5)
Each membrane was subjected to pressure pre- time(h)x effectivemembranearea(m2) x pressure(bar)
treatment at 500 kPa for 1 h before the permeation
experiments. The flux was equilibrated for the
passage of first 20 ml permeates and the following 3. Results and discussion
10 ml permeate was collected for the concentration
analysis. The observed rejection (Rob) was based 3.1. Pure water permeabdity o f the membranes
on the permeate and average bulk feed concen- It was found that the flux for both membranes
tration: increased linearly with the transmembrane pres-
C sure. Fig. 1 shows that the water flux for modified
Rob~ = 1 Cj membranes was higher compared to the unmodi-
(1)
fied membrane under all pressures. The pure water
permeabilities as calculated from Eq. (5) were
where C is the permeate concentration (mol.m-~)and 9.71 1.h-l.m-2.bar-1 and 11.94 1.h-l.m-2.bar-~ for
Cf is thePaverage bulk feed concentration (mol.m-a) unmodified and modified membrane respectively.
218 A.L. Ahmad et aL / Desalination 168 (2004) 215-221

60.0 - MgSO4, Na2SO 4 and MgC12 became closer at a

50.0
higher pressure.
y = 11.9394x /1~ A
The phenomenon could be explained by
~'~. 40.0 looking at the salt diffusion coefficient ( D ) and
30.0 the solute size (r). Data for D a n d r are given in
-~ 20.0
Table 1 [16,18].
IJ.
As shown in Table 1, the ion diffusivity ( D )
10.0
f • unmodified 0 modified follows the sequence CI- > Na ÷ > SO42- > Mg 2+
0.01 r while the solute size follows the order Mg 2÷ >
0 1 2 3 4 5 SO42- >Na ÷ >CI-. The trends could explain why
Pressure (bar) the rejection profiles shown in Fig. 2 were
Fig. 1. Water flux for unmodified and modified mem- obtained because higher diffusivity and smaller
branes. solute size could enhance mass transport through
the membrane material. Higher solute transport
resulted in a poorer rejection of the membrane.
The PWP was increased as much as 23% by mere-
Such results were also reported in the literature
ly the addition of 0.05% 3,5-diaminobenzoie acid.
by other researchers [19,20].
The hydrophilization effect of3,5-diaminobenzoic
According to the Donnan exclusion theory, a
acid resulted in the increased water flux as des-
higher valence counter-ion leads to a lower
cribed in our previous work [ 17].

3.2. Effect of pressure on NaCI, Na2SO4, MgCIe Table 1

and MgSO 4 rejection Diffusion coefficient and solute size for ions
It appears that the rejection increased with the
increasing permeate volume flux for all the salts. Ion D , xl0 -9 m2s-1 rs, nm
As shown in Figs. 2a and 2b, the real rejection Na + 1.33 0.18
sequence for both membranes was MgSO 4 > Mg 2+ 0.70 0.35
Na2SO 4 > MgCI2 > NaCI. This order could be seen Cl- 2.01 0.12
SO42- 1.06 0.23
at a low pressure but the rejection ability of

1.00
1.00
0.90 0.90 j 4=

0.80 IZ 0.80 -
v
C t-
. 0m3
0.70 O 0.70
"5 E! n
03 0.60 i"1 03
0.60 13 El
[]
0.50 i-i
0.50
E! NaCI • Na2SO4 n,, D
0.40 EINaCI • Na2SO4
o &MgCI 2 XMgSO4 0.40
r-= /t MgCI2 XMgSO 4
0.30 i i
0.30
100 200 300 400 500
100 200 300 400 500
(a) Pressure (kPa) (b) Pressure (kPa)

Fig. 2. Effect of pressure on real rejection ofMgSO4, Na2SO4, MgCI 2 and NaCI: (a) unmodified membrane (b) modified
membrane.
 A.L. Ahmad et al. / Desalination 168 (2004) 215-221 219

rejection of the salt [19]. However, neither Mg 2÷
nor SO42- give a poor rejection, therefore it could
be concluded that the electromigration effect
seems not to play an important role compared to
the steric hindrance mechanism.
3.3. Comparison of unmodified and modified
membranes
Figs. 3a-d compare the rejection ability of the
unmodified and modified membrane using NaC1,
Na2SO 4, MgCI 2 and MgSO 4 respectively.
Fig. 3a shows that the NaC1 rejection was better
for the unmodified membrane compared to the
modified membrane. The same rejection profile
was also observed for MgCI 2(Fig. 3c). This might
be due to the bigger pore size of the modified
membrane after the addition of 3,5-diamino-
benzoic acid. The steric hindrance effect for the
bigger pore size is poorer than the smaller pore
size. As a result, more ions will be transported
through the modified membrane therefore reduc-
ing its rejection ability.
However, Fig. 3b and Fig. 3d show the reverse
trend - - the rejections for Na2SO4 and MgSO 4
were higher for the modified membrane compared
to the unmodified membrane. This phenomenon
could be explained by the electromigration effect.
The carboxyl group (-COOH) contributed by 3,5-
diaminobenzoic acid is negatively charged and
according to Donnan exclusion theory, divalent
co-ions like SO42- will be highly repelled by the
negatively charged membrane. Consequently, the
rejection for "sulphate-containing salt" was higher
for the modified membrane. The negative charge
of the modified membrane could be further

0.80 1.00
•= 0.70
n,
'- 0.60 = 0.95
._o 0
t3 0
-~, 0.50 e 13
0 " f 0.90 e
"~ 0.40
n~ e unmodified n modified 0
r~ • unmodified 0 modified
0
0.30 i i , -3 0.85 - t E i

100 200 300 400 500 100 200 300 400 500
(a) Pressure (kPa) Co) Pressure (kPa)

1.00 1.00

lili • •
0.95 ! vt - 0.95
o
~ 8 8
"~ 0.90 ' ~ 0.90
0 J
n," [ • unmodified [ ] modified n"
• unmodified [ ] modified
0.85 ~ . . . . 0.85 i i

100 200 300 400 500 IO0 200 300 400 500
(c) Pressure (kPa) (d) Pressure (kPa)

Fig. 3. Comparison of unmodified and modified membranes on real rejection: (a) NaC1, (b) Na2SO4, (c) MgCI2 and
(d) MgSO 4.
220 A.L. Ahmad et al. / Desalination 168 (2004) 215-221
Table 2
Salt rejections of unmodified and modified membranes
at 450 kPa
Salt Real rejection (Rr,~t)
Unmodified Modified
NaC1 0.6668 0.6259
Na2SO4 0.9505 0.9613
MgC12 0.9481 0.9368
MgSO4 0.9679 0.9786
confirmed by the poorer rejection o f the counter-
ions (Mg 2+) although the solute size o f the Mg 2÷
was the biggest among the ions.
The rejection o f multivalent ions is excellent
compared to the monovalent ions. Table 2 shows
that for both membranes, the sulphate containing
salt could be removed more than 95% with a
slightly improved rejection for the modified
membrane. For MgCI2, both membranes gave a
mild rejection of 93% to 94%, with the unmodified
membrane showing a slightly better rejection. The
poorest rejection was shown by the monovalent
ions o f NaC1 which is a typical characteristic of
nanofiltration membranes.
4. Conclusion
By incorporating 3,5-diaminobenzoic acid, the
hydrophilicity o f the membrane was increased.
The highly hydrophilic membrane could improve
the water permeability as much as 23% which
indicates that the product rate could be increased.
Besides, the membrane rejection ability towards
divalent ions was excellent compared to the
monovalent ions. The rejection ofmultivalent ions
especially sulphate-containing salt was more than
95% at the operating pressure as low as 450 kPa.
The modified membrane was more negatively
charged compared to the unmodified membrane.
However, the rejection ability o f divalent counter-
ions was not reduced. The membranes developed
could open up the avenue for pre-treatment in a
desalination plant. It can also be applied to reduce
the hardness o f water and improve the quality o f
water treatment process while keeping a higher
production rate.
5. Symbols
C l,p - - Concentration in permeate, mol m -3
D, - - Bulk diffusivity, m2s-I
Jv - - Volume flux (based on membrane area),
m3m-2s-I
k - - Mass transfer constant, ms -~
k' - - Mass transfer constant defined by Eq.
(4)
r -- Radius of stirrer, m
Rob, -- Observed rejection
R,~t -- Real rejection
co -- Stirring speed, rad.s -1
Acknowledgements
The authors are grateful to the financial support
provided by Ministry of Science and Technology
Malaysia through its Fundamental Research and
IRPA grants.
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