See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/228498658

Filtration of Solution Containing Heavy Metals

and Dyes by Means of Ultrafiltration
Membranes Deposited on Support...

Article in Desalination August 2004

DOI: 10.1016/j.desal.2004.07.013

CITATIONS READS

45 465

7 authors, including:

Saffaj Nabil Saad. Alami Younssi

University Ibn Zohr - Agadir Facult des sciences et techniques Rsultats
45 PUBLICATIONS 389 CITATIONS 69 PUBLICATIONS 770 CITATIONS

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Biosorption of aldrin pesticide onto natural adsorbent View project

Development of a new TiO2 ultrafiltration membrane on flat ceramic support made from natural
bentonite and micronized phosphate and applied for dye removal View project

All content following this page was uploaded by Saffaj Nabil on 16 February 2016.

The user has requested enhancement of the downloaded file.

 Desalination 168 (2004) 301306

Filtration of solution containing heavy metals and dyes by

means of ultrafiltration membranes deposited on support made
of Moroccan clay
N. Saffaja*, H. Loukilia, S. Alami Younssia, A. Albizanea, M. Bouhriaa,
M. Persinb, A. Larbotb
a
Laboratoire des Matriaux Catalyse et Environnement, Facult des Sciences et Techniques,
Mohammedia BP 146, Mohammedia 20650, Morocco
Tel +212 (63) 323683; Fax +212 (23) 315353; e-mail: saffaj@hotmail.com
b
Institut Europen des Membranes, UMR 5635 CNRS ENSCM UMII, 1919 Route de Mende,
34293 Montpellier, Cedex 5, France

Received 13 February 2004; accepted 20 February 2004

Abstract

The use of inorganic membranes in pollution treatment is actually limited by the cost of such membranes.
Advantages of inorganic membranes over organic ones are their chemical, thermal and pH resistance. In this
study, low cost ZnAl2O4-TiO2 ultrafiltration membranes were tested for removing Cd(NO3)2, Pb(NO3)2,
Cr(NO3)3, methylene blue and orange acid from water. The electrical interactions between ionic species and sur-
face material govern the rejections of heavy metals and charged species. Retentions of dyes methylene blue and
orange acid are also important but the adsorption of the species leads to fouling when the concentration in-
creases.

Keywords: Ceramic membrane; Ultrafiltration; Heavy metals; Colour; Fouling

* Corresponding author

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 lEau Potable, Marrakech, Morocco, 30 May2 June, 2004.

0011-9164/04/$ See front matter 2004 Elsevier B.V. All rights reserved
302 N. Saffaj et al. / Desalination 168 (2004) 301306
1. Introduction
Nowadays the preservation of water re-
sources to prevent their pollution by toxic ele-
ments is one of the more important challenges
for the human race because the progress of tex-
tile, leather, surface treatment, mining, motor-
car and chemical industries generate toxics such
as heavy metals and dyes which are ejected into
the environment. The consequence of the pollu-
tion of the water resources is an increase of the
concentration of toxics [1] in the drinking water
which also increases the cost of water potabili-
sation.
Traditional methods to remove the toxic
elements from wastewaters are flocculation, co-
agulation, ion exchange, electrodeposition, ex-
traction, crystallization, etc. Most of these have
great disadvantages by operating in a success-
sion of steps of heterogeneous reactions, or
distribution of substances between different
phases which usually require a lengthy operat-
ing period. Moreover, the final metal recovery
requires additional treatments, which com-
plicate the process [2].
Membrane processes are interesting as they
reduce the number of unit operations and are
now used to obtain effluents without contamin-
ants, they recycle process water, and recover
valuable products, which can be reused in the
process itself or in other applications [3].
For the last 20 y most of the scientific work-
ers have focused their attention on the appli-
cation of the ultrafiltration membrane in pollu-
tion prevention [46], but the use of organic
membrane is actually more developed when
inorganic membranes display a number of a-
dvantages, such as better thermal, chemical
resistance and mechanical strength [7].
In this work, in order to reduce the polluting
substances from wastewater, we will present the
preparation of a new low cost asymmetric
ceramic ultrafiltration membrane and we will
give some results of filtration tests of solution
containing heavy metal cations, (Pb(NO2)3,
Cr(NO3)3 and Cd(NO3)2 ), and dyes (methylene
blue and acid orange).
2. Membrane preparation
The support used to deposit the ultrafil-
tration membrane is made of natural Moroccan
clay which is a low cost material. The chemical
analysis of the clay powder reveals the presence
of a large amount of silica (80%) and alumina
(12%). The particle size repartition diagram
shows an important fraction of the clay presents
a diameter lower than 5 m.
A plastic paste with rheological properties to
allow extrusion shaping is prepared mixing a
sample of Moroccan clay with organic additives
and water [810]. The paste is then extruded to
obtain a tubular support of 10 mm outer dia-
meter. After drying and sintering at 1250C for
consolidation, the average pore diameter of the
support is 11m; its porosity is 43% and its
mechanical strength 10MPa.
An intermediate ZrO2 microfiltration layer
[910]. was then coated on the clay support
before depositing the final sol-gel layer. This
intermediate layer allows the ultrafiltration
membrane to be maintained without infiltration
into the support, it was prepared using the sus-
pended powder technique by means of pure
ZrO2 of 8 m2 specific area. After firing at
1100C for 2 h, a ZrO2 layer of 0.23 m pore
diameter and a thickness of 10m were ob-
tained.
The final ultrafiltration membrane was
prepared by slip casting of the ZnAl2O4/TiO2
sol in the inner portion of the clay tubular
support [8,9,11]. The sol used was prepared
after mixing the pure TiO2 sol and the pure
ZnAl2O4 sol with 10g of hydroxyethyl cellu-
lose. The coating time was 2 h, after drying for
24 h at room temperature and sintering at
400C for 2 h, the ultrafiltration membrane was
obtained.
 N. Saffaj et al. / Desalination 168 (2004) 301306 303

3. Membrane characterization 5. Filtration of colorants

The pore diameter of the membrane mea- 5.1. Filtration of methylene blue
sured by nitrogen adsorption-desorption are
In order to evaluate the behaviour of the
centered on 5 nm. Tangential filtration tests
membrane for removal of the dyes in waste-
were performed on a laboratory scale filtration
water, the filtration of methylene blue (cationic
plant, using a recycling configuration. The pilot
dye) was performed and the effects of
was equipped with an adjustable out-flow pump,
concentration, pH and pressure were investi-
a thermostated feed tank and a vertical mem-
gated.
brane module (length 15 cm). The transmem-
brane pressure (TMP) was fixed between 0 and 5.1.1. Pressure effect
10 bars by means of a nitrogen gas bottle. The
water permeability of the membrane is 9.42 Figs. 1 and 2 show the variation of fluxes
l/h.m2.bar. and retentions vs. time for methylene blue solu-
The molecular weight cut off (MWCO) of
this membrane was determined using a solution
containing polyethylene glycol of different
molecular weights from 6005000 at a con-
centration of 103 mol.l1 and is about 4500 Da.

4. Filtration of heavy metals

The filtration of different solutions which

contained respectively Pb(NO2)3, Cr(NO3)3 and
Cd(NO3)2 were carried out to evaluate the
efficiency of the ultrafiltration membranes pre-
pared for the rejection of toxic metals. The
Fig. 1. Variation of flux of methylene blue as a func-
rejection rates are shown in Table 1.
tion of time at different pressure, C=50 ppm, pH=5.8.
Whatever the salts, the rejection rates are
above 90%. Such rejections can be explained
taking into account the strong interactions de-
veloped between the divalent cations and the
positive surface charge of the membrane at pH5
[8,9,11].

Table 1
Rejection rates of different heavy metals, P= 10 bar
Salt Concentration, pH Retention, %
mol/l
Cd(NO3)2 103 5.1 93
3
Pb(NO3)2 10 5.2 93.4
Fig. 2. Retention of methylene blue as a function of
Cr(NO3)3 103 3.6 96 time at different pressure, C=50 ppm, pH=5.8.
304 N. Saffaj et al. / Desalination 168 (2004) 301306

tions at different pressures. The flux and reten-

tion increase with increasing pressure. This is
the classical behaviour for ultrafiltration mem-
branes.
5.1.2. pH effect
The rejection rates decrease from 86% at
pH20% at pH9 (Fig. 3). This behaviour is in
agreement with the decrease of the electric
interactions between the methylene blue cation
and the charged surface membrane of which the
positive charge becomes lower as the pH in-
creases [89].
5.1.3. Concentration effect Fig. 4. Variation of flux of methylene blue as a fun-
ction of time at different concentration, P=10 bar,
Since the purpose of ultrafiltration mem-
pH=5.8.
branes is to concentrate the effluent, it was im-
portant to have an idea of the influence of the
concentration on the performance. In the ultra-
filtration membrane (diameter of pore<10 nm)
the concentration plays a significant role. In
general, the higher the concentration, the higher
the osmotic pressure and therefore the lower the
permeate flux. For the solution of methylene
blue, it can be observed in Fig. 4 that the per-
meate flux decreases as the concentration in-
creases. This may be caused by dye adsorption
on the membrane surface during the experiment
runs which was confirmed by the blue colora-

Fig. 5. Retention of methylene blue as a function of time

at different concentration, P= 10 bar, pH=5.8.

tion of the membrane after filtration. Similar

Fig. 3. Evolution of methylene blue rejection versus pH
at P=10 bar, C=50 ppm.
observations were reported in the literature
[12].
Fig. 5 shows the retention of methylene blue
vs. time for different concentrations. The reten-
tion increases with increasing dye concen-
tration. This behaviour can be explained by the
formation of a gel layer. The gel layer formed
by the rejected dye on the membrane surface
may operate as an additional resistance to the
 N. Saffaj et al. / Desalination 168 (2004) 301306 305

transport through the membrane. Higher dye

concentration increases the dye accumulation
on the membrane surface and color removal be-
comes more important than those of the lower
dye concentration; moreover the presence of the
gel layer should modify the apparent pore size
of the membrane and can be explained by the
best rejection observed when the concentrations
increase.

5.2. Filtration of orange acid

The behaviour of orange acid 74 (anionic
dye) has also been evaluated and the effects of
concentration and pressure were studied.
5.2.1. Pressure effect Fig. 7. Retention of orange acid as a function of time at
Figs. 6 and 7 show that the flux and different pressure, C=50ppm, pH=6.9.
retention increase with increasing pressure. The
high retention of the anionic orange acid species
(90% at 10 bars) can be explained by its strong
adsorption on the membrane surface according
to the reaction (1).
MOH2+ + n(DyeSO3) (DyeSO3)n (MOH2+)
(Ionic bond)
(1)
In this condition the membrane surface be-
comes negatively charged at pH 6.9, this effect

Fig. 8. Variation of flux of orange acid as a function of

time at different concentration, P= 10 bar, pH=6.9.

leads to develop strong repulsive interactions

between the SO3 groups and the negative
membrane [13].

5.2.2. Concentration effect

Fig. 6. Variation of flux of orange acid as a function of
time at different pressure, C=50 ppm, pH=6.9.
The flux decreases with increasing dye
concentration (Fig. 8) as for the blue methylene
dye filtration. The retention also increases with
increasing dye concentration (Fig. 9). A gel
layer formation should also be responsible for
 306 N. Saffaj et al. / Desalination 168 (2004) 301306
Fig. 9. Retention of orange acid as a function of time at
different concentration, P=10 bar, pH=6.9.
this phenomenon which is suggested by the
coloration of the membrane after the filtration
test.
6. Conclusion
The performances of a low cost
TiO2/ZnAl2O4 ultrafiltration membrane deposit-
ed on a tubular support made of Moroccan clay
were studied. The membrane presents interest-
ing retention properties with regard to the heavy
metal ions and dyes, their retention depends
strongly on the concentration and on the pH of
the filtered solution. The retention evolution for
the different species can be interpreted by
taking into account the electric interactions be-
tween the ions and the residual charges on the
surface of the filtering material. Such mem-
branes will be tested now for removing
polluting metallic species in wastewater pro-
duced by surface treatment industry. This should
find interesting applications for the treatment of
liquid effluents in emergent countries.
View publication stats
Acknowledgement
This joint program was made possible
thanks to the French-Moroccan Inter-University
Mixed Committee (A.I. 213/SM/00). We grate-
fully acknowledge funding through Institut
Europen des Membranes for technical support
and analytical screening of samples.
References
[1] J.A. Hestekin, D. Bhattacharrya, S.K. Sikdarand
and B.M. Kim, Membranes for treatment of
hazardous wastewater, in: R.A. Meyers (ed.), En-
cyclopedia of Environmental Analysis and Pre-
meditation, John Wiley and Sons Inc., 1998.
[2] P. Caizares, . Prez and R. Camarillo, Desali-
nation, 144 (2002) 279285.
[3] K.S. Scott and R. Hughes, Industrial Membrane
Separation Technology, Kluwer Academic Publi-
shers, 1996.
[4] C.-H. Xing, E. Tardien, Y. Qian and X.-H. Wen,
J. Membr. Sci., 177 (2000) 7382.
[5] M. Marcucci, G. Nosenzo, G. Capannelli, I.
Ciabatti, D. Corrieri and G. Ciardelli, Desali-
nation, 138 (2001) 7582.
[6] V.N. Mynin and G.V. Terpugov, Desalination,
119 (1998) 361362.
[7] A.J. Burggraf and L. Cot, Fundamentals of Inor-
ganic Membranes Science and Technology, Else-
vier Science and Technology Series 4, Elsevier,
Amsterdam, 1996.
[8] N. Saffaj, S. Alami-Younssi, A. Albizane, A.
Messouadi, M. Bouhria, A. Larbot, M. Persin and
M. Cretin, Rcents progrs en gnie des procds,
89 (2003) 507514.
[9] N. Saffaj, S. Alami-Younssi, A. Albizane, A.
Messouadi, M. Bouhria, A. Larbot, M. Persin and
M. Cretin, Sep. Purif. Technol., 36 (2004) 107
114.
[10] L. Broussous, E. Prouzet, L. Beque and A. Larbot,
Sep. Purif. Technol., 24 (2001) 205221.
[11] Y. Elmarraki, M. Cretin, M. Persin, J. Sarrazin
and A. Larbot, Mater. Res. Bull., 36 (2001) 227
237.
[12] I. Koyuncu, Desalination, 143 (2002) 243253.
[13] A. Akbari, J.C. Remigy and P. Aptel, Chem. Eng.
Process., 41 (2002) 601609.