Powder Technology 208 (2011) 427–432

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Powder Technology
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p ow t e c

Preparation of a new ceramic microfiltration membrane from mineral coal fly ash:

Application to the treatment of the textile dying effluents
Ilyes Jedidi a,b,c, Sabeur Khemakhem a, Sami Saïdi a, André Larbot b, Najoua Elloumi-Ammar c, Amine Fourati c,
Aboulhassen Charfi c, Abdelhamid Ben Salah a, Raja Ben Amar a,⁎
a
Laboratoire Sciences des Matériaux et Environnement, Faculté des sciences de Sfax, Rte. de Soukra Km 4, 3018, Sfax, Tunisia
b
Institut Européen des Membranes, UMR 5635 (CNRS, ENSCM, UM II), 1919 Route de Mende, 34293, Montpellier, CEDEX 5, France
c
Groupe Chimique Tunisien, Centre de Recherche de Sfax, B.P: S, Route de Gabes km 4,5, Sfax, 3018, Tunisia

a r t i c l e i n f o a b s t r a c t

Available online 26 August 2010 New microfiltration membranes from mineral coal fly-ash material are obtained using ceramic method. Paste from
mineral coal fly ash (obtained by calcinations at 800 °C of non-grinded mineral coal) is extruded to elaborate a
Keywords: porous tubular configuration used as supports. The support heated at 1125 °C, shows an average pore diameter and
Mineral coal fly ash porosity of about 4.5 μm and 51%, respectively. The properties in terms of mechanical and corrosion resistances are
Paste extrusion process very interesting. The elaboration of the layer based on fly-ash powder (obtained by sintering at 700 °C of a finely
Macroporous support
grinded mineral coal) is performed by slip-casting method. The heating treatment at 800 °C leads to an average
Ceramic microfiltration membrane
Slip-casting process
pore size of 0.25 μm. The water permeability determined of this membrane is 475 L/h m2 bar. This membrane can
Dying effluents be used for crossflow microfiltration. The application to the treatment of the dying effluents generated by the
washing baths in the textile industry shows an important decrease of turbidity (inferior to 1 NTU), of chemical
oxygen demand (COD) values (retention rate of about 75%) and a total color removal. The performances in term of
permeate flux and efficiency were determined and compared to those obtained using a commercial alumina
microfiltration membrane. Almost the same stabilised permeate flux was obtained (about 100 L h−1 m−2). So, it
seems that the prepared membrane is suitable for such wastewater treatment.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction
Interest in separation by the use of membranes has rapidly
increased during the last 10–15 years. The membrane technologies
are utilized in various fields: chemistry, food, biotechnology and
recently wastewater treatment [1]. For economic consideration, a
great deal of research has been devoted to the development of
newtype of inorganic membranes, which have displayed improved
resistance to heat, chemicals and corrosion. Rapid development and
innovation have already been realised in this area [2–4].
Mineral coal fly ash obtained from coal-fired power stations could be
also a good material to make low cost membranes. Indeed, this way
allows a good management of this subproduct which represents a major
problem in many parts of the world due to the resulting pollution. It is
noticed, by the same way, that significant quantities are being used in
some range of applications like in construction and other civil
engineering applications [5] where fly ash is used as a substitute for
cement in concrete [6]. During the last years, some researches have been
performed concerning the integration of fly ash in the manufacture of
bricks and tiles which use a large volume of silicate-based raw materials
⁎ Corresponding author.
E-mail address: raja.rekik@fss.rnu.tn (R.B. Amar).
[7,8]. Conventional porous ceramic products prepared using only fly ash
have been also investigated [9,10]. Little research work has focused on
upgrading this material in the membrane preparation field like the
preparation of stainless-steel/fly-ash membrane suitable for hot gas
cleaning [11].
This work describes the elaboration of a ceramic fly-ash micro-
filtration membrane (macroporous support and active layer) applied
to the clarification and the decolouration of the effluents coming from
the dying industry.
2. Results and discussion
Microfiltration ceramic membranes were developed and prepared
in the laboratory. They consist of a mineral coal fly-ash skin layer
prepared by slip-casting method [12,13] deposited on a support made
of the same material.
2.1. Fly-ash characterisation
2.1.1. Chemical composition
For this study, the supports were prepared from mineral coal fly
ash. The chemical composition of the used fly ash, given in Table 1,
was determined by spectroscopic techniques, as X-ray fluorescence
for metals and by atomic absorption for alkaline earth metals. It is

0032-5910/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.powtec.2010.08.039
428 I. Jedidi et al. / Powder Technology 208 (2011) 427–432

Table 1
Chemical composition of the used fly ash.

Elements Proportion (wt.%)

SiO2 49.09
Al2O3 24.34
Fe2O3 8.93
CaO 4.88
MgO 3.15
K2O 1.74
SO3 2.15
LOIa 1.07
a
Loss on ignition.

shown that the major components were SiO2 (49%–58%), Al2O3

(23%–28%) and Fe2O3 (4%–16%) independently of the fly-ash origin.
In addition, in the used fly ash, the percentages of other components
such as CaO (4.88%), SO3 (2.15%) and MgO (3.15%) are relatively
high.
2.1.2. Phase identification
Phases present in the powder composition were analysed using an
X-ray diffractometer (Siemens, Germany) with Cu Kα radiation
(λ = 0.154 nm).
Fig. 1 presents the XRD patterns of fly ash obtained by calcination of a
mineral coal powder sintered at 1125 °C and 800 °C. The major
crystalline phases identified were quartz (SiO2), anorthite (CaAl2Si2O8),
gehlenite (Ca2Al2SiO7), hematite (Fe2O3) and mullite (3Al2O3·2SiO2). A
minority of anhydrite (CaSO4) can be seen on the spectrum. Cristobalite
which is obtained at the high temperature of quartz is formed when the
sintering temperature is 1125 °C and quartz peak intensity decreases.
Gehlenite and anhydrite intensity decreases in the fly ash with the
increase of the sintering temperature. In opposite, the intensities of the
peaks associated with mullite and anorthite increase significantly as a
result of rise of the sintering temperature. These results are in
accordance with the Ilic et al. study who found the same results [9].
2.1.3. Thermal analysis
Thermogravimetric analysis (TGA) and differential scanning
calorimetry (DSC) were performed with simultaneous DSC-TGA
Fig. 2. The DSC-TGA data of the fly-ash powder.
2960 TA instrument. The sample was heated from room temperature
to 1000 °C at a rate of 5 °C/min under static atmospheric conditions.
The data shows a very low mass loss (1.5%) which is attributed to
burning of some impurities or a small percentage of unburned mineral
coal powder, since the phenomenon started at 250 °C and continued
to 800 °C (Fig. 2).
2.2. Support shaping and characterisation
2.2.1. Particle size distribution of the fly-ash powder used in the support
elaboration
The adequate powder (P1) needed to make the macroporous
support was obtained after burning to a cinder a non-grinded mineral
coal rock at 800 °C. The duration of burning was 15 h for 1 kg of
mineral coal. The particle size analysis of the obtained powder was
determined using a Particle Sizing Systems (Inc. Santa Barbara,
California, USA Model 770 AccuSizer). The particle diameters range
varied from 0.5 to 20 μm (Fig. 3).
2.2.2. Elaboration process of the macroporous support
Plastic pastes are prepared from ceramic powder of fly ash mixed
with organic additives as follows:
• 84% of fly-ash powder.
• 4% methocel: cellulose derivative, as binder (The Dow Chemical
Company).
• 4% amijel: pregelated starch, as plasticizer (Cplus 12072, cerestar).
• 8% starch: porosity agent (RG 03408, cerestar).

For the paste preparation, a quantity of 130 ml of water per 250 g

of the mixed powder was added.

Fig. 1. XRD data for fly ash sintered at 800 °C and 1125 °C. Quartz (Q), anorthite (A), Fig. 3. Fly-ash particle size distribution of powder P1 used to make the macroporous
mullite (M), hematite (H), cristobalite (C), gehlenite (Ge), and anhydrite (An). supports.
 I. Jedidi et al. / Powder Technology 208 (2011) 427–432 429

60 5.5
59 Pore volume (%)
5.3
58 Average pore size

Average pore size (µm)

57 5.1

Pore volume (%)

56 4.9
55
4.7
54
53 4.5
52 4.3
51
50 4.1
49 3.9
48
3.7
47
46 3.5
1095 1100 1105 1110 1115 1120 1125 1130 1135
Sintering temperature (°C)

Fig. 6. Variation of pore diameter and pore volume with sintering temperature.

and porous volume of the final product but also allows obtaining the
final morphology and mechanical strength. Sintering was performed at a
temperature ranging from 1100 to 1130 °C.
By controlling the sintering temperature of the ceramic, it is possible
to increase the pore size and to obtain a higher mechanical strength.

2.2.3. Mercury porosimetry

Fig. 4. Main steps of the processing route for support preparation.
A plastic paste obtained was aged for 24 h to homogenize the water
within the paste and then extruded into tubes of 10 mm external
diameter and 8 mm of internal diameter. The tubes were dried for 24 h
then sintered to obtain the final macroporous support. Fig. 4 details the
main steps of the processing route for support preparation.
Sintering experiments were carried out under air. Two steps have
been determined: the first one for the elimination of organic additives at
250 °C and the second one for the sintering at different temperatures
[14]. The temperature–time schedule not only affects the pore diameters
The sintering temperature was optimised at 1125 °C for the
supports elaborated in this work. The supports sintered at this
temperature presented the optimum ratio of the highest mean pore
diameter for the highest mechanical strength. Mercury porosimetry
showed a mean pore diameter and porosity of about 4.5 μm and 51%,
respectively, for the supports sintered at 1125 °C (Fig. 5).
It can also be observed that the porosity and the pore size
parameters are strongly dependent on the sintering temperature
(Fig. 6).
2.2.4. Mechanical and chemical resistances
The measurement of the mechanical resistance of the sintered
material was carried out by the three point bending method (LLOYD
Instrument) applied to sintered parallelepipedic test bars. The size of
samples was 32 mm/10 mm/2 mm and the distance separating the
two points is 28 mm.
Fig. 7 shows the variation of tensile strength with sintering
temperature of samples prepared using the powder P1. An average
tensile strength value obtained by testing 10 bar is marked on the
figure for each temperature. The increase of the sintering temperature
is accompanied with a densification phenomenon and consequently
an increase in the tensile strength (from 9.8 MPa at 1100 °C to
22.9 MPa at 1130 °C). The material sintered at 1125 °C has a tensile
strength of 19.5 MPa, witch represents a good support mechanical
resistance.

29
Tensile strength (MPa)

25

21

17

13

5
1095 1100 1105 1110 1115 1120 1125 1130 1135
Sintering temperature (°C)

Fig. 5. Pore diameters of the mineral coal fly-ash supports. Fig. 7. Variation of tensile strength with sintering temperature.
430 I. Jedidi et al. / Powder Technology 208 (2011) 427–432

The sintered fly ash presents a chemical resistance towards the

acid and basic solutions. In fact the weight loss is negligible when a
sample is exposed during 120 h into a soda aqueous solution at 80 °C
and a pH of 14 and does not exceed 2% when it is exposed to a nitric
acid aqueous solution and a pH of 2 in the same conditions in terms of
time and temperature.

2.3. Microfiltration layer deposition and characterisation

2.3.1. Particle size distribution of the fly-ash powder used in the support
elaboration
The mineral coal fly-ash powder (P2) was used for the microfiltra-
tion layer preparation. This powder was obtained after burning to a
cinder a finely grinded mineral coal powder at 700 °C. The mineral
coal was crushed for 15 h with a planetary crusher at 300 rtm and
calibrated with 50 μm. The fly-ash powder had a particle diameters
range from about 0.5 to 2 μm (Fig. 8).
2.3.2. Microfiltration layer deposition by “slip-casting” process
The active microfiltration layer from fly ash was prepared by a slip-
casting process on fly-ash support (closed-end tubes of 150 mm in
length, with an inner diameter of 5 mm) in dip solution containing the
powder and an aqueous solution of polyvinyl alcohol (PVA)
(Rhodoviol 25/140 (Prolabo)), used as a binder.
Fig. 9. Evolution of the shear stress (τ) versus shear rate (γ) for the fly-ash slip
composition: 4% fly ash/66% water/30% PVA.
2 h, after debonding at 250 °C for 1 h. The pore diameters measured
by mercury porosimetry were centred near 0.25 μm (Fig. 10).
2.3.5. Scanning electron microscopy (SEM)
Scanning electron microscopy (SEM) images of the resulting
membrane are shown in Fig. 11. This figure gives information on the
texture of the elaborated membrane surface. A defect-free membrane
was obtained with a thickness around 22 μm which is acceptable for a
microfiltration layer.

2.4. Filtration tests

2.3.3. Slip characterisation
For preparing a microfiltration layer with mineral coal fly-ash Crossflow microfiltration tests were performed on a homemade
powder (P2), a deflocculated slip was obtained by mixing 4% (w/w) of fly pilot plant (Fig. 12) using 150 mm long tubular membrane. The
ash, 30% (w/w) of polyvinyl alcohol (PVA) (12% w/w aqueous solution) corresponding membrane area is of 11.8 cm2. The tests conditions
as binder and water (66% w/w). The thickness of microfiltration layer were: a temperature of 25 °C and transmembrane pressure (TMP)
can be controlled by the percentage of the clay powder added to the range between 1 and 4 bar. The TMP is adjusted using an inert gaz
suspension and the deposition time. The viscosity of the slip elaborated (N2). The flow rate was fixed at 1.76 m s−1 using a pump with a
according to the protocol described previously has been studied right velocity command witch leads to a turbulent regime inside the
before deposition. The used viscosimeter (LAMY, TVe-05) permits to use filtration cartridge with a Reynolds number Re = 10560. Before the
5 speeds of rotation for the determination of the dynamic viscosity of the
tests, the membrane was conditioned by immersion in pure
substance to characterize. Fig. 9 shows the rheogram of the slip used. It is
done by the curve of shear stress (τ) versus shear rate (γ). Fly-ash slip
was found to exhibit rheo-thickener behaviour, controlled by the
presence of PVA. The PVA percentage optimisation is a crucial parameter
to obtain stable suspension.

2.3.4. Mercury porosimetry

Support
The slip-casting deposition time and the sintering temperature are
the main parameters controlling the final pore diameter and the
nature of the layer texture (with defect of defect free).
A deposition time of 10 min was chosen. After drying at room
temperature for 24 h, the fly-ash membrane was sintered at 800 °C for

Microfiltration Layer

0.25

Fig. 8. Fly-ash powder (P2) particle size distribution used to prepare the microfiltration
layer. Fig. 10. Pore diameters of the fly-ash membrane.
 I. Jedidi et al. / Powder Technology 208 (2011) 427–432 431

Fig. 11. SEM micrographs of the elaborated microfiltration membrane. a) Cross-section and b) surface.

deionised water for a minimum of 24 h. The working pressure was 3. Conclusion

obtained using a nitrogen gas source. The membrane was initially
characterized by the determination of water permeability which This study reports the development and the characterisation of a
was 475 L h−1 m−2 bar−1. new ceramic microfiltration membrane made of mineral coal fly ash.
The fly-ash powder characterisation was performed. It was found that
2.5. Application to the treatment of textile dye waste water the crystalline phase's composition changes with the increase of the
sintering temperature and that the weight loss is very slight. The fly-
The treatment of industrial waste water can be achieved by ash powder used to make the macroporous support was obtained
membrane process. Thus, microfiltration was used in this study to the after heating at 800 °C without prior grinding a mineral coal rock. In
decolourisation of textile dye waste water. the other hand, the powder used to deposit the active layer was
The variation of the permeate flux with time is given in Fig. 13 at a obtained after firing at 800 °C a finely grinded mineral coal powder.
transmembrane pressure (TMP) of 1 bar and a temperature of 25 °C.
The flux drops fast in the first 15 min from 410 L/h m2 to 135 L/h m2
then stabilises at a permeate flux (Jf) of about 90 L/h m2. This
behaviour can be attributed to the membrane fouling establishment.
Three filtration runs were performed. After each run, the
membrane was cleaned with an 80 °C soda (2%) aqueous solution
flowed in the pilot plant for 20 min, followed by deionised water
rinsing until neural pH. Then, a 60 °C nitric acid (2%) aqueous solution
was flowed for 20 min followed by deionised water rinsing until
neutral pH.
Fig. 14 shows that for all the performed runs, the membrane
recovers its initial permeability.
Table 2 gives the main characteristics of the raw and treated
effluent. It can be noticed that the permeate turbidity is very low
(inferior to 1 NTU), the COD retention rate is about 75% and a 90%
removal of colour is obtained. These results prove the high efficiency
of the microfiltration using the elaborated fly-ash membrane to the
dying effluent treatment.
Fig. 13. Variation of permeate flux with time (T = 25 °C, TMP = 1 bar).

2000
1800 First filtration-cleaning cycle

1600 Second filtration-cleaning cycle

1400 Third filtration-cleaning cycle

Jw (L/h.m²)

1200
1000
800
600
400
200
0
0 1 2 3 4 5
Pressure (bars)

Fig. 12. Scheme of experimental apparatus. Fig. 14. Permeability of the elaborated membrane after three filtration-cleaning cycle.
432 I. Jedidi et al. / Powder Technology 208 (2011) 427–432

Table 2 References
Characteristics of the effluent before and after microfiltration at 1 bar.
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