Chemosphere 60 (2005) 1401–1407

www.elsevier.com/locate/chemosphere

A comparative study of dye removal using fly ash

treated by different methods
Shaobin Wang *, Y. Boyjoo, A. Choueib
Department of Chemical Engineering, Curtin University of Technology, GPO Box U1987, Perth, WA 6845, Australia

Received 7 October 2004; received in revised form 19 January 2005; accepted 28 January 2005
Available online 9 April 2005

Abstract

The effect of different methods for fly ash treatment using conventional chemical, sonochemical and microwave
method on dye adsorption in aqueous solution was investigated. Three basic dyes, methylene blue, crystal violet and
rhodamine B, are employed for adsorption testing. It is found that fly ash shows different adsorption capacity depend-
ing on type of dyes. Chemical treatment using HCl will increase the adsorption capacity. The adsorption capacity of
HCl treated fly ash varies with the preparation conditions. Microwave treatment is a fast and efficient method while
producing the sample with the highest adsorption capacity. Solution pH and inorganic salts in dye solution can signif-
icantly influence the adsorption. The adsorption data have been analysed using Langmuir, Freundlich and Redlich–
Peterson isotherms. The results indicate that the Freundlich and Redlich–Peterson models provide the better
correlations with the experimental data.

2005 Elsevier Ltd. All rights reserved.

Keywords: Fly ash; Sonochemical treatment; Microwave heating; Basic dyes; Wastewater; Adsorption

1. Introduction is the most popular adsorbent but certain problems with

In recent years, colour stuff discharged from textile
and pulp mills has become one of the important prob-
lems in wastewater treatment. These coloured com-
pounds are not only aesthetically displeasing but also
inhibiting sunlight penetration into the stream and
reducing the photosynthetic reaction. Some dyes are also
toxic and even carcinogenic. Therefore, it is highly nec-
essary to reduce dye concentration in the wastewater
(Vandevivere et al., 1998). Adsorption has been used
extensively in industrial processes for separation and
purification. In wastewater treatment, activated carbon
*
Corresponding author. Tel.: +61 8 9266 3776.
E-mail address: wangshao@vesta.curtin.edu.au (S. Wang).
the high cost and regeneration limit the applications. At
present, there is a growing interest in using other low-
cost adsorbents for adsorption. If a sorbent is inexpen-
sive and ready for use, the adsorption process will be a
promising technology.
Fly ash is one of solid wastes largely produced from
power generation. Currently, its applications are only
limited to civil engineering including cement and brick
production and as a filling in road works. Research is
therefore needed to develop new alternative environ-
mental friendly applications that can further exploit fly
ash. Recently, various kinds of fly ash have been used
as low-cost sorbents for removal of heavy metals, organ-
ics and dyes from waters (Alemany et al., 1996; Rama-
krishna and Viraraghavan, 1997; Kao et al., 2000;
Banerjee et al., 2003; Janos et al., 2003). Most efforts

0045-6535/$ - see front matter
2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2005.01.091
1402 S. Wang et al. / Chemosphere 60 (2005) 1401–1407
are focused on the research of adsorption property.
However, an applicability of the fly ashes for the water
treatment depends strongly on their origin and few
research has been attempted to improve the adsorption
capacity.
Sonochemical (Suslick and Price, 1999; Thompson
and Doraiswamy, 1999) and microwave (Cundy, 1998;
Rao et al., 1999) technologies have been applied for
materials synthesis recently and they show much higher
efficiency than traditional methods. We have reported
that chemical treatment of fly ash can improve the
adsorption capacity (Wang et al., 2004). In this paper
we report our further investigation in utilisation of fly
ash treated by different chemical methods for dye
removal from wastewater. We employed different methods,
conventional chemical and heat treatment, sonochemical
treatment and microwave heat treatment, to compare the
effect of the treatment on adsorption behaviours.
2. Experimental
2.1. Adsorbent materials and dyes
A sample of raw fly ash (FA) was collected from the
electrostatic precipitator from a power station in Wes-
tern Australia, where a sub-bituminous black coal is
fired. The chemical compositions of the fly ash are
SiO2 (55%), Al2O3 (29%), Fe2O3 (8.8%), CaO (1.6%)
and MgO (1.0%). Trace elements include As, B, Ba,
Cd, Co, Cr, Cu, Pb, Mn, Ni, and Zn. The samples
(5 g) were treated by 1 M HCl solution (10 ml) under
various heating conditions, otherwise indicated. Two
H3C + CH3
N S N
CH3 Cl CH3
Methylene Blue
(C2H5)2N
Rhodamine B
Fig. 1. Chemical structure of dyes.
samples were prepared by treatment of the received
FA at room temperature and 100 C for 24 h, respec-
tively, using a conventional oven, referred to as FA-
HCl-RT and FA-HCl-100. One sample (FA-HCl-S)
was treated with HCl solution in an ultrasonic bath
(40 Hz, 300 W, FXP14M, Unisonics, Australia) for
1 h. Two another samples were obtained by treating
with HCl solution under microwave heating at 2 and
10 min, respectively (Samung domestic microwave
800 W), which are referred to FA-HCl-M1 and FA-
HCl-M2. After treatment, all samples were filtrated,
washed and dried at 100 C overnight.
Three basic dyes, methylene blue (MB), crystal violet
(CV), and rhodamine B (RB) were selected for adsorp-
tion tests. They were obtained from AJAX Chemical.
Their chemical structures are displayed in Fig. 1. A
stock solution with a concentration at 10
4 M was pre-
pared and the solutions for adsorption tests were pre-
pared from the stock solution to the desired
concentrations.
2.2. Characterisation of adsorbents
The XRD patterns of all the adsorbents were deter-
mined with an automated Siemens D500 Bragg-Brent-
ano instrument using Cu Ka radiation at 40 kV and
40 mA over the range (2h) of 5–70.
The surface areas of samples were determined by N2
adsorption under
196 C using Autosorb (Quanta-
chrome Corp.). All samples were degassed at 200 C
for 4 h, prior to the adsorption experiments. The BET
surface area was obtained by applying the BET equation
to the adsorption data.
H3C + CH3
N Cl
H3C CH3
N N
CH3 CH3
Crystal Violet
O N+(C2H5)2
Cl
COOH
 S. Wang et al. / Chemosphere 60 (2005) 1401–1407 1403

The pH of the various samples were measured as fol- Table 1

lows: 0.1 g samples were mixed with 10 ml of distilled Physico-chemical properties of the adsorbents
water and were shaken at 30 C for 24 h and then the slurry Adsorbent SBET (m2 g
1) pH
was filtered and the pH of the solution was measured FA 15.6 4.4
by a pH meter (Radiometer PHM250 ion analyser). FA-HCl-RT 28.3 6.0
FA-HCl-100 30.1 5.6
2.3. Adsorption studies FA-HCl-S 30.5 6.9
FA-HCl-M1 35.7 6.8
The adsorption was performed by batch experiments. FA-HCl-M2 28.6 6.3
Solid (0.05 g) in 100 ml of dye solution of varying con-
centration was shaking at 100 rpm for 72 h (Certomat
R shaker from B. Braun) at a constant temperature ples display acid property with different strength. Raw
(30 ± 1 C). The contact time was determined by a pre- FA exhibits the lowest pH, indicating that it has stron-
liminary investigation (Wang et al., 2004). The determi- ger acid functional groups. After acid treatment, the
nation of dyes was done spectrophotometrically on a pH values of all samples are increased at varying extents.
Spectronic 20 Genesis Spectrophotometer (USA) by Microwave acid treatment and sonochemical treatment
measuring absorbance at kmax of 665, 590 and 556 nm results in higher pH than those from conventional heat-
for MB, CV and RB, respectively. To investigate the ing treatment. The enhancement of pH is probably due
effect of pH on adsorption, a series of dye solution was to destruction of acid functional groups by the strong
prepared by adjusting pH over a range of 2–11 using acid and microwave chemical and sonochemical treat-
1 M HNO3 or NaOH solution. The pH of solutions ment induce stronger interactions of surface functional
was measured with a pH meter (Radiometer PHM250 groups with acid.
ion analyser). The effect of inorganic salts on adsorption The results of N2 adsorption on textural properties
was also investigated using KCl. also demonstrate that HCl treatment can improve the
surface areas of fly ash samples. This is probably due
to the removal of some soluble inorganic materials in
3. Results and discussion unburned carbons of fly ash. The SBET of samples by
sonochemical and microwave treatment show a higher
3.1. Characterisation of the adsorbents value than conventional chemical treatment.

The XRD patterns of some adsorbents treated by dif-
ferent methods are shown in Fig. 2. It is seen that there
are not significant difference for all XRD profiles. But
acid-treated samples present higher intensity of diffrac-
tion peaks. The major phases for all samples are quartz
and mullite. Some minor phases, hematite and magne-
tite, are also existed. Those results suggest that acid-
treatment will not induce bulk phase changes.
The pH of the prepared adsorbents is given in Table
1. As shown that the untreated FA and treated FA sam-
3.2. Adsorption tests
3.2.1. Effect of FA weight:HCl volume ratio
Fig. 3 presents the effect of ratio of acid volume to
solid weight on methylene blue adsorption. One can
see that the amount of adsorption increases with the
increasing equilibrium concentration. Acid treatment
can significantly influence the adsorption capacity.
Higher ratio of acid volume to solid weight results in a
3.0e-5

FA
FA-HCl-RT 2.5e-5
FA-HCl-S
30000 FA-HCl-M1
2.0e-5
Qe (mol/g)
Intensity (a.u.)

1.5e-5
20000
1.0e-5

10000 5.0e-6 FA:HCl=5:0

FA:HCl=5:10
FA:HCl=5:20

0.0
0.0 5.0e-6 1.0e-5 1.5e-5 2.0e-5 2.5e-5 3.0e-5 3.5e-5
0
0 20 40 60 80 Ce (M)
2θ
Fig. 3. Effect of HCl:FA ratio on MB adsorption isotherm;
Fig. 2. XRD patterns of various fly ash adsorbents. pH = 5.2.
1404 S. Wang et al. / Chemosphere 60 (2005) 1401–1407

higher adsorption capacity with the adsorption capacity 3.2.2. Effect of different methods
increasing from 1.2 · 10
5 to 2.5 · 10
5 mol/g when the Fig. 4 shows a comparison of adsorption by various
ratio is changed from 5:0 to 5:20. adsorbents for MB, CV and RB. As shown that acid
treatment will generally increase the adsorption of dyes
and all the adsorbents demonstrate higher adsorption
2.00E-05
MB to methylene blue than crystal violet and rhodamine B.
CV
The mode of chemical treatment results in different
Amount adsorbed (mol/g)

R-B
1.50E-05 effects on adsorption behaviour. Higher temperature
treatment under conventional heating process will defi-
nitely enhance the adsorption. Sonochemical treatment
1.00E-05

1e-5
5.00E-06
(a)
8e-6
0.00E+00
FA FA-HCl-RT FA-HCl-100 FA-HCl-M1F A-HCl-M2F A-HCl-S

Qe (mol/g)
6e-6
Fig. 4. Comparison of dye adsorption on various adsorbents:
[MB]0 = 2.7 · 10
5 M, pH = 5.2; [CV]0 = 2.0 · 10
5 M, pH =
4e-6
5.9; [RB]0 = 2.4 · 10
5 M, pH = 6.4.
Experiment
2e-6 Langmuir
Freudlich
Redlich-Peterson
4e-5 MB
CV 0
Amount adsorbed (mol/g)

RB 0.0 5.0e-6 1.0e-5 1.5e-5 2.0e-5 2.5e-5

Ce (M)
3e-5

1e-5

2e-5 (b)
8e-6

1e-5
Qe (mol/g)

6e-6

0 4e-6
2 4 6 8 10 12
pH
2e-6
Fig. 5. Effect of solution pH on dye adsorption. Adsorbent:
FA, [MB]0 = 2.3 · 10
5 M, [CV]0 = 2.1 · 10
5 M, and [RB]0 = 0
1.8 · 10
5 M. 0.0 5.0e-6 1.0e-5 1.5e-5 2.0e-5 2.5e-5
Ce (M)

2.5e-5 1e-5
CV (c)
MB
2.0e-5 RB 8e-6
Amount adsorbed (mol/g)

Qe (mol/g)

1.5e-5 6e-6

1.0e-5 4e-6

5.0e-6 2e-6

0.0 0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.0 5.0e-6 1.0e-5 1.5e-5 2.0e-5 2.5e-5

KCl concentration (M) Ce (M)

Fig. 6. Effect of inorganic salt KCl in dye solution on Fig. 7. Comparison of RB adsorption isotherms on various
adsorption. Dye: MB, adsorbent: FA. adsorbents: (a) FA; (b) FA-HCl-S; (c) FA-HCl-M1.
 S. Wang et al. / Chemosphere 60 (2005) 1401–1407
seems to have a better effect than the conventional chem-
ical treatment. Microwave chemical treatment will incur
the best effect on adsorption. For the adsorption of dif-
ferent dyes, it is also seen that the adsorption capacity of
dyes follows the order of MB > CV > RB. The difference
is probably due to the structure of the dyes. From Fig. 1,
we can see that crystal violet and rhodamine B molecules
are much bigger than methylene blue, which will prevent
the molecules entering the smaller pores of adsorbents,
resulting in lower adsorption.
3.2.3. Effect of pH
The pH of the dye solution plays an important role in
the whole adsorption process and particularly on the
adsorption capacity. The variation of adsorption of
three basic dyes on fly ash over a broad range of pH is
shown in Fig. 5. As shown, the adsorption is lower at
pH < 7 and then is increased to higher value at pH > 7
for methylene blue and crystal violet. Quite significant
enhancement in the adsorption of dye is reached at
pH = 10 than the pH = 8. This variation is quite similar
to the previous reports (Mohan et al., 2002; Janos et al.,
2003). For rhodamine B, the figure displays that the
adsorption shows a slight decrease at higher pH. This
is due to the presence of an acidic group in the dye which
will dissociate with the increasing pH, giving rise to a
negative charge on the dye molecule. It is known that
ionic dyes upon dissolution release coloured dye anions/
cations into solution. The adsorption of these charged
dye groups onto the adsorbent surface is primarily influ-
enced by the surface charge on the adsorbent which is in
turn influenced by the solution pH. Above the zero point
of charge (pHpzc) the negative charge density on the sur-
face of the fly ash favours the sorption of basic (cationic)
dyes (Janos et al., 2003).
3.2.4. Effect of inorganic salts
The effect of inorganic salt (KCl) on adsorption of
basic dyes is presented in Fig. 6. As seen, the presence
Table 2
Comparison of adsorption isotherm models
Model Parameters
Fly ash
Langmuir isotherm Qm = 9.29 · 10
6 mol/g
Freundlich isotherm K = 2.10 · 10
5 mol/g
Redlich–Peterson isotherm K = 31.6 l/g
FA-HCl-S
Langmuir isotherm Qm = 8.08 · 10
6 mol/g
Freundlich isotherm K = 2.00 · 10
5 mol/g
Redlich–Peterson isotherm K = 16.4 l/g
FA-HCl-M1
Langmuir isotherm Qm = 8.69 · 10
6 mol/g
Freundlich isotherm K = 1.24 · 10
5 mol/g
Redlich–Peterson isotherm K = 18.0 l/g
1405
of inorganic salt will significantly influence the adsorp-
tion of MB and CV while it exerts less effect on RB
adsorption. The dye adsorption will increase with the
increasing KCl concentration. This is different from
the investigation reported by Janos et al. (2003). They
tested the effect of inorganic salts (NaCl and CaCl2)
on some acid and basic dye adsorption and found that
the dye adsorption was not affected. But in their investi-
gation, the highest concentration of salts is only 2 mM,
which is quite different from this investigation. Our
results show that higher concentration of salts will pro-
mote the adsorption of dyes on adsorbents.
3.2.5. Adsorption isotherms
The equilibrium adsorption isotherm is of impor-
tance in the design of adsorption systems. Several iso-
therm equations are available and the three important
isotherms are selected in this study, the Langmuir, Fre-
undlich and Redlich–Peterson isotherms.
The Langmuir adsorption isotherm assumes that
adsorption takes place at specific homogeneous sites
within the adsorbent and has found successful applica-
tion to many sorption processes of monolayer adsorp-
tion. The Langmuir isotherm can be written in the form
Qm KC e
Qe ¼ ð1Þ
1 þ KC e
Qe is the adsorbed amount of the dye, Ce is the equilib-
rium concentration of the dye in solution, Qm is the
monolayer adsorption capacity and K is the constant re-
lated to the free energy of adsorption.
The Freundlich isotherm is an empirical equation
employed to describe heterogeneous systems. The Fre-
undlich equation is
Qe ¼ KC 1=n
e ð2Þ
where K and n are Freundlich adsorption isotherm con-
stants, being indicative of the extent of the adsorption
R2
K = 1.53 · 106 M
1 0.928
1/n = 0.0796 0.994
a = 1.53 · 106 M
1 b = 0.926 0.964
K = 8.04 · 104 M
1 0.923
1/n = 0.0928 0.990
a = 8.04 · 104 M
1 b = 0.912 0.965
K = 1.03 · 106 M
1 0.860
1/n = 0.0440 0.963
a = 1.03 · 106 M
1 b = 0.934 0.901
1406 S. Wang et al. / Chemosphere 60 (2005) 1401–1407

and the degree of non-linearity between solution concen- Table 3

tration and adsorption, respectively. Parameters of Freundlich isotherms of various adsorbents
The Redlich–Peterson isotherm model combines ele- Sample Dyes K (mol/g) 1/n R2
ments from both the Langmuir and Freundlich equations, Fly ash MB 4.21 · 10
5 0.1181 0.982
and the mechanism of adsorption is a hybrid one and does CV 3.34 · 10
5 0.1228 0.972
not follow ideal monolayer adsorption. The Redlich– RB 2.10 · 10
5 0.0796 0.994
Peterson equation is widely used as a compromise be- FA-HCl-S MB 3.16 · 10
5 0.0555 0.963
tween Langmuir and Freundlich systems. It is expressed as CV 7.00 · 10
5 0.1495 0.949
KC e RB 2.00 · 10
5 0.0928 0.990
Qe ¼ ð3Þ
1 þ aC be FA-HCl-M1 MB 3.27 · 10
5 0.0462 0.993
CV 1.70 · 10
4 0.2132 0.956
RB 1.24 · 10
5 0.0440 0.963
2.5e-5
(a)
2.0e-5
K and a are the Redlich–Peterson isotherm constants
and b is the exponent, which lies between 1 and 0.
Qe (mol/g)

1.5e-5
Fig. 7 shows a comparison of adsorption isotherms
for curve fitting of the experimental results with above
1.0e-5
three adsorption isotherms. The model parameters from
FA
all isotherms obtained from non-linear regression are
5.0e-6 FA-HCl-S presented in Table 2. As seen that the Redlich–Peterson
FA-HCl-M1
Freundlich model model is better than the Langmuir model in simulation
0.0 of the adsorption isotherm and the Freundlich model
0.0 5.0e-6 1.0e-5 1.5e-5 2.0e-5 2.5e-5 3.0e-5 3.5e-5
Ce (M) will be the best (as evident from correlation coeffi-
cients). This suggests that some heterogeneity in the sur-
1.8e-5 face or pores of the fly ash will play a role in dye
1.6e-5 (b) adsorption.
1.4e-5
Fig. 8 presents the adsorption isotherms of three fly
ash samples, FA, FA-HCl-S and FA-HCl-M1, for
1.2e-5
MB, CV and RB adsorption at 30 C. The Freundlich
Qe (mol/g)

1.0e-5 isotherm is used for the description of adsorption iso-

8.0e-6 therms and the parameters are given in Table 3. As
6.0e-6 shown that three fly ash samples show the adsorption
4.0e-6 capacity in an order of FA-HCl-M1 > FA-HCl-
S > FA. The adsorption of MB, CV and RB on raw
2.0e-6
fly ash is around 1.2 · 10
5, 8.0 · 10
6 and 7.0 ·
0.0
0 5e-6 1e-5 2e-5 2e-5 10
6 mol/g, respectively, while the adsorption on FA-
Ce (M) HCl-M1 can reach to 2.0 · 10
5, 1.6 · 10
5, and 1.0 ·
10
5 mol/g, respectively. The enhancement in adsorp-
1e-5 tion can be attributed to the surface modification of
(c) the chemical methods because XRD patterns do not
8e-6 show significant difference for all the samples. However,
the BET surface area and the pH of solids in water are
6e-6 increased, suggesting that the more active sites for
Qe (mol/g)

adsorption are produced.

4e-6

4. Conclusion
2e-6

Various fly ash samples treated by HCl via conven-

0 tional heating, sonic and microwave heating have been
0.0 5.0e-6 1.0e-5 1.5e-5 2.0e-5 2.5e-5
Ce (M) investigated for removal of basic dyes, methylene blue,
crystal violet and rhodamine B from aqueous solution.
Fig. 8. Adsorption isotherms of various fly ash samples at It is found that the raw fly ash generally exhibits high
30 C: (a) MB; (b) CV; (c) RB. capacity and HCl treatment will improve the adsorption
 S. Wang et al. / Chemosphere 60 (2005) 1401–1407
capacity depending on heating method. Acid treatment
will induce changes in surface properties of adsorbent
while does not bring about the changes in bulk phases.
The dye adsorption was also influenced by solution pH
and inorganic salt. Higher pH will generally result in
higher adsorption for MB and CV, but will decrease
slightly the adsorption of RB. Presence of inorganic salts
will promote the adsorption of dyes. Adsorption
isotherm can be fitted by Langmuir, Freundlich, and
Redlich–Peterson models, in which the Freundlich and
Redlich–Peterson models are the better ones.
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