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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
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. samples were prepared by treatment of the received
However, an applicability of the fly ashes for the water FA at room temperature and 100 C for 24 h, respec-
treatment depends strongly on their origin and few tively, using a conventional oven, referred to as FA-
research has been attempted to improve the adsorption HCl-RT and FA-HCl-100. One sample (FA-HCl-S)
capacity. was treated with HCl solution in an ultrasonic bath
Sonochemical (Suslick and Price, 1999; Thompson (40 Hz, 300 W, FXP14M, Unisonics, Australia) for
and Doraiswamy, 1999) and microwave (Cundy, 1998; 1 h. Two another samples were obtained by treating
Rao et al., 1999) technologies have been applied for with HCl solution under microwave heating at 2 and
materials synthesis recently and they show much higher 10 min, respectively (Samung domestic microwave
efficiency than traditional methods. We have reported 800 W), which are referred to FA-HCl-M1 and FA-
that chemical treatment of fly ash can improve the HCl-M2. After treatment, all samples were filtrated,
adsorption capacity (Wang et al., 2004). In this paper washed and dried at 100 C overnight.
we report our further investigation in utilisation of fly Three basic dyes, methylene blue (MB), crystal violet
ash treated by different chemical methods for dye (CV), and rhodamine B (RB) were selected for adsorp-
removal from wastewater. We employed different methods, tion tests. They were obtained from AJAX Chemical.
conventional chemical and heat treatment, sonochemical Their chemical structures are displayed in Fig. 1. A
treatment and microwave heat treatment, to compare the stock solution with a concentration at 104 M was pre-
effect of the treatment on adsorption behaviours. pared and the solutions for adsorption tests were pre-
pared from the stock solution to the desired
concentrations.
2. Experimental
2.2. Characterisation of adsorbents
2.1. Adsorbent materials and dyes
The XRD patterns of all the adsorbents were deter-
A sample of raw fly ash (FA) was collected from the mined with an automated Siemens D500 Bragg-Brent-
electrostatic precipitator from a power station in Wes- ano instrument using Cu Ka radiation at 40 kV and
tern Australia, where a sub-bituminous black coal is 40 mA over the range (2h) of 5–70.
fired. The chemical compositions of the fly ash are The surface areas of samples were determined by N2
SiO2 (55%), Al2O3 (29%), Fe2O3 (8.8%), CaO (1.6%) adsorption under 196 C using Autosorb (Quanta-
and MgO (1.0%). Trace elements include As, B, Ba, chrome Corp.). All samples were degassed at 200 C
Cd, Co, Cr, Cu, Pb, Mn, Ni, and Zn. The samples for 4 h, prior to the adsorption experiments. The BET
(5 g) were treated by 1 M HCl solution (10 ml) under surface area was obtained by applying the BET equation
various heating conditions, otherwise indicated. Two to the adsorption data.
H3C + CH3
N Cl
H3C + CH3
N S N
CH3 Cl CH3
H3C CH3
N N
Methylene Blue
CH3 CH3
Crystal Violet
(C2H5)2N O N+(C2H5)2
Cl
COOH
Rhodamine B
The XRD patterns of some adsorbents treated by dif- 3.2. Adsorption tests
ferent methods are shown in Fig. 2. It is seen that there
are not significant difference for all XRD profiles. But 3.2.1. Effect of FA weight:HCl volume ratio
acid-treated samples present higher intensity of diffrac- Fig. 3 presents the effect of ratio of acid volume to
tion peaks. The major phases for all samples are quartz solid weight on methylene blue adsorption. One can
and mullite. Some minor phases, hematite and magne- see that the amount of adsorption increases with the
tite, are also existed. Those results suggest that acid- increasing equilibrium concentration. Acid treatment
treatment will not induce bulk phase changes. can significantly influence the adsorption capacity.
The pH of the prepared adsorbents is given in Table Higher ratio of acid volume to solid weight results in a
1. As shown that the untreated FA and treated FA sam-
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
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 · 105 to 2.5 · 105 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 · 105 M, pH = 5.2; [CV]0 = 2.0 · 105 M, pH =
4e-6
5.9; [RB]0 = 2.4 · 105 M, pH = 6.4.
Experiment
2e-6 Langmuir
Freudlich
Redlich-Peterson
4e-5 MB
CV 0
Amount adsorbed (mol/g)
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 · 105 M, [CV]0 = 2.1 · 105 M, and [RB]0 = 0
1.8 · 105 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
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 1405
seems to have a better effect than the conventional chem- of inorganic salt will significantly influence the adsorp-
ical treatment. Microwave chemical treatment will incur tion of MB and CV while it exerts less effect on RB
the best effect on adsorption. For the adsorption of dif- adsorption. The dye adsorption will increase with the
ferent dyes, it is also seen that the adsorption capacity of increasing KCl concentration. This is different from
dyes follows the order of MB > CV > RB. The difference the investigation reported by Janos et al. (2003). They
is probably due to the structure of the dyes. From Fig. 1, tested the effect of inorganic salts (NaCl and CaCl2)
we can see that crystal violet and rhodamine B molecules on some acid and basic dye adsorption and found that
are much bigger than methylene blue, which will prevent the dye adsorption was not affected. But in their investi-
the molecules entering the smaller pores of adsorbents, gation, the highest concentration of salts is only 2 mM,
resulting in lower adsorption. which is quite different from this investigation. Our
results show that higher concentration of salts will pro-
3.2.3. Effect of pH mote the adsorption of dyes on adsorbents.
The pH of the dye solution plays an important role in
the whole adsorption process and particularly on the 3.2.5. Adsorption isotherms
adsorption capacity. The variation of adsorption of The equilibrium adsorption isotherm is of impor-
three basic dyes on fly ash over a broad range of pH is tance in the design of adsorption systems. Several iso-
shown in Fig. 5. As shown, the adsorption is lower at therm equations are available and the three important
pH < 7 and then is increased to higher value at pH > 7 isotherms are selected in this study, the Langmuir, Fre-
for methylene blue and crystal violet. Quite significant undlich and Redlich–Peterson isotherms.
enhancement in the adsorption of dye is reached at The Langmuir adsorption isotherm assumes that
pH = 10 than the pH = 8. This variation is quite similar adsorption takes place at specific homogeneous sites
to the previous reports (Mohan et al., 2002; Janos et al., within the adsorbent and has found successful applica-
2003). For rhodamine B, the figure displays that the tion to many sorption processes of monolayer adsorp-
adsorption shows a slight decrease at higher pH. This tion. The Langmuir isotherm can be written in the form
is due to the presence of an acidic group in the dye which
will dissociate with the increasing pH, giving rise to a Qm KC e
Qe ¼ ð1Þ
negative charge on the dye molecule. It is known that 1 þ KC e
ionic dyes upon dissolution release coloured dye anions/
cations into solution. The adsorption of these charged Qe is the adsorbed amount of the dye, Ce is the equilib-
dye groups onto the adsorbent surface is primarily influ- rium concentration of the dye in solution, Qm is the
enced by the surface charge on the adsorbent which is in monolayer adsorption capacity and K is the constant re-
turn influenced by the solution pH. Above the zero point lated to the free energy of adsorption.
of charge (pHpzc) the negative charge density on the sur- The Freundlich isotherm is an empirical equation
face of the fly ash favours the sorption of basic (cationic) employed to describe heterogeneous systems. The Fre-
dyes (Janos et al., 2003). undlich equation is
Qe ¼ KC 1=n
e ð2Þ
3.2.4. Effect of inorganic salts
The effect of inorganic salt (KCl) on adsorption of where K and n are Freundlich adsorption isotherm con-
basic dyes is presented in Fig. 6. As seen, the presence stants, being indicative of the extent of the adsorption
Table 2
Comparison of adsorption isotherm models
Model Parameters R2
Fly ash
Langmuir isotherm Qm = 9.29 · 106 mol/g K = 1.53 · 106 M1 0.928
Freundlich isotherm K = 2.10 · 105 mol/g 1/n = 0.0796 0.994
Redlich–Peterson isotherm K = 31.6 l/g a = 1.53 · 106 M1 b = 0.926 0.964
FA-HCl-S
Langmuir isotherm Qm = 8.08 · 106 mol/g K = 8.04 · 104 M1 0.923
Freundlich isotherm K = 2.00 · 105 mol/g 1/n = 0.0928 0.990
Redlich–Peterson isotherm K = 16.4 l/g a = 8.04 · 104 M1 b = 0.912 0.965
FA-HCl-M1
Langmuir isotherm Qm = 8.69 · 106 mol/g K = 1.03 · 106 M1 0.860
Freundlich isotherm K = 1.24 · 105 mol/g 1/n = 0.0440 0.963
Redlich–Peterson isotherm K = 18.0 l/g a = 1.03 · 106 M1 b = 0.934 0.901
1406 S. Wang et al. / Chemosphere 60 (2005) 1401–1407
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)
4. Conclusion
2e-6
capacity depending on heating method. Acid treatment Janos, P., Buchtova, H., Ryznarova, M., 2003. Sorption of dyes
will induce changes in surface properties of adsorbent from aqueous solutions onto fly ash. Water Res. 37, 4938–
while does not bring about the changes in bulk phases. 4944.
The dye adsorption was also influenced by solution pH Kao, P.-C., Tzeng, J.-H., Huang, T.-L., 2000. Removal of
chlorophenols from aqueous solution by fly ash. J. Hazard.
and inorganic salt. Higher pH will generally result in
Mater. 76, 237–249.
higher adsorption for MB and CV, but will decrease Mohan, D., Singh, K.P., Singh, G., Kumar, K., 2002. Removal
slightly the adsorption of RB. Presence of inorganic salts of dyes from wastewater using fly ash, a low-cost adsorbent.
will promote the adsorption of dyes. Adsorption Ind. Eng. Chem. Res. 41, 3688–3695.
isotherm can be fitted by Langmuir, Freundlich, and Ramakrishna, K.R., Viraraghavan, T., 1997. Dye removal
Redlich–Peterson models, in which the Freundlich and using low cost adsorbents. Water Sci. Technol. 36, 189–196.
Redlich–Peterson models are the better ones. Rao, K.J., Vaidhyanathan, B., Ganguli, M., Ramakrishnan,
P.A., 1999. Synthesis of inorganic solids using microwaves.
Chem. Mater. 11, 882–895.
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