Chemosphere 60 (2005) 14011407 www.elsevier.

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A comparative study of dye removal using y ash treated by dierent 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 eect of dierent methods for y 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 y ash shows dierent adsorption capacity depending on type of dyes. Chemical treatment using HCl will increase the adsorption capacity. The adsorption capacity of HCl treated y ash varies with the preparation conditions. Microwave treatment is a fast and ecient method while producing the sample with the highest adsorption capacity. Solution pH and inorganic salts in dye solution can significantly inuence the adsorption. The adsorption data have been analysed using Langmuir, Freundlich and Redlich Peterson isotherms. The results indicate that the Freundlich and RedlichPeterson 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 In recent years, colour stu discharged from textile and pulp mills has become one of the important problems in wastewater treatment. These coloured compounds 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 necessary to reduce dye concentration in the wastewater (Vandevivere et al., 1998). Adsorption has been used extensively in industrial processes for separation and purication. In wastewater treatment, activated carbon

Corresponding author. Tel.: +61 8 9266 3776. E-mail address: wangshao@vesta.curtin.edu.au (S. Wang).

is the most popular adsorbent but certain problems with the high cost and regeneration limit the applications. At present, there is a growing interest in using other lowcost adsorbents for adsorption. If a sorbent is inexpensive 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 lling in road works. Research is therefore needed to develop new alternative environmental friendly applications that can further exploit y ash. Recently, various kinds of y ash have been used as low-cost sorbents for removal of heavy metals, organics and dyes from waters (Alemany et al., 1996; Ramakrishna and Viraraghavan, 1997; Kao et al., 2000; Banerjee et al., 2003; Janos et al., 2003). Most eorts

0045-6535/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.chemosphere.2005.01.091

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are focused on the research of adsorption property. However, an applicability of the y 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 eciency than traditional methods. We have reported that chemical treatment of y ash can improve the adsorption capacity (Wang et al., 2004). In this paper we report our further investigation in utilisation of y ash treated by dierent chemical methods for dye removal from wastewater. We employed dierent methods, conventional chemical and heat treatment, sonochemical treatment and microwave heat treatment, to compare the eect of the treatment on adsorption behaviours.

samples were prepared by treatment of the received FA at room temperature and 100 C for 24 h, respectively, using a conventional oven, referred to as FAHCl-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 FAHCl-M2. After treatment, all samples were ltrated, washed and dried at 100 C overnight. Three basic dyes, methylene blue (MB), crystal violet (CV), and rhodamine B (RB) were selected for adsorption tests. They were obtained from AJAX Chemical. Their chemical structures are displayed in Fig. 1. A stock solution with a concentration at 104 M was prepared and the solutions for adsorption tests were prepared from the stock solution to the desired concentrations. 2.2. Characterisation of adsorbents

2. Experimental 2.1. Adsorbent materials and dyes A sample of raw y ash (FA) was collected from the electrostatic precipitator from a power station in Western Australia, where a sub-bituminous black coal is red. The chemical compositions of the y 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 The XRD patterns of all the adsorbents were determined with an automated Siemens D500 Bragg-Brentano instrument using Cu Ka radiation at 40 kV and 40 mA over the range (2h) of 570. The surface areas of samples were determined by N2 adsorption under 196 C using Autosorb (Quantachrome 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

Cl

N H3C N CH3 S Cl
+

CH3 H3C CH3

CH3

Methylene Blue

N CH3 Crystal Violet

CH3

(C2H5)2N

N+(C2H5)2 Cl

COOH

Rhodamine B

Fig. 1. Chemical structure of dyes.

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The pH of the various samples were measured as follows: 0.1 g samples were mixed with 10 ml of distilled water and were shaken at 30 C for 24 h and then the slurry was ltered and the pH of the solution was measured by a pH meter (Radiometer PHM250 ion analyser). 2.3. Adsorption studies The adsorption was performed by batch experiments. Solid (0.05 g) in 100 ml of dye solution of varying concentration was shaking at 100 rpm for 72 h (Certomat R shaker from B. Braun) at a constant temperature (30 1 C). The contact time was determined by a preliminary investigation (Wang et al., 2004). The determination of dyes was done spectrophotometrically on a Spectronic 20 Genesis Spectrophotometer (USA) by measuring absorbance at kmax of 665, 590 and 556 nm for MB, CV and RB, respectively. To investigate the eect of pH on adsorption, a series of dye solution was prepared by adjusting pH over a range of 211 using 1 M HNO3 or NaOH solution. The pH of solutions was measured with a pH meter (Radiometer PHM250 ion analyser). The eect of inorganic salts on adsorption was also investigated using KCl.

Table 1 Physico-chemical properties of the adsorbents Adsorbent FA FA-HCl-RT FA-HCl-100 FA-HCl-S FA-HCl-M1 FA-HCl-M2 SBET (m2 g1) 15.6 28.3 30.1 30.5 35.7 28.6 pH 4.4 6.0 5.6 6.9 6.8 6.3

3. Results and discussion 3.1. Characterisation of the adsorbents The XRD patterns of some adsorbents treated by different methods are shown in Fig. 2. It is seen that there are not signicant dierence for all XRD proles. But acid-treated samples present higher intensity of diraction peaks. The major phases for all samples are quartz and mullite. Some minor phases, hematite and magnetite, are also existed. Those results suggest that acidtreatment 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 samFA FA-HCl-RT FA-HCl-S FA-HCl-M1

ples display acid property with dierent strength. Raw FA exhibits the lowest pH, indicating that it has stronger acid functional groups. After acid treatment, the pH values of all samples are increased at varying extents. Microwave acid treatment and sonochemical treatment results in higher pH than those from conventional heating treatment. The enhancement of pH is probably due to destruction of acid functional groups by the strong acid and microwave chemical and sonochemical treatment induce stronger interactions of surface functional groups with acid. The results of N2 adsorption on textural properties also demonstrate that HCl treatment can improve the surface areas of y ash samples. This is probably due to the removal of some soluble inorganic materials in unburned carbons of y ash. The SBET of samples by sonochemical and microwave treatment show a higher value than conventional chemical treatment. 3.2. Adsorption tests 3.2.1. Eect of FA weight:HCl volume ratio Fig. 3 presents the eect 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 signicantly inuence the adsorption capacity. Higher ratio of acid volume to solid weight results in a
3.0e-5 2.5e-5 2.0e-5 1.5e-5 1.0e-5

30000

Intensity (a.u.)

20000

Qe (mol/g)

10000

5.0e-6 0.0 0.0

FA:HCl=5:0 FA:HCl=5:10 FA:HCl=5:20

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

3.0e-5 3.5e-5

20

40

60

80

Ce (M)

Fig. 2. XRD patterns of various y ash adsorbents.

Fig. 3. Eect of HCl:FA ratio on MB adsorption isotherm; pH = 5.2.

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higher adsorption capacity with the adsorption capacity increasing from 1.2 105 to 2.5 105 mol/g when the ratio is changed from 5:0 to 5:20.
2.00E-05

Amount adsorbed (mol/g)

MB CV R-B

1.50E-05

3.2.2. Eect of dierent methods Fig. 4 shows a comparison of adsorption by various 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 to methylene blue than crystal violet and rhodamine B. The mode of chemical treatment results in dierent eects on adsorption behaviour. Higher temperature treatment under conventional heating process will denitely enhance the adsorption. Sonochemical treatment

1.00E-05

5.00E-06

1e-5

(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 = 5.9; [RB]0 = 2.4 105 M, pH = 6.4.

4e-6
Experiment Langmuir Freudlich Redlich-Peterson

2e-6

4e-5

Amount adsorbed (mol/g)

MB CV RB

0 0.0 5.0e-6 1.0e-5 1.5e-5

Ce (M)

2.0e-5

2.5e-5

3e-5
1e-5

2e-5
8e-6

(b)

Qe (mol/g)
2 4 6 8 10 12

1e-5

6e-6

4e-6

pH
2e-6

Fig. 5. Eect of solution pH on dye adsorption. Adsorbent: FA, [MB]0 = 2.3 105 M, [CV]0 = 2.1 105 M, and [RB]0 = 1.8 105 M.

0 0.0 5.0e-6 1.0e-5 1.5e-5 2.0e-5 2.5e-5

Ce (M)

2.5e-5
CV MB RB

1e-5

(c)
8e-6

Amount adsorbed (mol/g)

2.0e-5

Qe (mol/g)

1.5e-5

6e-6

1.0e-5

4e-6

5.0e-6

2e-6

0.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6

0 0.0 5.0e-6 1.0e-5

Ce (M)

1.5e-5

2.0e-5

2.5e-5

KCl concentration (M)

Fig. 6. Eect of inorganic salt KCl in dye solution on adsorption. Dye: MB, adsorbent: FA.

Fig. 7. Comparison of RB adsorption isotherms on various adsorbents: (a) FA; (b) FA-HCl-S; (c) FA-HCl-M1.

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seems to have a better eect than the conventional chemical treatment. Microwave chemical treatment will incur the best eect on adsorption. For the adsorption of different dyes, it is also seen that the adsorption capacity of dyes follows the order of MB > CV > RB. The dierence 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. Eect 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 y 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 signicant 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 gure 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 inuenced by the surface charge on the adsorbent which is in turn inuenced by the solution pH. Above the zero point of charge (pHpzc) the negative charge density on the surface of the y ash favours the sorption of basic (cationic) dyes (Janos et al., 2003). 3.2.4. Eect of inorganic salts The eect 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 Fly ash Langmuir isotherm Freundlich isotherm RedlichPeterson isotherm FA-HCl-S Langmuir isotherm Freundlich isotherm RedlichPeterson isotherm FA-HCl-M1 Langmuir isotherm Freundlich isotherm RedlichPeterson isotherm Parameters Qm = 9.29 106 mol/g K = 2.10 105 mol/g K = 31.6 l/g Qm = 8.08 106 mol/g K = 2.00 105 mol/g K = 16.4 l/g Qm = 8.69 106 mol/g K = 1.24 105 mol/g K = 18.0 l/g

of inorganic salt will signicantly inuence the adsorption of MB and CV while it exerts less eect on RB adsorption. The dye adsorption will increase with the increasing KCl concentration. This is dierent from the investigation reported by Janos et al. (2003). They tested the eect of inorganic salts (NaCl and CaCl2) on some acid and basic dye adsorption and found that the dye adsorption was not aected. But in their investigation, the highest concentration of salts is only 2 mM, which is quite dierent from this investigation. Our results show that higher concentration of salts will promote the adsorption of dyes on adsorbents. 3.2.5. Adsorption isotherms The equilibrium adsorption isotherm is of importance in the design of adsorption systems. Several isotherm equations are available and the three important isotherms are selected in this study, the Langmuir, Freundlich and RedlichPeterson isotherms. The Langmuir adsorption isotherm assumes that adsorption takes place at specic homogeneous sites within the adsorbent and has found successful application to many sorption processes of monolayer adsorption. The Langmuir isotherm can be written in the form Qe Qm KC e 1 KC e 1

Qe is the adsorbed amount of the dye, Ce is the equilibrium concentration of the dye in solution, Qm is the monolayer adsorption capacity and K is the constant related to the free energy of adsorption. The Freundlich isotherm is an empirical equation employed to describe heterogeneous systems. The Freundlich equation is
=n Qe KC 1 e

where K and n are Freundlich adsorption isotherm constants, being indicative of the extent of the adsorption

R2 K = 1.53 106 M1 1/n = 0.0796 a = 1.53 106 M1 K = 8.04 104 M1 1/n = 0.0928 a = 8.04 104 M1 K = 1.03 106 M1 1/n = 0.0440 a = 1.03 106 M1 0.928 0.994 0.964 0.923 0.990 0.965 0.860 0.963 0.901

b = 0.926

b = 0.912

b = 0.934

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S. Wang et al. / Chemosphere 60 (2005) 14011407 Table 3 Parameters of Freundlich isotherms of various adsorbents Sample Fly ash Dyes MB CV RB MB CV RB MB CV RB K (mol/g) 4.21 105 3.34 105 2.10 105 3.16 105 7.00 105 2.00 105 3.27 105 1.70 104 1.24 105 1/n 0.1181 0.1228 0.0796 0.0555 0.1495 0.0928 0.0462 0.2132 0.0440 R2 0.982 0.972 0.994 0.963 0.949 0.990 0.993 0.956 0.963

and the degree of non-linearity between solution concentration and adsorption, respectively. The RedlichPeterson isotherm model combines elements from both the Langmuir and Freundlich equations, and the mechanism of adsorption is a hybrid one and does not follow ideal monolayer adsorption. The Redlich Peterson equation is widely used as a compromise between Langmuir and Freundlich systems. It is expressed as Qe KC e 1 aC b e 3

FA-HCl-S

FA-HCl-M1

2.5e-5

(a)
2.0e-5

1.5e-5

1.0e-5
FA FA-HCl-S FA-HCl-M1 Freundlich model

5.0e-6

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

Ce (M)
1.8e-5 1.6e-5 1.4e-5

(b)

Qe (mol/g)

1.2e-5 1.0e-5 8.0e-6 6.0e-6 4.0e-6 2.0e-6 0.0 0 5e-6 1e-5 2e-5 2e-5

Ce (M)
1e-5

(c)
8e-6

Qe (mol/g)

6e-6

K and a are the RedlichPeterson isotherm constants and b is the exponent, which lies between 1 and 0. Fig. 7 shows a comparison of adsorption isotherms for curve tting of the experimental results with above three adsorption isotherms. The model parameters from all isotherms obtained from non-linear regression are presented in Table 2. As seen that the RedlichPeterson model is better than the Langmuir model in simulation of the adsorption isotherm and the Freundlich model will be the best (as evident from correlation coecients). This suggests that some heterogeneity in the surface or pores of the y ash will play a role in dye adsorption. Fig. 8 presents the adsorption isotherms of three y ash samples, FA, FA-HCl-S and FA-HCl-M1, for MB, CV and RB adsorption at 30 C. The Freundlich isotherm is used for the description of adsorption isotherms and the parameters are given in Table 3. As shown that three y ash samples show the adsorption capacity in an order of FA-HCl-M1 > FA-HClS > FA. The adsorption of MB, CV and RB on raw y ash is around 1.2 105, 8.0 106 and 7.0 106 mol/g, respectively, while the adsorption on FAHCl-M1 can reach to 2.0 105, 1.6 105, and 1.0 105 mol/g, respectively. The enhancement in adsorption can be attributed to the surface modication of the chemical methods because XRD patterns do not show signicant dierence for all the samples. However, the BET surface area and the pH of solids in water are increased, suggesting that the more active sites for adsorption are produced.

Qe (mol/g)

4e-6

2e-6

4. Conclusion Various y ash samples treated by HCl via conventional heating, sonic and microwave heating have been investigated for removal of basic dyes, methylene blue, crystal violet and rhodamine B from aqueous solution. It is found that the raw y ash generally exhibits high capacity and HCl treatment will improve the adsorption

0 0.0 5.0e-6 1.0e-5 1.5e-5 2.0e-5 2.5e-5

Ce (M)

Fig. 8. Adsorption isotherms of various y ash samples at 30 C: (a) MB; (b) CV; (c) RB.

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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 inuenced 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 tted by Langmuir, Freundlich, and RedlichPeterson models, in which the Freundlich and RedlichPeterson models are the better ones. References
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