Equilibrium and kinetic modeling of Malachite green and Cu (II) adsorption by surface enhanced Aegle marmelos correa shell

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ABSTRACT This paper reports on the investigation of adsorption of malachite green (MG) and Cu (II) using aegel marmelos correa shell (AMCS) as a low cost adsorbent. Aegel marmelos correa shells were activated with HCl acid for the removal of MG and Cu (II) from aqueous solution. Adsorption of MG and Cu (II) was done with various operating parameters such as pH, initial concentration and contact time. Highest percentage adsorption was obtained at pH 5 for both MG and Cu (II). The Freundlich and Langmuir isotherms fit the equilibrium data. With increased initial MG and Cu (II) concentration the percentage adsorption decreased whereas the adsorption capacity of the adsorbent found to increase. The pseudo-second-order kinetics described the adsorbate-adsorbent interactions very well with AMCS adsorbent for both MG and Cu (II). Experimental results show that the HCl treated aegel marmelos correa shell (AMCS) is found to be effective and economical adsorbent for the removal of both MG and Cu (II) from aqueous solution. Keywords: Aegle marmelos correa shell; malahite green ; Cu (II); chemical activation. 1. INTRODUCTION The discharge of dyes and toxic metal bearing wastewater are worrying for both toxicological and esthetical reasons in this modern world. Especially disposal of metals and dyes from various process industries like leather tanning, electroplating, textile industries, etc. poses severe environmental problems to water bodies. Some of the existing techniques for the removal of Cu (II) and basic dye are chemical precipitation, ion exchange, reverse osmosis and adsorption are available. But adsorption is one of the simple, economic and efficient techniques for dye and metal removal. Till now, diverse

natural materials like Brazilian pine fruit shell, dehydrated wheat bran, carbon plum kernels, etc. [1,2,3] have been employed as adsorbent. This study aimed at investigating the feasibility of using aegle marmelos correa shell (AMCS), a solid waste, abundantly available in india and south asia, for the sorption of malachite green (MG) and copper from aqueous solution. 2. 2.1 MATERIALS AND METHODS Sorbate and sorbent

Figure. 1 Chemical structure of malachite green Table 1: Characteristics of malachite green Parameters Common / suggested name Other name C.I. Number C.I. name Absorption maximum Empirical formula Formula weight Description Malachite green (MG) Aniline green 42000 Basic green 4 616-620 nm (C23H25N2)2.3C2H2O4 929.0

The stock solution of MG and Cu (II) (1000 mg/l) was prepared by dissolving the appropriate quantity of MG and CuSO4.5H2O (LOBA Chemie and BDH India Ltd.) in 1000 ml of double distilled water. All working solutions of the desired concentration were obtained by diluting the stock solution with distilled water. Chemical activation of the precursor was done by using excess amount of HCl acid and then precursor was washed with distilled water until it reaches the neutral pH. Finally, the adsorbent was dried at 110 C for 2 h, cooled and used for the present study [4]. 2.2 Batch adsorption experiments

Batch experiments were carried out at 30oC temperature for a 50 ml of predetermined MG and Cu (II) solution concentration in a 250 ml conical flask containing the desired dose of adsorbent using isothermal shaker. Samples were withdrawn at different time intervals. Supernatant was separated by filtration. Initially the effect of pH on adsorption was carried out at different pH values. The effect of other parameters on adsorption such as contact time and initial concentration was studied at optimum pH. Residual MG and Cu (II) concentration in filtered solution was analyzed using spectrometer and AAS (Varian, Spectra AA 240FS), respectively. Three replicate measurements per sample were done and the average results are taken for calculation. To estimate the sorption capacity of MG and Cu (II) on AMCS from aqueous solution the following equation was used: qe = (Co Ce )v 1000 w

where qe (mg/g) is the amount of adsorbate adsorbed, Co (mg/l) is the initial adsorbate concentration, Ce is equilibrium adsorbate concentration (mg/l), v is the volume of adsorbate solution (ml) and w (g) is the adsorbent weight added in the test solution. 3. 3.1 RESULTS AND DISCUSSION Effect of pH The pH range of solutions was adjusted to 25 because copper ions precipitated as Cu(OH)2 in a solution with a pH value above 6. Similarly, pH can affect the structural stability of MG and its color intensity above pH 6. It was observed by naked eye during the adjustment of solution pH in the experiment that the dye color reduction began from pH 6. The dye and Cu (II) removal was increased sharply over a pH range of 25. At pH 5 maximum removals of dye (98.9%) and metal (82.4%) was achieved for the initial concentration of 200 mg/l and 75 mg/l at the fixed dose of adsorbent (0.05 g), agitation time (15 h) and temperature (30oC).

3.2

Effect of initial concentration and agitation time With increase in metal ion and dye concentration, there was a considerable

decrease in percentage adsorption but the adsorption capacity (qe) of the adsorbent

increases. With increasing initial concentration, the number of available metal and dye ions near the adsorption site increases and hence the adsorption capacity of the adsorbent increases. Adsorption contact time study reveals that with increase in agitation time the amount of adsorbed sorbate increases up to the equilibrium and then it remains nearly constant as the time elapsed [5]. 3.3 Adsorption isotherm and kinetic studies To determine the relationship between adsorbent and adsorbate at equilibrium and the maximum sorption capacity of adsorbent, sorption isotherm models are widely used for fitting the data, of which the Langmuir and Freundlich equations are most widely used. [2], Langmuir equation: 1 1 1 qe = + ab Ce a
3

log qe

0 -1 0 1 log Ce 2 3

0.5 0.4
Ce/qe

0.3 0.2 0.1 0 0 50

Figure. 2 Isotherm plot for different initial MG concentration (a) Langmuir isotherm (b) Freundlich isotherm
100
Ce

150

200

1 Freundlich equation: log qe = log K + log Ce n where, qe is the amount of dye and Cu (II) ions adsorbed per unit mass of adsorbent (mg/g), Ce is the equilibrium concentration of dye and Cu (II) ions (mg/l), a is a measure of adsorption capacity expressed (mg/g), b is the constant, which is a measure of energy of adsorption expressed (l/mg), K is the measure of adsorption capacity and 1/n is the adsorption intensity. Langmuir and Freundlich adsorption isotherm plots for MG

adsorption are shown in Fig. 2a & 2b respectively. The adsorption kinetics described by the relationship between contact time and adsorbate uptake by AMCS for various initial dye and metal concentrations gives the interaction mechanism between the adsorbate with adsorbent. The linerized-integral form of pseudo-second-order model:

t 1 t = + qt k ' qe 2 qe Experimental result showed that pseudo-second-order kinetics can describe the adsorbate-adsorbent interactions very well with AMCS adsorbent for both MG and Cu (II) [5]. 4. CONCLUSION In the present study, the adsorption capacity of HCl activated AMCS adsorbent for the removal of malachite green Cu (II) has been investigated. Batch equilibrium tests showed that the extent of MG and Cu (II) metal removal was found to be dependent on initial concentration, contact time and pH. The amount of dye and metal adsorbed was found to vary with increasing initial solution pH for the sorption of MG and Cu (II) onto AMCS sorbent. The optimum pH for the effective removal of dye and Cu (II) on AMCS adsorbent was 5. The isotherm studies for both MG and Cu (II) showed to fit for both Langmuir and Freundlich model. These results demonstrate that AMCS adsorbent could be an effective low cost adsorbent for malachite green and Cu (II) adsorption from aqueous solution. References [1] El Qada, E.N., Allen, S.J., Walker, G.M., 2008. Adsorption of basic dyes from aqueous solution onto activated carbons. Chem. Eng. J. 135, 174-184 (2008). [2] Ozer, A., Dursun, G., Removal of methylene blue from aqueous solution by dehydrated wheat bran carbon, J. Hazard. Mater. 146 262-269 (2007). [3] Wu, F., Tseng, R., Juang, R., Pore structure and adsorption performance of the activated carbons prepared from plum kernels, J. Hazard. Mater. B69, 287-302 (1999). [4] Anandkumar, J., Mandal, B., Removal of Cr(VI) from aqueous solution using Bael fruit (Aegle marmelos correa) shell as an adsorbent, J. Hazard. Mater. 168 633640 (2009).

[5] S. Al-Asheh, Z. Duvnjak, Adsorption of copper by canola meal, J. Hazard. Mater. 48, 83-93 (1996).

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