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Adsorption of heavy metal ions from aqueous solution by y ash

I.J. Alinnor
Department of Pure and Industrial Chemistry, Federal University of Technology, P.M.B. 1526, Owerri, Imo State, Nigeria Received 27 October 2005; received in revised form 9 July 2006; accepted 2 August 2006 Available online 18 September 2006

Abstract The removal characteristics of lead and copper ions from aqueous solution by y ash were investigated under various conditions of contact time, pH and temperature. The inuence of pH of the metal ion solutions on the uptake levels of the metal ions by y ash were carried out between pH 4 and 12. The level of uptake of Pb2+ and Cu2+ ions by the y ash generally increased, but not in a progressive manner, at higher pH values. The eect of temperature on the uptake of Pb2+ and Cu2+ ions was investigated between 30 C and 60 C, the adsorption of being enhanced at the lowest temperature. Rate constants were evaluated in terms of a rst-order kinetics. The rate constant, k for uptake of Pb2+ and Cu2+ ions were 1.77 102 s1 and 2.11 102 s1, respectively. The experimental results underline the potential of coal y ash for the recovery of metal ions from waste water. The main mechanisms involved in the removal of heavy metal ions from solution were adsorption at the surface of the y ash and precipitation. 2006 Elsevier Ltd. All rights reserved.
Keywords: Adsorption; Kinetics; Mechanism

1. Introduction There have been previous reports [1,2] on the accumulation of toxic metals in aqueous environment and on economic materials that may be useful to life. These toxic metals have received much attention in recent years, especially in Nigeria. The problem is the removal of these toxic metals using a low-cost adsorbent. Precipitation and ionexchange, the two removal/recovery techniques that have found wide application require the use of chemicals and synthetic resins which are expensive. Many agricultural by-products that are available at little or no cost have been reported to be capable of removing substantial amounts of toxic metals from aqueous solutions [3,4]. Apart from using agricultural by-products for removal of toxic metals from aqueous solutions, other researchers have found y ash, to be a waste product obtained from burning of coal, a useful adsorbent. Given the large amount of y ash generated during burning of coal and large dumping sites required for the

E-mail address: alijuiyke@yahoo.com 0016-2361/$ - see front matter 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2006.08.019

safe disposal, any means of reuse and recycling are welcome. Fly ash is a valuable and desirable additive to cement concrete and it has also been used eectively in many other areas such as soil amendment and llers [5 7]. Some research articles reported that alkaline y ash can serve as stabilizer or binding reagent for the xing of heavy metal and nutrients contained in hazardous wastes and organic wastes [810]. Many researchers have reused y ashes as adsorbents for waste-water or air pollutants control [11,12]. Fly ash eectiveness has been reported in the neutralization of soil acidity and help in increasing the availability of certain nutrients in the soil, and reduction of plant parasitic nematodes in soil [1317]. The rate of increase in demand of y ash for these various applications is less than the rate of increase in production of y ash. Therefore, there are growing concerns about the disposal of y ash. A lot of research work has been carried out for eective removal of toxic metals [1825] and organic materials [2629] from aqueous solution using y ash. The most important characteristics of y ash are the calcium content that provides alkalinity in the system raising pH to strongly alkaline values (12) and the (SiO2 + Al2O3 + Fe2O3) content [30].

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In the present study, an attempt was made to investigate the use of y ash as a low-cost adsorbent for the removal of toxic metals from aqueous solutions. The aim of the present study was to investigate the kinetics and mechanism of Pb2+ and Cu2+ ions uptake by the y ash. 2. Experimental

stated water bath. At the end of the agitation period, the mixture was centrifuged and the metal ions uptake determined as described above. All the chemicals used were of analytical reagent grade. 3. Results and discussion 3.1. Reaction kinetics

The y ash used as the adsorbent in this study was obtained from Nigeria Coal Corporation, Enugu. The y ash samples were dried at 105 C for 2 h before tests. The y ash samples were ground and sieved to a particle size of 250 lm before use. Table 1 shows the chemical composition of the y ash samples used in this study. SiO2 and Al2O3 contents make up about 79% of the y ash, while Fe2O3 and CaO compose about 11%. Batch adsorption experiments were carried out by mechanically shaking series of bottles containing y ash sample and heavy metal ions at dierent pHs. Ig of y ash samples was mixed with 50 ml of distilled water in polyethylene bottles to obtain y ash slurry. The pH of the slurry was adjusted to the desired value in the range of pH 4 to pH 12 with 0.1 m HCL and NaOH [31]. The slurry was agitated with a mechanical shaker at (27 2 C) for 1 h until the pH was stabilized. Then lead and copper ions in the form of nitrate salts were added to the bottles to various concentrations (0.0540.00 mg/g) and the bottles were further agitated for 1 h until equilibrium was attained [32,33]. At the end of agitation period the mixture was centrifuged at 3500 rpm for 10 min [32,31], and the residual concentration of the metal ions in the supernatant was determined using atomic absorption spectrophotometry (AAS) [34]. The amount of Pb2+ and Cu2+ ions adsorbed by y ash was taken as the dierence between the initial and residual concentration of the metal ion. The reported value of Pb2+ and Cu2+ ions adsorbed by y ash in each test were the average of at least three measurements. For the kinetic studies, the y ash was shaken for predetermined time intervals; otherwise a 2 h contact time was found to be adequate. At the end of the equilibrium time, the mixture was centrifuged and the concentration of metal ions determined as above. The inuence of temperature on the uptake behaviour of Pb2+ and Cu2+ ions on the y ash were carried out between 30 C and 60 C using thermoTable 1 Chemical composition of the y ash Constituent SiO2 Al2O3 Fe2O3 CaO MgO SO3 TiO2 K2O Others Wt.% 57.25 22.03 8.36 2.97 0.97 0.76 0.68 0.52 6.49

Fig. 1 shows the amount of metal ions adsorbed on the y ash as a function of contact time. The rate of uptake of metal ions by y ash increases with time initially. The pH was 6.4 where precipitation was relatively low. The metal ion removal in the rst 10 min was 1.4 mg/g and 1.8 mg/g for copper and lead ions, respectively. Equilibrium was attained within 2 h for both these ions. At equilibrium, 5.1 mg/g of lead ion and 4.4 mg/g of copper ion were removed from the solution by the y ash. The results show that the metal ion uptake by y ash depends on the metal ion type. The dierence in the amount of metal ions uptake may be explained in terms of the dierence in the ionic size of the metal ions. The rate constants for adsorption of metal ions on y ash were determined using rst-order kinetics [35]: lnC 0 =C t kt 1

where C0 is the initial metal ions solution concentration, Ct is the concentration at time t, and k is the rate constant. Fig. 2 shows that the initial rate of metal ions uptake conforms to rst-order kinetics as shown in Eq. (1). A plot of

Fig. 1. Eect of contact time on adsorption of dierent metal ions on y ash at pH 6.4.

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Fig. 2. First-order kinetic plot for metal ions adsorption on y ash.

ln C0/Ct versus t should yield a straight line from the slope of which the rate constant k was calculated to be 1.77 102 s1 and 2.11 102 s1 for Pb2+ and Cu2+ ions, respectively. 3.2. Eect of pH The pH of the solution plays a very important role on the uptake of metal ions, since it determines the surface charge of the adsorbent. Fig. 3 shows the amount of heavy metal ions removed from aqueous solution as a function of pH at a heavy metal concentration of 21.00 mg/g. The

amount of Cu2+ ions removed from solution increases rapidly from pH 4 to pH 6. At pH 4, 15.7 mg/g or 74.8% of copper ion was removed, while at pH 6, 19.2 mg/g or 91.4% of copper ion was removed. Above pH 6, the amount of Cu2+ ion removed from the solution by the y ash, steadily increased. 20.6 mg/g or 98.1% at a pH 12. The uptake of Pb2+ ions decreases from pH 4 to pH 6. At pH 4 and 6 the amount of Pb2+ ions removed from solution by the y ash were 17.2 mg/g or 81.9% and 16.3 mg/g or 77.6%, respectively. After pH 6 there was a gradual increase on the Pb2+ ion uptake up to pH 10 and then remaining almost constant up to pH 12. In general, the amount of heavy metal ions removed from solution increased as the pH increased, although this did not occur in a steady progression. The dependence of heavy metal ion adsorption on pH was dierent for the two metal ions studied. Metal ion adsorption on the oxide surfaces is related to the hydrolysis reaction it will undergo in solution [18]. The divalent metal cations in aqueous solution hydrolyze according to the expression: M2 (aq) + nH2 O = M(OH)2n + nH
2+ 2+ 2+

where M = Pb or Cu . At low pH the surfaces of the y ash were positive and there was a formation of complex [Pb(OH)4]2 and [Cu(OH)4]2, the complex formed will be adsorbed on the y ash surfaces. Hydroxyl-metal complex has higher anity for adsorption than hydrated metal ion, because the formation of an OH group of the metal ion reduces the free energy required for adsorption [36]. Similar results have been reported by other workers working on the adsorption of heavy metal ions on y ash [25,3739]. At higher pH, the surfaces of the adsorbent were negative and there was an increase on the uptake of Pb2+ and Cu2+ ions by the y ash. The increase on metal ion uptake, may be explained in terms of electrostatic interaction. This can be seen by the sharp increase on the amount of metal ions uptake as pH increase from 6 to 10 for Pb2+ ions. The increase in metal ions uptake by y ash at higher pH values may be attributed to calcium content and (SiO2 + Al2O3 + Fe2O3) content that provides alkalinity in the system raising the pH to strongly alkaline values, thereby facilitating the uptake of Pb2+ and Cu2+ ions by the y ash. At lower pH values between 4 and 6, Cu2+ and Pb2+ ions may be removed from solution by precipitation and can be adsorbed on the surface of y ash. This is shown by decrease in adsorption by lead ions at lower pH values between 4 and 6. Whereas, at higher pH values higher degree of precipitation of metal ions occur, because hydration of y ash increases its pH between 10 and 13. Similar results have been reported by some workers working on the adsorption of heavy metal ions on y ash [4042]. 3.3. Eect of temperature The removal of heavy metal ions from solution is temperature dependent. Fig. 4 shows the amount of heavy

Fig. 3. Eect of pH on adsorption of dierent metal ions on y ash.

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water. The kinetic study shows that lead and copper ions were adsorbed onto the y ash very rapidly within the rst 20 min, while equilibrium was attained within 2 h for both lead and copper ions. The hydration of y ash increases its pH between 10 and 13, at these pH values higher degree of precipitation of metal ions can be expected, thereby enhancing the removal of heavy metal ions from solution by the y ash. This investigation revealed that increase in temperature decreases uptake of metal ions by the y ash.

Acknowledgements The author is grateful to Opara Jane for technical assistance in performing some measurements. The author is also grateful to University of Uyo, Nigeria, for making use of their facilities in the Central Research Laboratory. References
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Fig. 4. Eect of temperature on adsorption of dierent metal ions on y ash.

metal ions removed from aqueous solution as a function of temperature at a heavy metal concentration of 26.0 mg/g. There was a sharp increase on the uptake of Pb2+ ions by y ash from 30 C to 40 C. At 30 C the amount of Pb2+ ion adsorbed was 20.55 mg/g or 70.0%, whereas at 40 C 22.0 mg/g or 84.6% of Pb2+ ion was adsorbed by the y ash. Beyond 40 C there was a progressive decrease on the uptake of Pb2+ ions by the y ash, until, at 60 C the uptake of metal ion had decreased to 79.0%. Copper ion uptake by the y ash followed a similar pattern of behaviour with a sharp increase between 30 C and 40 C followed by a sharp decrease, the amount of Cu2+ ion uptake by the y ash at 60 C being down to 78.8%. It can be seen that the metal ions uptake follow a similar pattern, but the amount adsorbed at a particular temperature dier. These results indicate that the uptake of metal ions increases at lower temperature. The decrease on the uptake of heavy metal ions with increase in temperature may be explained as a result of increase in the average kinetic energy of the metal ions; thus making the attractive force between metal ions and y ash insucient to retain the metal ions at the binding site. This could lead to desorption or cause the metal ions to bounce o the surface of the y ash instead of colliding and combining with it. Therefore, increase in temperature may be associated with decrease in the stability of metal ion-adsorbent complex. Similar ndings have been reported by other workers working on removal of heavy metal ions from aqueous solution by y ash [43]. 4. Conclusion This study revealed the application of coal y ash as an adsorbent for removal of heavy metal ions from waste

I.J. Alinnor / Fuel 86 (2007) 853857 [33] Okieimen FE, Osuide MO, Oriakhi CO. Niger J Appl Sci 1985;3(1):121. [34] Egila JN, Okorie EO. J Chem Soc Niger 2002(1):95. [35] Eligwe CA, Okolue NB. Fuel 1994;73(4):569. [36] Elliot HA, Denneny CM. J Environ Qual 1982;11:658. [37] Cho H, Oh D, Kim K. J Hazard Mater 2005;B127:187. [38] Benjamin MM, Leckie JO. J Colloid Interface Sci 1981;79:209.

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