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Adsorption of heavy metal ions from aqueous solution by fly 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 fly ash were investigated under various conditions of contact time, pH and temperature. The influence of pH of the metal ion solutions on the uptake levels of the metal ions by fly ash were carried out between pH 4 and 12. The level of uptake of Pb2+ and Cu2+ ions by the fly ash generally increased, but not in a progressive manner, at higher pH values. The effect 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 first-order kinetics. The rate constant, k for uptake of Pb2+ and Cu2+ ions were 1.77 · 10À2 sÀ1 and 2.11 · 10À2 sÀ1, respectively. The experimental results underline the potential of coal fly 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 fly ash and precipitation. Ó 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 fly ash, to be a waste product obtained from burning of coal, a useful adsorbent. Given the large amount of fly ash generated during burning of coal and large dumping sites required for the

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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 effectively in many other areas such as soil amendment and fillers [5– 7]. Some research articles reported that alkaline fly ash can serve as stabilizer or binding reagent for the fixing of heavy metal and nutrients contained in hazardous wastes and organic wastes [8–10]. Many researchers have reused fly ashes as adsorbents for waste-water or air pollutants control [11,12]. Fly ash effectiveness 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 [13–17]. The rate of increase in demand of fly ash for these various applications is less than the rate of increase in production of fly ash. Therefore, there are growing concerns about the disposal of fly ash. A lot of research work has been carried out for effective removal of toxic metals [18–25] and organic materials [26–29] from aqueous solution using fly ash. The most important characteristics of fly 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].

36 2.97 0. All the chemicals used were of analytical reagent grade. The results show that the metal ion uptake by fly ash depends on the metal ion type.31]. At the end of the equilibrium time. Batch adsorption experiments were carried out by mechanically shaking series of bottles containing fly ash sample and heavy metal ions at different pH’s. and the residual concentration of the metal ions in the supernatant was determined using atomic absorption spectrophotometry (AAS) [34].68 0.8 mg/g for copper and lead ions. Enugu.1. At the end of the agitation period. The metal ion removal in the first 10 min was 1. Ig of fly ash samples was mixed with 50 ml of distilled water in polyethylene bottles to obtain fly ash slurry. The amount of Pb2+ and Cu2+ ions adsorbed by fly ash was taken as the difference between the initial and residual concentration of the metal ion.52 6.76 0. The reported value of Pb2+ and Cu2+ ions adsorbed by fly ash in each test were the average of at least three measurements. Reaction kinetics The fly ash used as the adsorbent in this study was obtained from Nigeria Coal Corporation.00 mg/g) and the bottles were further agitated for 1 h until equilibrium was attained [32. 5. SiO2 and Al2O3 contents make up about 79% of the fly ash.% 57.4 mg/g of copper ion were removed from the solution by the fly ash.854 I. the mixture was centrifuged and the concentration of metal ions determined as above. The influence of temperature on the uptake behaviour of Pb2+ and Cu2+ ions on the fly ash were carried out between 30 °C and 60 °C using thermoTable 1 Chemical composition of the fly ash Constituent SiO2 Al2O3 Fe2O3 CaO MgO SO3 TiO2 K2O Others Wt. Then lead and copper ions in the form of nitrate salts were added to the bottles to various concentrations (0. The pH was 6. Fig. while Fe2O3 and CaO compose about 11%. The rate constants for adsorption of metal ions on fly ash were determined using first-order kinetics [35]: lnðC 0 =C t Þ ¼ kt ð 1Þ where C0 is the initial metal ions solution concentration. The aim of the present study was to investigate the kinetics and mechanism of Pb2+ and Cu2+ ions uptake by the fly ash. Equilibrium was attained within 2 h for both these ions.49 Fig. 1 shows the amount of metal ions adsorbed on the fly ash as a function of contact time. At the end of agitation period the mixture was centrifuged at 3500 rpm for 10 min [32.05–40. an attempt was made to investigate the use of fly ash as a low-cost adsorbent for the removal of toxic metals from aqueous solutions. 2 shows that the initial rate of metal ions uptake conforms to first-order kinetics as shown in Eq. 3. The slurry was agitated with a mechanical shaker at (27 ± 2 °C) for 1 h until the pH was stabilized.1 m HCL and NaOH [31]. The fly ash samples were dried at 105 °C for 2 h before tests.03 8. respectively. At equilibrium. The pH of the slurry was adjusted to the desired value in the range of pH 4 to pH 12 with 0. 2. 1. The difference in the amount of metal ions uptake may be explained in terms of the difference in the ionic size of the metal ions. For the kinetic studies. Table 1 shows the chemical composition of the fly ash samples used in this study. The fly ash samples were ground and sieved to a particle size of 250 lm before use. and k is the rate constant.25 22. Experimental stated water bath. (1). otherwise a 2 h contact time was found to be adequate. The rate of uptake of metal ions by fly ash increases with time initially. Ct is the concentration at time t. the mixture was centrifuged and the metal ions uptake determined as described above.33].1 mg/g of lead ion and 4. Results and discussion 3.97 0. Effect of contact time on adsorption of different metal ions on fly ash at pH 6.4 where precipitation was relatively low.4 mg/g and 1.J. the fly ash was shaken for predetermined time intervals. . Alinnor / Fuel 86 (2007) 853–857 In the present study. A plot of Fig.4.

because the formation of an OH group of the metal ion reduces the free energy required for adsorption [36]. Effect of pH The pH of the solution plays a very important role on the uptake of metal ions. 4 shows the amount of heavy Fig. The amount of Cu2+ ions removed from solution increases rapidly from pH 4 to pH 6.37–39].6%. Alinnor / Fuel 86 (2007) 853–857 855 Fig. The increase on metal ion uptake. Hydroxyl-metal complex has higher affinity for adsorption than hydrated metal ion. the complex formed will be adsorbed on the fly ash surfaces. the amount of Cu2+ ion removed from the solution by the fly ash. Whereas. At pH 4. This is shown by decrease in adsorption by lead ions at lower pH values between 4 and 6.2.2 mg/g or 91. 3. although this did not occur in a steady progression. The uptake of Pb2+ ions decreases from pH 4 to pH 6. Similar results have been reported by other workers working on the adsorption of heavy metal ions on fly ash [25.6 mg/g or 98. Similar results have been reported by some workers working on the adsorption of heavy metal ions on fly ash [40–42]. The dependence of heavy metal ion adsorption on pH was different for the two metal ions studied. Above pH 6.3. respectively. Cu2+ and Pb2+ ions may be removed from solution by precipitation and can be adsorbed on the surface of fly ash.2 mg/g or 81. at higher pH values higher degree of precipitation of metal ions occur. Effect of pH on adsorption of different metal ions on fly ash. 15. 20. 3. since it determines the surface charge of the adsorbent. .9% and 16. 19. while at pH 6. because hydration of fly ash increases its pH between 10 and 13. The increase in metal ions uptake by fly 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. 2. Fig.3 mg/g or 77. may be explained in terms of electrostatic interaction.J.1% at a pH 12.I. At lower pH values between 4 and 6. In general. At pH 4 and 6 the amount of Pb2+ ions removed from solution by the fly ash were 17. respectively. the amount of heavy metal ions removed from solution increased as the pH increased. At higher pH.00 mg/g.4% of copper ion was removed.77 · 10À2 sÀ1 and 2. steadily increased. thereby facilitating the uptake of Pb2+ and Cu2+ ions by the fly ash. At low pH the surfaces of the fly ash were positive and there was a formation of complex [Pb(OH)4]2À and [Cu(OH)4]2À. Fig. 3. ln C0/Ct versus t should yield a straight line from the slope of which the rate constant k was calculated to be 1. the surfaces of the adsorbent were negative and there was an increase on the uptake of Pb2+ and Cu2+ ions by the fly ash. First-order kinetic plot for metal ions adsorption on fly ash. 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.8% of copper ion was removed.7 mg/g or 74. Effect of temperature The removal of heavy metal ions from solution is temperature dependent. Metal ion adsorption on the oxide surfaces is related to the hydrolysis reaction it will undergo in solution [18]. 3 shows the amount of heavy metal ions removed from aqueous solution as a function of pH at a heavy metal concentration of 21. 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. The divalent metal cations in aqueous solution hydrolyze according to the expression: M2þ (aq) + nH2 O = M(OH)2n + nHþ 2+ 2+ 2+ ð 2Þ where M = Pb or Cu .11 · 10À2 sÀ1 for Pb2+ and Cu2+ ions.

This investigation revealed that increase in temperature decreases uptake of metal ions by the fly ash. Egereonu UU. At 30 °C the amount of Pb2+ ion adsorbed was 20. Jain KK. Environ Health Perspect 1978.2:401.247:137. Brendel GF. Water Res 1990.9:333. Meeren P. In: 11th international symposium on use and management of coal combustion by-products.0%. J Plant Nutr 1981. There was a sharp increase on the uptake of Pb2+ ions by fly ash from 30 °C to 40 °C. Hugul M. These results indicate that the uptake of metal ions increases at lower temperature. until. Paspaliaris I.856 I. 4.2:4. Vishwa S.39:129. Gupta GS. Apak R.32:430. Ser B 1983. Nigeria. Network Newsl 1985.J. A: Physicochem Eng Aspects 2004. USA. Acknowledgements The author is grateful to Opara Jane for technical assistance in performing some measurements. Fuel 1998.24:45. Sancho J. Effect of temperature on adsorption of different metal ions on fly ash. Page AL. J Hazard Mater 2002. Environ Pollut.49:213. Biocycle 1995.0 mg/g or 84. Conclusion This study revealed the application of coal fly ash as an adsorbent for removal of heavy metal ions from waste . Water Res 1998. Therefore. Elseewi AA. Guu P. Willmer PG. Weng CH. Bartzas G.9:176. Straughan IR. Sivanesan S. Grimm SR. PA. Singh VN. Nwoko CIA. at 60 °C the uptake of metal ion had decreased to 79. 1995. The author is also grateful to University of Uyo. Alinnor / Fuel 86 (2007) 853–857 water. Biosour Technol 1994. metal ions removed from aqueous solution as a function of temperature at a heavy metal concentration of 26. Int Nematol. Singh RP. Tutem E. increase in temperature may be associated with decrease in the stability of metal ion-adsorbent complex. Ramamurthi V. Garcia P. Eiceman GA. Fig.33:55. Haq S. Page AL.19:397.36:88. Copper ion uptake by the fly ash followed a similar pattern of behaviour with a sharp increase between 30 °C and 40 °C followed by a sharp decrease. Pittsburgh. J Environ Eng 1994. thus making the attractive force between metal ions and fly ash insufficient to retain the metal ions at the binding site. 177. Saxena SK. 1990. Wang S. Environ Sci Technol 1996. This could lead to desorption or cause the metal ions to bounce off the surface of the fly ash instead of colliding and combining with it. Roels M. Similar findings have been reported by other workers working on removal of heavy metal ions from aqueous solution by fly ash [43].8%.24:70.55 mg/g or 70. Bianco F. Kumar P. Water Res 1985. Straughan IR. Water Res 2005.29(4):1109. J Environ Sci Health. Global Nest: Int J 2004. Colloids Surf. Vandiver VJ. Viraraghavan T. J Chem Technol Biotechnol 1979.3:409. Burba P. Beyond 40 °C there was a progressive decrease on the uptake of Pb2+ ions by the fly ash.29: 36. Rovatti P. Rao GAK. Singh VN. while equilibrium was attained within 2 h for both lead and copper ions. Huang CP. Hsin HC. Panday KK. It can be seen that the metal ions uptake follow a similar pattern. at these pH values higher degree of precipitation of metal ions can be expected. Bayat B. Beaver T. Kumari K. Pratt PL. p. whereas at 40 °C 22. Sci Total Environ 1980.27:275. thereby enhancing the removal of heavy metal ions from solution by the fly ash. The kinetic study shows that lead and copper ions were adsorbed onto the fly ash very rapidly within the first 20 min. Talanta 1983. Lutgen P. Hizal J. Chemosphere 2003.19:869. USA. Jones DG. J Polym Sci 1981. Peloso MA. The hydration of fly ash increases its pH between 10 and 13.5:381.B95:251. Adriano DC.53:655. Rodriguez P.0 mg/g. Choueib A. Nollet H.6% of Pb2+ ion was adsorbed by the fly ash. J Chem Soc Niger 1999. but the amount adsorbed at a particular temperature differ. Silva S. Bayat B.77:1147. Carini F.1:137.B95:275. 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. Huang CP. Verstraete W.15:275. A 1991. Orlando FL. Dara SS. J Hazard Mater 2002. Ferraiolo G. Ndiokwere CL. Prasad G. Eligwe CA. Saxena SK. Prasad G. Atmos Environ 1983.6(1):81. Elseewi AA. Singh RP. for making use of their facilities in the Central Research Laboratory. 4. the amount of Cu2+ ion uptake by the fly ash at 60 °C being down to 78.284:14. Straughan IR. Vincini M. Komnitsas K. Material Research Society. References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] Warren LJ. Weng CH. Resour Conserv Recycl 1988. Zhu ZH.120:1470. Boyjoo Y.0%.26(5):721. Ser B 1981. A Rev Environ Pollut.6:263. J Environ Qual 1980. Ayala J. Kumar KV. Lin CF. J Colloid Interface Sci 2005. Colloids Surf 1988.

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