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War. Res.Vol. 21. No. 8, pp. 885-888, 1987 Prlnled in Great Britain.

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ASIT K. SEN and ARNAB K. DE Department of Chemistry, Visva-Bharati University, Santiniketan
(Received July 1985)

731235, West Bengal,India

Abstract--Coal fly ash, an industrial solid waste, was found to have a good adsorption capacity for mercury(H). Adsorption of mercury(H) on coal fly ash conforms to Freundlichs adsorption model. Several parameters such as time of equilibration, effect of pH, effect of initial concentration of solute, effect of fly ash dose etc. were studied. The maximum adsorption was observed after shaking for 3 h. Solution pH was the most important parameter affecting the adsorption. The optimum pH range was 3.w.5. There was total adsorption of mercury below 10 mg I-. The performance of coal fly ash as an adsorbent was found to be significant when compared with activated powdered charcoal.

Key words*oal

fly ash, adsorption, mercury, flameless atomic absorption


Water pollution due to heavy metal such as mercury, is a serious global problem. The toxicological effects (Manahan, 1979) of mercury are neurological damage, including irritability, paralysis, blindness or insanity, chromosome breakage. The health hazards due to the toxic effect of mercury at Minamata, Japan (1953) and Iraq (1972) are well known (Bockris, 1977). Mercury is used in a wide variety of industries such as chloralkali, paint, fungicides etc. Therefore, a systematic study of the removal of mercury from waste water is of considerable significance from an environmental point of view. Activated carbon filtration, preceded by treatment with lime or ferric chloride or alum is a known method for the removal of heavy metals (Cohen, 1977), but the high cost of activated carbon limits its large scale use for the abatement of heavy metal pollution in developing countries. Coal fly ash, an industrial solid waste of thermal power plants, is one of the cheapest and most unconventional adsorbents. Zinc and organic acids have been removed from aqueous solutions using coal fly ash (Prabhu er al., 1981; Ahmed et al., 1983). In this paper, systematic laboratory investigations on the removal of mercury(H) from aqueous solutions using coal fly ash by a batch operation technique have been reported. No such work has previously been reported in literature for the removal of mercury(H) from water using coal fly ash.

Adsorbafe. A stock solution of mercury(I1) (2.99 mg ml-) was prepared by dissolving Hg(NO,),.H,O (BDH, Anala R) in 0.04N HNO, and standardized complexometrically with EDTA (disodium salt) using xylenol orange indicator.

Aahbenf. The adsorbent. coal fly ash was collected from thermal power plants of Durgapur Projects Ltd, West Bengal. It was sieved to IO&200 mesh size, washed with dilute HNO, (0.05 N) to remove soluble metal oxides (CaO, MgO, etc.), filtered, and washed again with doubly deionized water until it was free from acid. Then it was dried at 100C and finally kept in closed polythene bottles. Activated powdered carbon (E. Merck, India) was washed with doubly deionized water, filtered, dried and finally kept in closed polythene bottles. The composition of fly ash, as determined by Sfandnrd Methods (Welcher, 1963)is given below: SiO, 63.87%, Al,O, 14.39%. Fe,O, - , 4.62%. CaO 3.70%. Me0 - 0.22%. other oxides 2.3 I %, loss on ignition I 1.S%, moisture 0.1%. It was free from mercury. The actual composition of the fly ash depends on the variety of coal used, the degree of burning and the method of collection. Physically, By ash is characterized by its fineness, large surface area per unit weight, and wide particle size distribution. Reagenu. All the chemicals used were of analytical grade (BDH or E. Merck). Appararus. A flameless atomic absorption mercury analyzer, Model MA 5800B, Electronics Corp. of India Ltd. was used for determination of mercury concentrations. A pH meter, Model LI IOT, Elico Private Ltd (India) was used for pH measurements and a single pan analytical balance, Nagema, Model AV/VS/3-3 (GDR) was used for weighing. Procedure. Batch operations were conducted in which aliquots of mercury(I1) solutions of known concentrations were introduced into stoppered glass bottles (125 ml) containing accurately weighed amounts of the adsorbent. The weight ranged from I .O to I. I g per 50 ml for both fly ash and activated charcoal. Doubly deionized water was added to make the volume 50ml. The bottles were shaken at room temperature (30 f 1C) using an electric shaker for a prescribed length of time to attain equilibrium. The adsorbent was then removed by filtration. The equilibrium concentration of mercury(I1) was estimated by flameless atomic absorption mercury analyzer after proper dilution. Blank solutions were similarly treated (without adsorbent) and the recorded concentration by the end of each operation was taken as the initial one. The equilibrium pH was noted in each case using a pH meter. Adsorpfion model. To quantify the adsorption capacity of



SEN and


fly ash for the removal of mercury(I1) from water, the Freundlich adsorption equation was applied (Glasstone, 1981), in the form logLogk+~ logC, In where x is the amount of solute (mercury) adsorbed, m is the amount of adsorbent required to adsorb X, k and l/n are empirical constants (Freundlich parameters), and C, is the equilibrium concentration. The values of k and l/n are equal to the intercept and slope of the line obtained by plotting log x/m vs log C,. The parameters are indicative of the capacity and intensity of adsorption respectively.

40 30 1 2 4

1 PH

I 6

I 6

Fig. 2. Effect of pH on adsorption of Hg(ll). Initial concn of Hg(l1) = 11.71 mg/lOO ml. Symbols as in Fig. 1. Though the time of equilibration in the case of fly ash is higher in comparison to activated charcoal, it is not insignificant when coal fly ash is considered for the removal of mercury(I1) from waste water. Effect of pH. The effect of pH on the adsorption process is presented in Fig. 2. The percentage adsorption of mercury(II), C, - C/C, x 100, [C, = initial concentration of mercury(II), C, = equilibrium concentration of mercury(II)], increased with increasing pH up to a certain range and then decreased with further increase in pH. The maximum adsorption took place in the pH range 3.54.5 for fly ash and 3.5-5.5 activated charcoal. The figure shows that adsorption on fly ash is more sensitive to pH than on activated charcoal. This may be due to the difference in composition of fly ash and activated charcoal. Fly ash mainly consists of quartz, alumina, silica, coesite, amorphous carbon and a very small amount of lime (Ahmed et al., 1983). Aiurnina, silica and coesite are well known inorganic cation exchangers. The bond between the adsorbent and adsorbate is formed due to surface charge chemical adsorption. Hence pH exerts a significant effect in the adsorption of metal ions by coal fly ash. Silicates, alumina, etc. present in coal fly ash, have generally small exchange capacities in comparison to activated charcoal, yet they are not to be considered less important for the removal of mercury(I1) from slightly acidic waste water.




Time of equilibrium. The dependence of adsorption of mercury(H) on time is presented in Fig. I. The equilibrium was attained after shaking for 3 h, in the case of fly ash and 30 min in the case of activated charcoal. Therefore, in each experiment, the shaking period was 3.5 h for fly ash and 45 min, for activated charcoal. Mercury(H) exhibited a greater affinity towards activated charcoal particularly at low pH. This is probably due to the neutralization of negative charges at the surface of carbon with an increase in hydrogen ion concentration. It reduces hindrance to diffusion and makes available more of the active surface of the carbon for adsorption. The difference in the rate of adsorption on fly ash and activated charcoal is probably due to the fact that fly ash is composed of different chemical compounds, so uniform diffusion of adsorbate is not possible, whereas activated charcoal is a microcrystalline form of graphite (Cotton, 1980), where uniform diffusion may be possible. The surface area of the fly ash (225 m2 gg) is also less than that of activated charcoal used (630 m2 g-l).





50 1 0

I 40

1 60

I 120

1 160

I 200

I 240

Fig. 1. Dependence of adsorption of Hg(l1) on time. Initial concn of Hg(l1) = 11.71 mg/lOO ml, equilibrium pH = 4.3. 0, On fly ash; 0, on activated charcoal.




Hg (II)



Fig. 3. Effect of initial concentration of Hg(l1) on the adsorption. Equilibrium pH = 4. I.


of mercury(II) by coal fly ash




0.6 log







I 0.9

I 1.7

I 2.5





Fig. 4. Freundlich adsorption isotherms at different pH temperature 30 f 1C. Symbols as in Fig. 1.

Fig 5. Effect of fly ash dose on the adsorption of Hg(I1). Initial concn of Hg(II) = 17.51 mg/lOO ml, pH = 4.9.

Effect of adrorption



of solute

on the


Process. Figure 3 shows that, the percentage ad-

sorption of mercury(I1) decreased with increasing initial concentration of mercury(I1). At low concentrations (below 10mgll), there was total adsorption. This suggests that coal fly ash can remove 100% mercury(I1) from water if its concentration is below 10 ppm. Asorption isotherms. Adsorption of mercury(I1) on fly ash was found to conform to Freundlich adsorption isotherm. The Freundlich isotherms at three different pH values are presented in Fig. 4. The isotherm for activated charcoal at pH 1.8 is also shown. The Freundlich adsorption parameters, k and l/n are given in Table 1, which indicates the variation of adsorption capacity with pH in accordance with Fig. 2. The values of l/n and k increased as pH increased, indicating that adsorption increased with increasing pH in the chosen pH range.
Effect of ~?y ash dose on the adsorption process

Adsorption of mercury(I1) on coal fly ash was found to proceed in accordance with Freundlichs adsorption equation. The optimum pH range was 3.5-4.5 and optimum shaking period was 3 h. There was total adsorption of mercury(I1) at concentrations below 10 mg 1-i. The performance of coal fly ash as adsorbent was found to be significant when compared with that of activated powdered charcoal. Coal fly ash is a promising adsorbent for the removal of mercury(I1) from waste water.

From the above studies, it is evident that coal fly ash, an industrial solid waste product of thermal power plants, is a good adsorbent for mercury(I1) from aqueous solutions and it can be utilized for the removal of mercury(I1) from waste water. It will help solid waste management of the thermal power plants as well as provide a method for the removal of mercury(I1) from industrial waste water.
Acknowledgements-The financial assistance from the Council of Scientific & Industrial Research, New Delhi, to one of the authors (A.K.D.) is gratefully acknowledged. The authors are also thankful to Professor A. K. De, Head of the Department of Chemistry, Visva Bharati University, for providing necessary facilities and encouragement.

The effect of fly ash dose on the adsorption of mercury(I1) is presented in Fig. 5. The figure indicates that the adsorption increased with increasing fly ash dose upto a certain value and then there was no further increase of adsorption.

Table I. Freundlich Adsorbent Fly ash Ply ash Fly ash Activated


parameters k I.014 1.094 I.230 3.388 I n 0.053 0.333 0.361 0.572

pH of solution 2.2 3.1 4.2 I.8

Ahmad S. R., Ali I., Rathore H. S. and Kumari K. (1983) Adsorption of organic acids from aqueous solutions on fly ash and granular charcoal. IA WPC Tech. Annual 10,


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Analysis, Parr B, 6th edition. Van Nostrand-Reinhold, New York. Prabhu P. V. S. S., Narayana Swamy M. S. and Narasa Raju T. S. S. (1981) Adsorption of zinc from aqueous solutions by fly ash. IA WPC Tech. Annual 8, 46-52.