Separation and Purication Technology 40 (2004) 8796

Adsorption kinetics and column operations for the removal and recovery of malachite green from wastewater using bottom ash
V.K. Gupta a, , Alok Mittal b , Lisha Krishnan b , Vibha Gajbe b
b a Department of Chemistry, Indian Institute of Technology, Roorkee, Roorkee 247667, India Department of Applied Chemistry, Maulana Azad National Institute of Technology, Bhopal 462007, India

Received in revised form 26 January 2004; accepted 26 January 2004

Abstract The thermal power plant waste material, bottom ash was utilized as a potential adsorbent for the toxic textile dye malachite green. Preliminary information was gathered by batch adsorption studies, which include effect of pH, adsorbent dose, contact time, adsorbate concentration and temperature. Plausible mechanism of the on-going adsorption process and thermodynamic parameters involved were obtained by carrying out kinetic measurements. The data obtained was successfully used to equate Langmuir and Freundlich adsorption isotherm models. A xed-bed column was designed and necessary parameters were calculated by applying mass transfer kinetic approach. Attempts were also made to recover dye and regenerate the column. 2004 Elsevier B.V. All rights reserved.
Keywords: Malachite green; Bottom ash; Adsorption; Waste material; Kinetics

1. Introduction The wastewater disposed by textile industries is causing major hazards to the environment and drinking water due to presence of a large number of contaminants like acids, bases, toxic organic, inorganic, dissolved solids and colour. Out of all such contaminants, the colour seems to be the most undesired one, as human eyes can most easily recognize it. It is now a well-established fact that the coloration of water is mainly caused by dyes, which are generally toxic, non-degradable and stable. The stability of dyes towards light and oxidizing agents also create a problem for their removal by different waste treatment procedures. Hence, their removal methods are selected with a great deal of care and thoughtfulness [1]. Formerly, conventional methods adopted by textile industries for removal of coloration from their disposed waste includes, froth otation, occulation etc. However, all such methods were found inefcacious and incompetent. During the last 10 years, the attention has been shifted towards adsorption technique, which has emerged as one of the widely
Corresponding author. Tel.: +91-1332-285801; fax: +91-1332-273560. E-mail address: vinodfcy@iitr.ernet.in (V.K. Gupta). 1383-5866/$ see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.seppur.2004.01.008

accepted methods for the removal of all such contaminants. The literature survey reveals that a large number of waste products have been utilized as adsorbent, these include peat [2,3], coal [4], bagasse y ash [5,6], activated carbon [79], iron slag [9], shale oil ash [10], zeolites [11,12], magnesium chloride [13,14], maize cob [15], wool [16], silica gel [17] etc. The present paper is an attempt to explore a possibility to utilize a waste material adsorbent, bottom ash to remove a well-known dye malachite green. Malachite green (MG) is a tri-phenyl methane dye, which is most widely used for coloring purpose, amongst all other dyes of its category. It is generally used for the dying wool, silk and leather and also used in distilleries. Though its role as an antiseptic has been well-established [14,18] but only for external applications on the wounds and ulcers, however, its oral consumption is toxic, hazardous and carcinogenic [19] due to presence of nitrogen. The bottom ash is a waste material obtained by thermal power generation plants after combusting solid fuels. It is an undesired collected material, which is transported and dumped near the surrounding land. Its disposal has always been a matter of concern to the station authorities, as the dumped ash is considered highly unsuitable for the agricultural utilization. Though it has been used as a potential adsorbent for the removal of metals [2022] in

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Nomenclature b B BSS C Cb C0 Cx d D0 Di D Ea f F Fm G H H k Kad b, b1 , b2 KF qe qt Q0 r0 R S# S M Langmuir constant time constant British standard size mass concentration of the solute in the efuent (M) concentration of efuent at the break point (M) initial concentration of the adsorbate (M) concentration of efuent during exhaustion (M) average distance between the two successive sites of adsorbent pre-exponential factor effective diffusion coefcient length of column energy of activation fractional capacity fractional attainment mass rate of ow to the adsorber Gibbs free energy (kJ mol1 ) entropy change of the process (kJ mol1 ) Plancks constant Boltzmann constant rate constant Langmuir constants at 30, 40 and 50 C, respectively Freundlich constant amount of adsorbate adsorbed at equilibrium (mg g1 ) amount of adsorbate adsorbed at any time t (mg g1 ) Langmuir adsorption capacity radius of the adsorbent particle (assumed to be spherical) gas constant entropy of activation (J K1 mol1 ) entropy of adsorption (J K1 mol1 ) amount of adsorbate adsorbed in primary adsorption zone from break point to exhaustion Freundlich constant (dimensionless) total time involved for the establishment of primary adsorption zone time for primary adsorption zone to move down its length time for initial formation of primary adsorption zone half-life period eluted volume (ml) volume of efuent at break point (ml) volume of efuent during exhaustion (ml) length of primary adsorption zone

previous years, however, its capability to adsorb organic substances [23] is not much exploited so far. Keeping these in view it was considered worthwhile to use bottom ash as an adsorbent for the removal of malachite green. The paper presents adsorption dynamics and equilibrium uptake of MG over bottom ash. In order to develop an industrial application of the under taken research, column operations were also carried out.

2. Experimental Malachite green was used in the form of its oxalate compound (molecular formula C52 H54 N4 O12 ) and obtained from M/s Merck. Its stock solution (1 mM) was prepared in doubly distilled water. All other reagents used were of A.R. grade.

H3C

CH3 +N OOCCOOH

C CH3 N CH3

.(COOH)

2 Malachite Green Oxalate

n tx t tf t1/2 V Vb Vx

The chemical analysis of the bottom ash was achieved by conventional methods as reported by Vogel [24]. X-ray measurements were carried out using Philips X-ray diffractophotometer employing Ni ltered Cu-K-radiations. Quantasorb Model QS-7 surface area analyzer was used to calculate surface area of the bottom ash particles. Mercury Porosimeter and specic gravity bottles determined the porosity and density of the material, respectively. Philips SEM 501 electron microscope was used for the scanning electron microscopic analysis. The pH of each solution was measured by using microprocessor based pH meter; model number HI 8424 (M/s Henna Instruments, Italy). The absorbance measurements were carried out on UV-Vis spectrophotometer model number 117 (M/s Systronics, Ahmedabad, India) over the wavelength range 200500 nm. The bottom ash was procured from thermal power station (TPS) of M/s Bharat Heavy Electrical Limited (BHEL), Bhopal (India) in the form of grayish black dust spherical granules. The coal used by TPS, BHEL, Bhopal was obtained from M/s South Eastern Coal Field Limited, Chirmiri, Sarguja (India). 2.1. Preparation of activated bottom ash The bottom ash obtained from the TPS was washed with doubly distilled water and dried. The dried material was

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treated with hydrogen peroxide to oxidize the adhering organic material. The product was then subjected to the temperature about 100 C for the removal of moisture contents and further kept in furnace at 500 C for 15 min in presence of air. The adsorbent thus obtained was sieved to desired particle size such as 170100 (0.080.15 mm), 10035 (0.150.30 mm) etc. and were stored in a vacuum desiccator until required. 2.2. Adsorption studies Adsorption studies were performed by the batch technique at 30, 40 and 50 C, temperatures. For each isotherm study, a series of 100 ml ask were used and each ask was lled with 25 ml of dye solution of varying concentration (1.0 105 to 1.0 104 M). The selected concentrations were decided after a good deal of preliminary investigations. A known amount of adsorbent was then added into each ask and agitated intermittently. About 12 h reaction period was found quite sufcient to establish the equilibrium. After this period, the supernatant liquid was ltered off using Whatman lter paper (number 42) and the uptake of the dye was monitored spectrophotometrically at 426 nm. 2.3. Kinetic studies Kinetic investigations were carried out by batch technique, because of its simplicity. Twenty-ve milliliter solution of MG of known concentration and 0.1 g of adsorbent was taken in airtight 100 ml conical asks. Keeping the asks in a water bath, maintained at desired temperature, mixture was mechanically agitated. After a denite interval of time, the solution of the asks was ltered and ltrate was analyzed for the uptake of dye. 2.4. Column studies The activated bottom ash (mesh size 170100) was lled in the form of slurry over a glass wool support, in the glass column of total length 30 cm and i.d. 1 cm and length of the column bed was kept 1.5 cm. The slurry was made by a weighed quantity of the adsorbent and kept overnight before preparing the column. To avoid air entrapment [25] the water was rst lled in the column and then slurry was carefully fed, which slowly settled down by displacing the heel of water. The column was then loaded with the dye solution of appropriate amount, which was allowed to percolate downwards under the gravity at a ow rate of 0.5 ml min1 . The column operations were stopped after about 90% exhaustion. 2.5. Dye recovery and column regeneration In the wastewater treatment retrieving adsorbed material and reusing exhausted column play important role. Keeping this in view, experiments were carried out by eluting

proper solvent through the used column. As malachite green exhibits exceptionally good solubility in acetone, hence, 5 aliquots of acetone, 10 ml each, were passed through the column at a ow rate 0.5 ml min1 . After complete recovery of the dye, column was washed with hot water.

3. Results and discussion 3.1. Characterization of adsorbent material Physical and chemical analysis of the bottom ash were carried out by using conventional chemical methods and available analytical techniques. Major chemical constituents of the bottom ash and its important physical parameters are presented in Table 1. DTA curves plotted for the activated bottom ash exhibit its thermal stability and negligible weight loss was accounted, even at high temperatures. d-Spacing values provided by X-ray spectrum of the adsorbent reect the presence of mainly alumina (Al2 O3 ), gypsum (CaSO4 2H2 O), beaverite [Pb(Cu, Fe, Al)3 (SO4 )2 (OH)6 ], borax (Na2 B4 O7 10H2 O) and kaolinite [2{Al2 Si2 O5 (OH)4 }]. Scanning electron microscopic photographs (Fig. 1) of the activated bottom ash clearly reveals its surface texture and porosity. Based on these photomicrographs, particles of the bottom ash can approximated as spheres. 3.2. Adsorption studies The adsorption behavior of the dye over a wide pH range (pH 211) and its prole is presented in the Fig. 2. It can be observed from the plot that the maximum uptake of MG takes place at a pH of 5.0 and beyond that pH it attains the same maximum value. In fact the amount of MG adsorbed per gram of bottom ash rises from 0.253 mg (45.8%) at pH 2.1 to 0.71 mg (100%) at pH 5.06. The behavior clearly indicates the protonation of MG (pKa = 10.3) in acidic medium and with the rise in pH the dye becomes more and more de-protonated. In lower pH range, the low adsorption of dye also exhibits possibility of development of positive charge at bottom ash particles, which inhibits the adsorption of dye over it. However, in the basic medium the formation of electric double layer changes its polarity and consequently the dye uptake increases.
Table 1 Results of chemical and physical analysis of bottom ash Chemical analysis Constituent SiO2 Al2 O3 CaO FeO PbO wt.% 37.43 32.35 12.36 4.78 0.34 Physical analysis Parameter Surface area Porosity Density Loss on ignition Value 870.5 cm2 g1 46% 0.6301 g ml1 1.14%

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Fig. 2. Effect of pH on percentage amount of malachite green adsorbed on bottom ash. Amount of bottom ash added = 0.1 g; sieve size of bottom ash = 0.080.15 mm; initial concentration of MG = 3 105 M.

at higher concentrations it systematically increases. The increase in adsorption with increasing temperature suggests an endothermic nature of the on-going adsorption process. The adsorption data of MG have been correlated with the Freundlich and Langmuir models. The linear form of Langmuirs isotherm is given by the following equation: 1 1 1 = + qe Q0 bQ0 Ce (1)

where, qe is the amount of MG adsorbed (mg g1 ), Ce is the equilibrium concentration of the MG (M) and Q0 and b are the Langmuir constants related to maximum adsorption capacity and energy of adsorption, respectively. When 1/qe was plotted against 1/Ce , straight lines with slope 1/bCe were obtained (Fig. 4), indicating that the adsorption of MG on bottom ash follows the Langmuir isotherm. The Langmuir constants b and Q0 were calculated from these isotherms and their values at three temperatures are given in Table 2. To conrm the favourability of the adsorption process the separation factor (r) was calculated by the following equation, described by Hall et al. [26]. r= 1 1 + bC0 (2)

The values of r obtained were found between 0 and 1 and conrms that the on-going adsorption process is favourable.

Fig. 1. Scanning electron microscopic photographs of the activated bottom ash particles at different magnications: (a) 1 320; (b) 1 160; and (c) 1 80.

The adsorption of MG was also monitored in its concentration range from 1.0 105 M to 1.0 104 M, at a xed pH of 5.0 and different temperatures (30, 40 and 50 C). The results are given in Fig. 3, which clearly shows that at each temperature, the adsorption increases with increase in concentration and then becomes almost constant in the higher concentration range. However, with rise in temperature adsorption remains almost constant at lower concentrations but

Fig. 3. Adsorption isotherm of malachite green on bottom ash at different temperatures. Amount of bottom ash added = 0.1 g; sieve size of bottom ash = 0.080.15 mm; pH = 5.

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Table 3 Calculated values of thermodynamic parameters for the malachite greenbottom ash adsorption process G (kJ mol1 ) 30 C 6.813 40 C 6.556 50 C 6.074 24.103 97.712 H (kJ mol1 ) S (J K1 mol1 )

Fig. 4. Langmuir adsorption isotherm of MGbottom ash adsorption at different temperatures. Table 2 Calculated values of b and Q0 from Langmuir adsorption isotherm and values of KF and n from Freundlich adsorption isotherm at different temperatures Temperature ( C) 30 40 50 b (l mol1 ) 14.95 12.42 9.60 Q0 (g1 ) 1.618 103 1.398 103 1.386 103 KF (g) 3.168 104 4.022 104 4.750 104 n 0.1256 0.1515 0.1594

is pertinent to mention that Freundlich model ts slightly better then the Langmuir model in the present studies. The thermodynamic parameters change in Gibbs free energy ( G ), change in enthalpy ( H ) and change in entropy ( S ) obtained for the process under investigation were calculated using Eqs. (4)(6). The results obtained are presented in Table 3. G = RT ln b H = R S = T2 T1 T2 T 1 G ln b2 b1 (4) (5) (6)

H T

The same method has already been adopted [27] to conrm the favourability of a Langmuir type of adsorption. The well-known logarithmic form of Freundlich model is given by the following equation: log qe = log KF + (1/n) log Ce (3) where, qe is the amount adsorbed (mg g1 ), Ce is the equilibrium concentration of the adsorbate (M) and KF and n are the Freundlich constants related to adsorption capacity and adsorption intensity, respectively. The plot of log qe versus log Ce gives straight lines with slope 1/n (Fig. 5), which shows that the adsorption of MG also follows the Freundlich isotherm. Accordingly, Freundlich constants (KF and n) were calculated and the values of these at different temperatures are also recorded in Table 2. The table shows an increase in adsorption capacity (KF ) with increase in temperature. It

where, b, b1 and b2 are Langmuir constants at 30, 40 and 50 C. The negative value of free energy at each temperature (Table 3) indicates the feasibility as well as the spontaneous nature of the adsorption process. It can also be noted that the change in free energy decreases with increase in temperature, which exhibits an increase in adsorption with the rise in temperature. The endothermic nature of the process is once again supported by the positive value of enthalpy change ( H ), while positive value of S reects the afnity of the adsorbent material towards MG. 3.3. Kinetic studies In order to design a fast and effective model, investigations are deliberately made with the kinetic viewpoint. The kinetic studies involve effect of some major parameters, like contact time, amount and particle size of adsorbent and

Fig. 5. Freundlich adsorption isotherm of MGbottom ash adsorption at different temperatures.

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V.K. Gupta et al. / Separation and Purication Technology 40 (2004) 8796 Table 4 Effect of particle size of bottom ash on rate of uptake of malachite green Sieve size (mm) Amount adsorbed (g) Percentage removal (%) Amount adsorbed over per gram of adsorbent (g) 6.2 103 5.5 103 4.3 103 t1/2 (h1 )

0.08 0.080.15 0.150.3

6.2 104 5.5 104 4.3 104

89.8 79.7 62.3

0.22 0.30 0.42

Fig. 6. Dependence of uptake of malachite green with time at different temperatures. Amount of bottom ash added = 0.1 g; sieve size of bottom ash = 0.080.15 mm; initial concentration of MG = 3 105 M; pH = 5.

concentration of the adsorbate solution on the uptake of MG on the siliceous waste material. Preliminary investigations suggest that the rate of uptake of MG was rapid during the initial phase of the adsorption and within half an hour almost 5060% of the MG was adsorbed over the bottom ash at each temperature (Fig. 6). Fig. 6 also indicates that within next 45 min the equilibrium is attained and saturation takes place. In order to obtain optimum amount of adsorbent, the effect of the adsorbent dose on removal of MG was studied by varying its doses from 0.025 to 0.3 g at a xed pH, temperature and concentration of MG. It has been observed that the adsorption decreases from 0.76 mg g1 at 0.025 g dose to 0.158 mg g1 at 0.2 g dose and then becomes almost constant (Fig. 7). The half-life (t1/2 ) of the process was also calculated at different doses of the bottom ash and it was found that the half-life decreases with its increasing amount, conrming there by dependence of rate of adsorption on the amount of adsorbent. The batch adsorption experiments were also carried out using three different particle sizes at a xed pH, adsorbent dose, contact time and temperature. The selected particle sizes were 250170 BSS mesh, 170100 BSS mesh and 10035 BSS mesh and it was observed that adsorption capacity decreases with the increase in particle size (Table 4). The study also indicates that with the decrease in particle size the rate of adsorption increases, whereas the adsorption

of half the amount of MG (t1/2 ) decreases. Thus during the studies powdered bottom ash was preferred over granulated one. The measurement of kinetics of the process at different temperatures (30, 40 and 50 C) exhibits an increase in the rate of adsorption with the increase in temperature (Fig. 6). The result once again conrms endothermic nature of the on-going process. However, the half-life of the process found to decrease with increase in temperature. Considering the adsorption behavior of MG from liquid to solid phase as reversible reaction with equilibrium established in two phases, the specic rate constant for the process was calculated using following Lagergren rst order rate expression [28], which has been applied to determine specic rate constant of adsorption of MGbottom ash. log(qe qt ) = log qe Kad t 2.303 (7)

where, qe and qt are amount of MG adsorbed over per gram amount of bottom ash at equilibrium and at any time t and Kad is the specic rate constant for the reversible process. The plot of log (qe qt ) versus time (t) gives a straight line (Fig. 8) and conrms the applicability of the rst order rate expression of Lagergren in this case. The Kad values as calculated from the slope of this plot (Kad /2.303) were found as 2.303 102 , 2.372102 and 3.477 102 min1 at 30, 40 and 50 C, respectively. In order to identify the step governing the overall removal rate of the adsorption process, the model given by Boyd et al. [29] and Reichenberg [30] was applied. These models also helped in determining the mechanism of the undergoing process. It is now well-established that during the adsorption of

Fig. 7. Effect of amount of adsorbent on malachite green uptake at 30 C. Sieve size of bottom ash = 0.080.15 mm; initial concentration of MG = 3 105 M; pH = 5.

Fig. 8. Time vs. log (qe qt ) plot for the adsorption of malachite green on bottom ash at different temperatures.

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a solid chemical substance over a porous adsorbent following three consecutive steps take place. a. Transport of the adsorbate ions to the external surface of the adsorbent (lm diffusion). b. Transport of the adsorbate particles within the pores of adsorbent, excluding the small amount of adsorption occurring at the external surface of the adsorbent (particle diffusion). c. Adsorption of the adsorbate ions on the interior surface of the adsorbent. Out of the above three steps the step c is very fast and thus can not be considered as a rate determining step [31]. However, for the remaining two steps following three possibilities exists during the adsorption process: Case I Case II Case III External transport < internal transport External transport > internal transport External transport internal transport

B=

2 Di = time constant (r0 )2

(10)

It is now clear that Case I take place for the particle diffusion, while Case II is governed by lm diffusion process. However, in the Case III, the transport of the adsorbate ions to the boundary may not be possible with a signicant rate because of which there is a possibility of formation of a liquid lm around the solid adsorbent particles. The quantitative treatment of the sorption dynamics is in accordance with the observations of Reichenberg [30], as given by the following equation. F =1 6
2

(1/n)2 exp(n2 Bt)

1

(8)

where, F is the fractional attainment of equilibrium at time t and is obtained by the use of Eq. (9) and n is Freundlich constant of the adsorbate. Qt F= (9) Q where, Qt and Q are amounts adsorbed after time t and after innite time respectively.

where, Di is the effective diffusion coefcient of adsorbate in the adsorbent phase and r0 is the radius of adsorbent particles assumed to be spherical. The kinetics of the process was observed at different concentrations of MG and the values of F are calculated using Eq. (9). The corresponding values of Bt have been obtained from Reichenbergs table [30] and the linearity test was carried out for the Bt versus time plot at each concentration (Fig. 9). The Fig. 9 clearly indicates that at low concentrations (<5 105 M) the linearity deviates, while at higher concentrations (5 105 M) the linearity is maintained and straight lines obtained pass through origin. This phenomenon suggests involvement of lm diffusion and particle diffusion mechanisms as the rate-controlling step at lower and higher concentrations respectively. The further verication of the above observations was carried out by Mckays graph. The typical Mckays plots of log(1 F) versus time are drawn at different concentration of MG and presented in Fig. 10. Here straight lines are obtained in the lower concentration range, while graphs at higher concentrations are curved. The observations further supports the fact that rate of adsorption of MG at bottom ash takes place by external transport at low concentration and at higher concentrations the internal transport of adsorbate particles is more prominent [32]. At temperatures 30, 40 and 50 C, the values of effective diffusion coefcient of MG in the adsorbent phase (Di ) were also calculated. The 1/T versus log Di plot was found linear with negative slope (Fig. 11) indicating thereby the increase in the mobility of ions and a decrease in the retarding forces acting on the diffusing ions with the temperature. The energy of activation (Ea ), entropy of activation ( S# ) and pre-exponential constant (D0 ) analogous to the Arrhenius frequency factor are evaluated using Eqs. (11) and (12) and presented in Table 5. Di = D0 exp Ea RT (11)

Fig. 9. Time vs. Bt plot at different concentrations of malachite green.

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Fig. 10. Time vs. log(1 F ) plot at different concentrations of malachite green.

Fig. 11. Reciprocal of Kelvin temperature (1/T) vs. log Di plot.

D0 = (2.72 d 2 kT/h)exp

S# R

(12)

where, d is the average distance between the successive exchange sites. The negative value of S# obtained for the adsorption is in accordance to the value reported elsewhere [3335]. 3.4. Column studies Though different workers [36,37] have suggested various types of columns but if the rate to establish equilibrium of adsorbate concentration between aqueous and adsorbed phase is known, then it is always advisable to follow a straightforward approach by using xed-bed adsorber. In the present studies, parameters like length of primary adsorption zone (), time involved in establishing the primary adsorption zone (tx ), time required by primary adsorption

zone to move down its length (t ), time of initial formation of primary adsorption zone (tf ), fractional capacity of the prepared column (f), mass rate of ow to the adsorbent (Fm ) and percent saturation of column at break point were calculated by using following equations [38]. tx = t = Vx Fm Vx V b Fm (13) (14) (15) (16) (17)

t t (Vx Vb ) = = = D tx tf tx + t Vb + f(Vx Vb ) f =1 tf Ms = t (Vx Vb )C0 D + (f 1) 100 D

Percentage saturation =

Table 5 Effective diffusion coefcient (D), pre-exponential constant (D0 ), activation energy (Ea ) and entropy of activation ( S# ) values for the diffusion of malachite green in activated bottom ash Di (m2 s1 ) 30 C 3.42 1013 40 C 1.25 1011 50 C 7.76 1010 8.57 1042 3.219 102 104.6 D0 (m2 s1 ) Ea (kJ mol1 ) S# (J K1 mol1 )

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Fig. 12. Breakthrough curve (collected volume vs. concentration) of malachite green on bottom ash. Initial concentration of adsorbate = 1 104 M.

Fig. 13. Desorption of malachite green by acetone.

where, Ms is the amount of adsorbate adsorbed in the primary adsorption zone from break point to exhaustion, C0 the initial concentration of adsorbate and D the length of column. Fig. 12 represents a typical breakthrough curve between concentration (C) and eluted volume (V) obtained during column operation of MG and bottom ash system. The breakthrough curve was used to nd out the values of Vb , Vx , Cb and Cx , which were then applied to calculate values of tx , tf , t , f, and percentage saturation at break point as given in Table 6. The breakthrough curve between concentration ratio (C/C0 ) and eluted volume (V) was also plotted and used for the calculation of column capacity at its complete exhaustion. The column capacity by dividing the total area under the points, where the efuent plot joins the efuent by weight of the adsorbent in the column. The column capacity is compared with the batch capacity, observed during

Table 7 Parameters for xed-bed adsorber tx (min) 1024 t (min) 426.6 tf (min) 56.6 f 0.867 (cm) 0.6615 Percentage saturation 94.13

adsorption isotherms and found greater (Table 7). This may be due to the continuous formation of a large concentration gradient at the interface zone during column operation, however, in case of batch adsorption isotherm studies such a concentration zone decreases with time. 3.5. Dye recovery and column regeneration The recovery of MG was achieved by eluting acetone through the exhausted xed-bed. Fig. 13 narrates the trend of collected volume of the eluent versus concentration of

Table 6 Fixed-bed adsorber calculations C0 (mg ml1 ) 0.093 Cx (mg ml1 ) 0.084 Cb (mg ml1 ) 0.015 Vx (ml) 60.0 Vb (ml) 35.0 Vx Vb (ml) 25.0 Fm (mg cm2 ) 0.058 D (cm) 1.5

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recovered amount of dye. It is evident from the graph that maximum attrition (about 60%) of the column took place with rst 10 ml of acetone and rest of the MG was desorbed by eluting four increments of 10 ml each. Total percentage recovery of the dye was almost 96%. The column is now washed with 70 ml of hot water in 10 ml fractions at the ow rate of 0.5 ml min1 . To check the adsorption efciency of the bottom ash, column was reloaded with the dye solution of known concentrations and breakthrough capacities for MG-BA system were found as 82, 68, 51, 42 and 38% mg g1 during rst, second, third, fourth and fth cycles, respectively. A well expected fall in the sorption capacity of the system indicates the need of regeneration treatment after each cycle. However, the calculated data may prove helpful in designing a bottom ash xed-bed for the treatment of MG of known concentration. 4. Conclusion A waste material bottom ash, obtained from the thermal power plant has been fruitfully employed for the removal of hazardous dye like MG. At lower concentrations almost bottom ash adsorbs almost 100% of the dye. However, at higher concentrations the adsorption takes place via particle diffusion process and the thermodynamic parameters reveal feasibility of the process. Experiments indicate that quantitative recovery of the dye can be achieved by eluting acetone through the column and adsorbent can be regenerated. The employed adsorbent is quite economic than commercially available adsorbents.

Acknowledgements Authors are thankful to the Council of Scientic and Industrial Research (CSIR), New Delhi, India for nancial support.

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