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Journal of the Chinese Institute of Chemical Engineers 39 (2008) 367373 www.elsevier.com/locate/jcice

Adsorption of chromium (III) ion from aqueous solution using rice hull ash
Li-Hua Wang, Chun-I Lin *
Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei 106, Taiwan Received 1 November 2007; accepted 4 February 2008

Abstract Rice hull was calcined to rice hull ash (RHA) at 500 8C under 20 mL air/s for 50 min. The RHA thus prepared has been found to be able to remove chromium (III) ion from aqueous solution, though not very efcient. The experiments indicated that the rate of removal of Cr3+ and the removal of Cr3+ at equilibrium was increased upon decreasing the RHA dosage. The removal could also be enhanced upon increasing the initial chromium concentration, or adsorption temperature. However, pH in the range of 2.55.4 or stroke speed higher than 120 stroke/min could not change the removal. The dependence of the RHA dosage and the initial chromium concentration on the removal have been found to be strong, while that of adsorption temperature is mild. An empirical equation correlating the relationship between the removal of Cr3+ and the adsorption time was determined. # 2008 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Adsorption; Chromium; Kinetics; Rice hull ash

1. Introduction Chromium (III) ion is one of the heavy metal ions in the galvanic rinsing water which is a threat to human health. The maximum contaminant level goals of chromium for the drinking water is 0.05 mg/L for the World Health Organization (WHO) set standard (World Health Organization, 2006). Therefore, the chromium concentration in the efuents of galvanic factory should be below this value. Adsorption is an efcient method to clean chromium (III) ions (Tarasevich and Klimova, 1999) and activated carbon is a widely employed adsorbent to remove it (Candela et al., 1995). However, because of the high cost of activated carbon, the possibilities of several wastes such as red mud (Gupta et al., 2001a) activated slag (Srivastava et al., 1997), activated carbon developed from fertilizer waste material (Srivastava et al., 1996), green algae spirogyra species (Gupta et al., 2001b), spent bleaching clay (Seng et al., 2001), bagasse y ash (Gupta et al., 1999; Gupta and Ali, 2004) as well as rice hull and its derivatives (Kim and Choi, 1998; Srinivasan et al., 1988) have been investigated to replace it. Rice hull, an agro-based waste, is normally disposed of by burning in the eld which results in environmental pollution in Taiwan. Therefore, developing new applications for rice hull is

encouraged. Rice hull ash (RHA), prepared by calcinating rice hull under air ow (20 mL/s) at 500 8C for 50 min, has been found to be an effective agent for bleaching sesame oil (Chang et al., 2001). This nding encourages us to explore the possibility of using this low cost RHA to uptake chromium (III) ion from aqueous solution. Unfortunately, reports on the performance of the rice hull or its derivatives to remove Cr3+ are scarce in the literature (Kim and Choi, 1998; Srinivasan et al., 1988). Srinivasan et al. (1988) prepared their activated carbon from rice hull by treating it with sulphuric acid and then activating it by air. This adsorbent can remove 88% of total chromium and greater than 99% hexavalent chromium. On the other hand, Kim and Choi (1998) observed that their activated carbon calcined from rice hull was not able to remove chromium from aqueous solution. This study aims to explore the feasibility of using RHA as an adsorbent to uptake chromium (III) ion from aqueous solution. Furthermore, the effects of various factors on the uptake were examined and an empirical expression relating the removal of Cr (III) and adsorption time was determined. 2. Experimental 2.1. Materials

* Corresponding author. Tel.: +886 2 2737 6614; fax: +886 2 2737 6644. E-mail address: cilin@mail.ntust.edu.tw (C.-I Lin).

Aqueous solution containing chromium (III) ion was prepared by dissolving reagent grade Cr(NO3)39H2O (Shima-

0368-1653/$ see front matter # 2008 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved. doi:10.1016/j.jcice.2008.02.004

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L.-H. Wang, C.-I Lin / Journal of the Chinese Institute of Chemical Engineers 39 (2008) 367373 Table 1 Values of operation variables for adsorption experiment Variables RHA dosage (g/L) Initial chromium concentration (mg/L) pH Stroke speed (stroke/min) Adsorption temperature (8C) Values 1 100 3.2 30 20 5 220 4.1 60 30 10 350 5.4 120 40 15 430 6.2 180 50 20 520

Nomenclature a b C C0 dp E1, E2 kd kf k1 k2 k20 m 1, m 2 n1, n 2 qe qe0 R Ss t T V w constant (mg/g s) constant (g/mg) concentration of Cr3+ in aqueous solution at time t = t (mg/L) concentration of Cr3+ in aqueous solution at time t = 0 (mg/L) RHA particle diameter (cm) activation energies (J/mol) rate constant appeared in Eq. (6) (1/s0.5) adsorption rate constant appeared in Eq. (3) (s/number of site) pseudo-rst-order rate constant (1/s) pseudo-second-order rate constant (g/mg s) constant (L/s mg2) dimensionless exponents dimensionless exponents amount of Cr3+ adsorbed per gram of RHA at equilibrium (mg/g) constant (mg/g) gas constant (8.314 J/mol K) outer surface area of RHA per unit volume of adsorbent-free slurry (1/cm) adsorption time (s) absolution temperature (K) volume of aqueous solution (L) mass of RHA used (mg)

Italic values are standard operation variables.

VP2, Quantachrome, Boynton Beach, FL, USA). The sample was heated to 170 8C and evacuated until the pressure was lower than 104 Torr. After that, liquid nitrogen (196 8C) was adsorbed on the surface of the sample and then desorbed. The relation between the change in mass of the sample and partial pressure of nitrogen during adsorption and desorption were recorded. The manufacturers software provided the total volume and the pore size distribution by the BJH theory (Barrett et al., 1951). The micropore volume and external surface area were obtained by employing the t-plot method (Greff and Sing, 1982; Lecloux, 1981) and the surface area due to micropores was obtained by the value difference between the overall and the external (Sousa-Aguilar et al., 1998). The results of the above measurements are summarized here: main component, Si; irregular granule with diameter 68.0 106 m; pH, 10.21; specic surface area, 91.8 m2/g; specic pore volume, 0.21 cm3/g; and average pore diameter, 9.22 nm. 2.2. Adsorption experiments Adsorption experiments were performed in a 250 mL highdensity polyethylene bottle immersed in a reciprocal shaking bath (B603D, Hsin An, Taipei, Taiwan). After loading 50 mL chromium (III) containing aqueous solution, the bottle was placed in the bath. When a predetermined temperature was reached and maintained for 20 min, a known amount of RHA was poured into the bottle and the adsorption started. The bottle with the sample was removed from the bath after a certain time and cooled to room temperature. The slurry was then ltered through a piece of 1 mm Advantec lter paper and the amount of chromium (III) ion in the ltrate was determined by an atomic absorption spectrometer (AAS6 Vario, Analytic jenaAG, Jena, Germany). Three runs were carried out under the same experimental conditions and the average value was employed. The experimental conditions for the adsorption are documented in Table 1. 3. Results and discussion 3.1. Efciency of removal The experimental results of removal of Cr3+, q against adsorption time, t are shown in Figs. 15, while removal of Cr3+ at equilibrium qe and percentage removal of Cr3+ at equilibrium, PRe are tabulated in Table 2. The denitions of removal of Cr3+, q and percentage removal of Cr3+, PR are

Greek symbols b mass transfer coefcient (cm/s) ep porosity of RHA particles n volume of RHA free solution (L) rp density of RHA particles (mg/L) kyus Pure Chemicals, Osaka, Japan) in deionized water and the ionic strength of it was kept at 0.1 M by reagent grade NaNO3 (Shimakyus Pure Chemicals, Osaka, Japan). The pH of the solution was regulated by 0.1 M HNO3 and 0.1 M NaOH (Kojima Chemicals, Tokyo, Japan), both of them were of reagent grade. Rice hull, obtained from Taichung county, was rst washed with distilled water three times. It was then dried at 105 8C for 24 h and calcinated at 500 8C under 20 mL air/s in a box furnace (VT-10, Kinghwang, Taipei, Taiwan) for 50 min. The composition of silicon and metals of the RHA were determined by an inductively coupled plasmamass spectrometer, ICP-MS (Sciex Elan 5000, PerkinElmer, Shelton MA, USA) and their morphologies were observed using a scanning electron microscope (S360, Cambridge, Cambridge, United Kingdom). Average particle diameter of the RHA was measured by a laser diffraction particle size analyzer (LS230, Beckman Coulter, CA, USA) and pH value was determined by a pH meter (PHB-9902, Ehun, Taipei, Taiwan). Specic surface area was obtained from nitrogen adsorption isotherms produced by a surface area analyzer (ASIMP-LP-

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Fig. 1. Plot of removal of Cr3+ against time. Effect of RHA dosage. Initial chromium concentration, 350 mg/L; pH, 4.1; stroke speed, 120 stroke/min; adsorption temperature, 30 8C.

Fig. 3. Plot of removal of Cr3+ against time. Effect of pH. RHA dosage, 20 g/L; initial chromium concentration, 350 mg/L; stroke speed, 120 stroke/min; adsorption temperature, 30 8C.

dened as Removal of Cr3 ; q  C 0 C V w C0 C 100% C0 (2) (1)

Percentage removal of Cr3 ; PR  qw 100% VC 0

where C and C0 are the concentrations of Cr3+ at t = t and t = 0, respectively (mg/L of the solution), V is the volume of aqueous solution (L), and w is the mass of RHA used (mg). It can be seen in the gures that the removal of Cr3+ increases very rapidly in the initial stage and levels off after 30 min. On the other hand, Table 2 indicates that the percentages of removal at equilibrium for experimental conditions studied are in the range of 60.0091.42%. The above reported data lead us to conclude that the rate of removal is satised but the nal removal is only fair.

Fig. 4. Plot of removal of Cr3+ against time. Effect of stroke speed. RHA dosage, 20 g/L; initial chromium concentration, 350 mg/L; pH, 4.1; adsorption temperature, 30 8C.

3.2. Kinetics of adsorption process Five series of experiments were performed to investigate the effects of RHA dosage, initial chromium concentration, pH, stroke speed and adsorption temperature on the removal of Cr3+ and the obtained data are shown in Figs. 15. The inuence of RHA dosage on the removal of Cr3+ is shown in Fig. 1. It can be seen that the lower the RHA dosage, the higher the removal of Cr3+ and the higher the removal of Cr3+ at equilibrium and the effect is found to be strong. It can be seen from Eq. (1) that low RHA dosage may increase the values of both denominator and numerator of Eq. (1) and the net result is increasing the value of q. Several authors reported similar results (Eligwe et al., 1999; Gupta et al., 1997). The effect of initial chromium concentration is shown in Fig. 2. The higher the initial chromium concentration, the faster the removal and the higher the removal at equilibrium. The

Fig. 2. Plot of removal of Cr3+ against time. Effect of initial chromium concentration. RHA dosage, 20 g/L; pH, 4.1; stroke speed, 120 stroke/min; adsorption temperature, 30 8C.

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Fig. 5. Plot of removal of Cr3+ against time. Effect of adsorption temperature. RHA dosage, 20 g/L; initial chromium concentration, 350 mg/L; pH, 4.1; stroke speed, 120 stroke/min.

inuence of this factor is also found to be signicant. A high initial chromium concentration increases the difference in concentration between the bulk liquid and the adsorption site which increases the rate of removal and the removal at equilibrium. The present nding agrees with the literature reports (Dimitrova and Mehandgiev, 1998; Lopez et al., 1995) The results of the inuence of pH on the rate of removal and removal at equilibrium are varied. Some reported that increasing
Table 2 Removals of Cr3+ at equilibrium, qe and percentage removals of Cr3+ at equilibrium, PRe, t = 180 min Adsorption conditions RHA dosage (g/L) 1 5 10 15 20 Initial copper concentration (mg/L) 100 220 350 430 520 pH 3.2 4.1 5.4 6.2 Stroke speed (stroke/min) 30 60 120 180 Adsorption temperature (8C) 20 30 40 50 qe (mg/g) 240.22 49.98 26.50 18.46 15.66 3.77 10.20 12.65 13.99 16.75 12.64 12.71 12.80 13.26 11.40 11.78 12.10 12.39 11.98 12.65 14.46 16.14 PRe (%) 60.00 60.77 64.08 67.03 75.76 79.49 91.73 71.64 63.87 64.39 71.61 71.89 72.41 75.00 64.48 66.68 68.53 70.18 67.84 71.64 81.81 91.42

pH may increase the removal (Ajmal et al., 2003; Vadivelan and Kumar, 2005), whereas Sharma and Forster (1993) and Hamadi et al. (2001) reported a reduction in the removal. It is found from Fig. 3 that the removal does not change with the variation of pH in the range 2.54.0, while the removal is increased when pH is increased to 6.2 due to precipitation. The purpose of varying the stroke speed is to nd out the ease with which the mass transfer of Cr (III) ion occurs through the articial boundary layer outside RHA. When the stroke speed is high, the Cr (III) ion is easy to diffuse through the boundary layer and hence afford a high rate of removal and a high level of removal at equilibrium (Ho and Mckay, 1999a; Wong et al., 2003). If the stroke speed is high enough, the resistance of mass transfer through the boundary layer can be neglected which results in constant removal. The experimental results of present work shown in Fig. 4 imply that the mass transfer resistance can be ignored when the stroke speed is higher than 120 stroke/min. The effect of stroke speed found in the present system is observed to be relatively mild. Experiments were conducted at four different temperatures, in the range of 2050 8C, and the results are depicted in Fig. 5. It can be seen in the gure that the increase in adsorption temperature accelerates the removal of Cr3+ and increases the level of removal of Cr3+ at equilibrium. However, the dependency is not strong. This result also implies that the adsorption of the present system is an endothermic process. Most other investigators have also observed a similar trend (Alinnor, 2007; Singh and Rawat, 1994). 3.3. Rate equation Three steps needed for the chromium (III) ion in bulk aqueous solution to be adsorbed on the pore surface of the RHA are as follows: (1) mass transfer of chromium (III) ion through an articial lm external to the RHA particle, (2) diffusion of chromium (III) ion through the pore inside the RHA, and (3) adsorption of chromium ion onto the pore surface. Any step that is much slower than the others may control the overall adsorption process and the rate of the overall adsorption equals the rate of that slowest step (Fogler, 1999). The rate equations for different controlling steps are depicted in the following: (1) Film mass transfer control (Choy et al., 2004)     C 1 mkf 1 mkf ln b Ss t ln C 0 1 mkf 1 mkf mkf (3) The values of m and Ss in Eq. (3) are calculated according to: w (4) m ; v 6m Ss ; (5) d p r p 1 ep where dp is the RHA particle diameter (cm), kf is the adsorption rate constant (s/number of site), t is the adsorp-

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tion time (s), v is the volume of RHA-free solution (L), b is the mass transfer coefcient (cm/s), ep is the porosity of RHA particle and rp is the density of RHA particle (mg/L). (2) Pore diffusion control (Morris and Weber, 1962): C kd t0:5 ; C0 where kd is the rate constant (1/s0.5). (3) Chemisorption control (Low, 1960): 1 1 q lnab ln t; b b (7) (6)

According to the results depicted in Figs. 15, RHA dosage d, initial chromium concentration C0 and adsorption temperature T are the inuencing factors on the removal. Hence, they are incorporated into the expressions of k2 and qe which appeared in the differential form of pseudo-second-order rate equation: dq k2 qe q2 : dt (10)

where a is the constant (mg/g s) and b is the constant (mg/g). Eq. (7) is normally called Elovich equation. (4) Physisorption control of pseudo-rst-order type (Lagergren, 1898): lnqe q ln qe k1 t;
3+

(8)

where qe is the amount of Cr adsorbed per gram of RHA at equilibrium (mg/g) and k1 is the pseudo-rst-order rate constant (1/s). (5) Physisorption control of pseudo-second-order type (Ho and Mckay, 1999b): t 1 1 t; q k 2 q2 q e e (9)

Due to the monotonic dependencies of k2 and qe on d and C0 shown in Figs. 1 and 2, the power law type expressions are employed, while the Arrhenius law is used for the temperature dependence. The expressions used for correlations are given by   E1 n2 k2 k20 exp ; (11) d n1 C 0 RT   E2 m2 qe qe0 exp ; (12) dm1 C0 RT where E1, E2 are the activation energies (J/mol), k20 is the constant (L/s mg2), m1, m2 is the dimensionless exponents, n1, n2 is the dimensionless exponents, qe0 is the constant (mg/g), R is the gas constant (8.314 J/mol K) and T is the absolute temperature (K). When RHA dosage is varied and the other factors such as initial chromium concentration and adsorption temperature are kept constant, after taking logarithm of both sides of Eqs. (11) and (12), the equations can be written in the following forms:     E1 n2 ln k2 ln k20 exp (13) n1 ln d; C0 RT     E2 m2 ln qe ln qe0 (14) C0 m1 ln d: RT The method for determining the values of the exponents n1 and m1 will be presented in the following. The rst step is to plot t/q against t using the data given in Fig. 1 for various RHA dosages. The values of k2 and qe are obtained from the slope, 1/qe and the intercept 1=kq2 e for each RHA dosage. Then, ln k2 and ln qe are plotted against ln d. The values of n1 and m1 can be determined from the slopes of these two plots, respectively. The obtained values for n1 and m1 are 0.10 and 0.93, respectively. The values of n2 and m2 can be determined in a similar way and they are as 0.70 and 0.87, respectively. Assuming that the adsorption temperature is changed while other variables remain constant, after taking logarithm of both sides, Eqs. (11) and (12) can be rewritten as
n2 ln k2 lnk20 d n1 C0

where k2 is the pseudo-second-order rate constant (g/mg s). If the three steps mentioned above inuence the overall adsorption rate, a mathematical model incorporating these rates should be developed and the obtained data should be correlated with the rate equation thus derived. Unfortunately, such phenomenological model, which is very complicated and useful for designing and operating an adsorption vessel of the system of Cr3+/RHA, has not been developed. Hence, the obtained data are regressed with ve equations, Eqs. (3) and (6)(9), separately. It is seen in Fig. 4 that lm mass transfer resistance can be neglected as the stroke speed is higher than 120 stroke/min. Furthermore, the stroke speed of other four series of experiments was set at 120 stroke/min. Therefore, the controlling step of the present system is not lm mass transfer. Consequently, correlation with Eq. (3) can be waived. During regressions, the values of determination coefcient, r2 for the correlations were also calculated and are listed in Table 3. The equation with the largest r2 value is the best t. Therefore, Eq. (9) is found to be the best one. This result implies that physisorption step is the slowest one and controls the overall adsorption process.
Table 3 Average values of determination coefcient, r2 Equations
C C0

Average r2 0.9378 0.9659 0.9657 0.9999

kd t0:5

E1 1 ; R T E2 1 m2 ln qe lnqe0 dm1 C0 : R T

(15) (16)

1 q1 b lnab b ln t lnqe q ln qe k1 t t 1 1 q k q2 q t
2 e e

As ln k2 and ln qe are plotted against 1/T, activation energies E1 and E2 can be calculated from the slopes of the straight lines obtained, respectively. Experimental data in Fig. 5 can be used for this purpose.

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The nal equation determined by employing the origin 7.0 subroutine (OriginLab, 2000) is written as t 1 1:46 q 4:375 exp15586=RT 8070=RT 2 d 0:76 C0 t 0:87 1:867 exp8070=RT d 0:93 C0 (17) or in the differential form   dq 15586 0:10 0:70 1:255 exp C0 d dt RT   2  8070 0:93 0:87 1:867 exp C0 q d RT

4. Conclusions The RHA prepared in this work could remove chromium (III) ion from aqueous solution, but is not very efcient. The rate of removal and removal at equilibrium could be enhanced by decreasing the RHA dosage or by increasing the initial chromium concentration or the adsorption temperature. The removal was found to be unaffected by the pH and stroke speed in the range of 2.55.4 and 30 as well 60 stroke/min, respectively. An empirical rate equation of chromium removal has been determined. References

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Ajmal, M., R. A. K. Rao, S. Anwar, J. Ahmad, and R. Ahmad, Adsorption Studies on Rice Husk: Removal and Recovery of Cd(II) from Wastewater, Bioresour. Technol., 86, 147 (2003). Alinnor, I. J., Adsorption of Heavy Metal Ions from Aqueous Solution by Fly Ash, Fuel, 86, 853 (2007). Barrett, E. P., J. G. Joyner, and P. P. Halenda, The Determination of Pore Volume and Area Distributions in Porous Substance. I. Computations from Nitrogen Isotherm, J. Am. Chem. Soc., 73, 373 (1951). Candela, M. P., J. M. M. Martinez, and R. T. Macia, Chromium (VI) Removal with Activated Carbons, Water Res., 29, 2174 (1995). Chang, Y. Y., C. I. Lin, and H. K. Chen, Rice Hull Ash Structure and Bleaching Performance Produced by Ashing at Various Times and Temperatures, J. Am. Oil Chem. Soc., 78, 657 (2001). Choy, K. K. H., D. C. K. Ko, C. W. Cheung, J. F. Porter, and G. Mckay, Film and Intraparticle Mass Transfer during the Adsorption of Metal Ions onto Bone Char, J. Colloid Interface Sci., 271, 284 (2004). Dimitrova, S. V. and D. R. Mehandgiev, Lead Removal from Aqueous Solutions by Granulated Blast-Furnace Slag, Water Res., 32, 3289 (1998). Eligwe, C. A., N. B. Okolue, C. O. Nwambu, and C. I. A. Nwoko, Adsorption Thermodynamics and Kinetics of Mercury (II), Cadmium (II) and Lead (II) on Lignite, Chem. Eng. Technol., 22, 45 (1999). Fogler, H. S., Elements of Chemical Reaction Engineering, 3rd Ed., p. 591, Prentice Hall, Upper Saddle River, New Jersey, U.S.A. (1999). Greff, S. J. and K. S. W. Sing, Adsorption Surface Area and Porosity, 2nd ed., Academic Press, New York, New York, USA (1982). Gupta, V. K., A. Rastogi, M. K. Dwivedi, and D. Mohan, Process Development for the Removal of Zinc and Cadmium from Wastewater Using Slag A Blast Furnace Waste Material, Sep. Sci. Technol., 32, 2883 (1997). Gupta, V. K., D. Mohan, S. Sharma, and K. T. Park, Removal of Chromium (VI) from Electroplating Industry Wastewater Using Bagasse Fly AshA Sugar Industry Waste Material, The Environmentalist, 19, 129 (1999). Gupta, V. K., M. Gupta, and S. Sharm, Process Development for the Removal of Lead and Chromium from Aqueous Solutions Using Red Mud-an Aluminum Industry Waste, Water Res., 35, 1125 (2001a). Gupta, V. K., A. K. Srivastava, and N. Jain, Biosorption of Chromium (VI) from Aqueous Solutions by Green Algae Spirogyra Species, Water Res., 35, 4079 (2001b). Gupta, V. K. and I. Ali, Removal of Lead and Chromium from Wastewater using Bagasse Fly Ash-a Sugar Industry Waste, J. Collid Interface Sci., 271, 321 (2004). Hamadi, N. K., X. D. Chen, M. M. Farid, and M. G. Q. Lu, Adsorption Kinetics for the Removal of Chromium (VI) from Aqueous Solution by Adsorbents Derived from used Tyres and Sawdust, Chem. Eng. J., 84, 95 (2001). Ho, Y. S. and G. Mckay, Batch Lead (II) Removal from Aqueous Solution by Peat: Equilibrium and Kinetics, Trans. Inst. Chem. Eng., 77B, 165 (1999a). Ho, Y. S. and G. Mckay, Comparative Sorption Kinetic Studies of Dye and Aromatic Compounds onto Fly Ash, J. Environ. Sci. Health, A34, 1179 (1999b).

Eq. (18) indicates that the rate of removal of Cr3+ and the removal of Cr3+ at equilibrium is inversely proportional to the RHA dosage d and directly proportional to the initial chromium concentration C0 as represented by the positive exponent of d and negative exponents of C0, respectively, while the direct proportional effect of adsorption temperature is fully represented by the exponential term. The solid lines drawn in Figs. 15 are based on the best values of k2 and qe of the regressions. The data of pH 6.2 and those of stroke speed = 30 and 60 stroke/min have not been regressed due to the precipitation and the mild inuence of lm mass transfer, respectively. Comparison of Cr3+ removal, q calculated by Eq. (17) with those measured is shown in Fig. 6. The calculated results are in good agreement with the experimental data with a standard deviation of 1.82 in q. The regressed rate equation, Eq. (17) or (18) is thought to be helpful for designing and operating a vessel for wastewater treatment of the system of Cr3+/RHA.

Fig. 6. Comparison of calculated and experimental removal of Cr3+, q (mg/g).

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