Batch and Dynamics Modeling of the Biosorption of

Cr(VI) from Aqueous Solutions by Solid Biomass
Waste from the Biodiesel Production
Muthusamy Shanmugaprakash,a Venkatachalam Sivakumar,b Manickavelu Manimaran,a and
Jeyaseelan Aravinda
Department of Biotechnology, Kumaraguru College of Technology, Coimbatore 641049, India
Department of Food Technology, Kongu Engineering College, Perundurai, Erode 638052, India;
(for correspondence)
Published online 30 April 2013 in Wiley Online Library ( DOI 10.1002/ep.11781
Pongamia oil cake (POC), a bio-residual
waste is obtained during the production of biodiesel as a
byproduct. This is used as biosorbent to evaluate the removal
of chromium (VI) ions from an aqueous synthetic solution.
The effects of various process parameters such as pH, contact
time, initial chromium ions concentration and adsorbent
dosage have been investigated. The FT-IR and SEM analysis
of the adsorbents was done in the native- and Cr(VI)-loaded
state, to explore the position of the functional groups available for binding of chromium ions and the structural morphology of the studied adsorbents respectively. Langmuir,
Freundlich, Temkin and Dubinin–Radushkevich isotherm
were used to study the adsorption mechanism, and it was
found that the equilibrium data was better represented by
the Freundlich isotherm. The maximal removal of hexavalent
chromium ion was found to be at a pH of 2.0 within 2 h.
The sorption kinetic follows the pseudo second order kinetic
model. The Cr(VI) ions bound to the biosorbent could be
effectively removed, using dilute H2SO4 (0.05 mM). The ability of POC to adsorb Cr(VI) ions in packed column was also
investigated through the column studies. Bed Depth Service
Time model and the Thomas model were used to analyze the
experimental data and evaluate the model parameters. POC
was shown to be a promising adsorbent for removal of Cr(VI)
2013 American Institute of
ions from aqueous solutions. V
Chemical Engineers Environ Prog, 33: 342–352, 2014

Keywords: biosorption; pongamia oil cake; hexavalent
chromium; isotherms; kinetics; column studies

The recent rapid industrialization in India has led to the
release of huge amounts of industrial effluents into the environment and the heavy metals such as Cr, Cu, Pd, Ni, Zn,
and so forth, present in these effluents are more stable and
persistent environmental contaminants; since they cannot be
degraded or destroyed. Thus they tend to accumulate in the
soil, ground water, seawater and sediments, which intensify
environmental pollution. Chromium have been widely used
in a variety of industrial applications such as mining, leather

C 2013 American Institute of Chemical Engineers


July 2014

tanning, cement industries, steel production units, other
metal alloys industries and so on [1]. The highest level of
Cr(VI) ions permitted in a discharge into inland surface and
potable waters, are 0.1 and 0.05 mg/L, respectively [2,3].
Chromium, especially that is present in electroplating effluents, remains in two oxidation states Cr(III) and Cr(VI), of
which the hexavalent form is more toxic, when compared to
the trivalent form. An increased risk of lung cancer is
reported among workers exposed to chromate production
environment [4]. Therefore, there is a major concern for the
elimination of such heavy metal from wastewater before disposal to the environment.
Out of the wide ranges of conventional methods which
are available for the removal of this heavy metal from aqueous solutions, include precipitation [5], oxidation-reduction
[6], ionic exchange [7], electrochemical treatment [8], and
membrane techniques [9]. However, the major drawbacks of
all these methods are that they involve high operating costs,
and may result in a large volume of solid wastes [10,11]. Biosorption is found to be an effective treatment technique
owing to its cost-effectiveness and environmental friendly
characteristics [12]. In biosorption, either metabolically active
or inactive biological material is used, to concentrate and
recover or eliminate these pollutants from effluents. Commercially available activated carbons are found be costly and
hence they have to be regenerated many times for reuse.
Reduction in activity during each stage of regeneration and
the short shelf life of activated carbon affect the economic viability of the process for real time operation. From the analysis of recent publications it was found that different
inexpensive, locally and abundantly available biosorbents
have been employed for removal of various heavy metals,
for example, sugarcane bagasse, maize corn cob, jatropha oil
cake [13], mustard oil cake [14], olivestone [15], sawdust, rice
husk [16], modified coconut coir pith [17], and so forth.
However, it is still found to be inadequate to address
these problems, more work and research are needed to identify other locally available, cheap adsorbents to eliminate
Cr(VI) ions from industrial wastewater samples with different
compositions and characteristics. Therefore, there is a need
to identify suitable sources of materials, which are locally
available in plenty with low-cost or generated as a waste

Environmental Progress & Sustainable Energy (Vol.33, No.2) DOI 10.1002/ep

13 22. No. The Bed Depth Service Time (BDST) and the Thomas models were analyzed. In this study. many industrial plants have been installed for extraction of oil from Pongamia seeds to prepare the biodiesel. were used as a desorbing agents for the recovery of Cr(VI) ions from the loaded adsorbent. Adsorbents Soya cake Coconut shell carbon Beech saw dust Jatropha seed press cake Rice husk carbon Saw dust carbon Modified coconut coir pith S. the cake generated from this is usually discarded as waste material (POC). The flasks were incubated at 303 6 2 K in an orbital shaker at 150 rpm. The supernatant was collected.48 76. Eð%Þ5   Co 2Ce 3100 Co (1) where Co and Ce are initial and equilibrium chromium concentrations in the solution (mg/L).0 2.33. The adsorption capacity. The residual concentration of Cr(VI) ions at the outlet of the column was determined at regular time intervals. Because of the huge volume of cake generated during oil extraction. The sieved material was stored in a desiccator for further adsorption studies. A stock solution of 1000 mg/L was prepared. Q is the flow rate which column (mL/min). of an adsorbent is the amount of chromium adsorbed per unit mass of the adsorbent.6 1. using the column breakthrough data. and also used to design the industrial fixed bed column. Column Studies It is necessary to generate the data by conducting the fixed bed column experiments in order to understand the adsorption characteristics. The main process parameters considered in the batch studies. were pH.0 2. The adsorption be determined by the equation as in slight modifications. Batch Adsorption Studies Batch experiments were carried out with various pH (210). In India.0 4. particularly in southern part. but with given as follows Environmental Progress & Sustainable Energy (Vol.727 48. Isotherm constants for the removal of Cr(VI) by POC.33 0. varlgaris POC Adsorption capacity (mg/g) pH References 0.95 Table 2. The cake was crushed into fine particles using a mortar and pestle. and a stirring speed of 150 rpm. A known concentration of the metal solution was pumped into the column at a desired flow rate using peristaltic pump (Miclins PP 20 Ex. Continuous flow sorption experiments were conducted in a glass column (2 cm internal diameter and 45-cm height) packed with required POC.5-diphenyl carbazide).2.2) DOI 10. contact time.1 mM).91 0.0 0. and the amount of Cr(VI) present in the supernatant was determined. hydrochloric acid (HCl) (0.286 0. Comparison of adsorption capacity of other adsorbents for Cr(VI) onto POC.1 M HCl and 0.0 [32] [33] [34] [35] [16] [16] [17] [36] [36] Present work from any process to remove Cr(VI) ions from industrial wastewater. India). and adsorbent dose.1002/ep (3) time(min). The removal efficiency (E %) was calculated using the following equation.0 2. The pH of the solution was adjusted with 0.91 33.0 2. Vef (mL) was calculated using the following equation Vef 5Qttotal where ttotal is the total circulates through the capacity qe (mg/g) can batch studies. an attempt has been made to explore the use of pongamia oil cake as suitable adsorbent for the removal of Cr(VI) ions from an aqueous system under different experimental conditions in the batch and continuous modes. After the extraction of oil. respectively.68 166. calibrated with buffers of pH 4. Synthetic wastewater was prepared by dissolving K2Cr2O7. It was dried in a hot air oven at 363 K for 24 h. Desorption Studies Chemicals such as sulfuric acid (H2SO4) (0.05–0. 7. using the pH meter (ELICO LI120.0.28 10.   Co 2Ce 3V qe 5 M (2) where M is the mass of the adsorbent (g) used and V is the volume of the solution (L).68 163. Langmuir isotherm Adsorbent POC Freundlich isotherm Temkin isotherm D-R isotherm Qo (mg/g) b (L/mg) R2 KF [(mg/g)(L/mg)1/n] n R2 qd (mg/g) ED (kJ/mol) R2 A (L/g) R2 166. this waste could be used as biosorbent for removal of heavy metals due to its potential adsorption characteristics. and 9.31 53. India). qe (mg/g). Japan).99 78.6 0.984 1. The volume of the effluent.0 2.1 mM) and ethylenediaminetetraacetic acid (EDTA) (0. and from this the working standards were diluted accordingly. In this method. The dried cake was filtered through a 250 mm size sieve. using DPC (1.0 2. Japan) at 5000 rpm for 15 min.0.1 M NaOH. The equation is July 2014 343 . concentration of Cr(VI) was determined by developing red-violet color with DPC and measuring the absorbance at 540 nm using a UV–vis Spectrophotometer(Shimadzu UV-1800. The Cr(VI) loaded biomass was wetted with distilled water and added to 100 mL of desorbing solution.00233 0.01–0.33 0.5 mM). Samples were withdrawn at specified time intervals and centrifuged in a refrigerated centrifuge (Kubota 3700.0 2. MATERIALS AND METHODS Preparation of the Adsorbent and Synthetic Wastewater Pongamia oil cake (POC) was acquired from the local pongamia processing industry.01–0. adsorbent doses (1–5 g/L) maintaining a temperature of 303 6 2 K.Table 1. platensis C.0 1. and it was calculated using the following equation. metal concentration (100–500 mg/L).H2O (AR grade) crystals in distilled water.3 188. initial Cr(VI) ions concentration.88 16.

27 7.42 0. FT-IR Spectrometer).00 0.1 0. A slight increase in intensity is observed at 1473 cm21 after biosorption.35 70..17 60. that is.5 0.0012 0. pectin.21 23. 1629. HCr4.316 0.Table 3.01 11.22 34. Scanning Electron Microscopy of the Adsorbents Scanning electron microscopy (SEM) is a primary tool for characterizing the surface morphology.818 0.3 0.351 3.042 4. Environmental Progress & Sustainable Energy (Vol.01 the acidic pH range and HCrO4.33 42.21 39. The changes in the band at 856 cm21 are indicative of CAH bending during biosorption process. which results in strong electrostatic attractions between the protons and the chromate ions. shifting and increase in peak intensities at 3411.891 0.81 59. 2143.21 0. the surface of the adsorbent seems highly protonated.924 0.00 0. An intense broad spectrum observed at 3411 cm21 corresponds to OAH stretching vibrations of cellulose.58 69. No.4 0.21 23.88 32.748 0. Cr3 O210 .998 0.22 27. At a higher pH. absorbed water and lignin in both native and desorbed biomass was shown in Figure 1 [23].053 21. The changes observed on peaks 1629 and 1563 cm21which reflect stretching vibrations of symmetrical or asymmetric ions carboxylic groups (ACOOH) present on the surface of POC.998 0.44 11. Modeling of Isotherm. Kinetic and Breakthrough Curves The various theoretical models for both batch and column adsorption studies (Tables 1–5) were applied to find a model adequacy to predict the isotherm. SEM micrographs of native POC and the adsorbed POC with Cr(VI) are shown in Figures 2(a) and 2(b).88 35.55 45. The changes seen in the peak at 2989 cm21 after biosorption indicate that there is possible involvement between symmetric or asymmetric CAH and the symmetric stretching vibrations of CH2. the POC has a considerable number of pores with high homogeneity and there is considerable decrease in the porous nature of Cr(VI) loaded biomass.77 48. A peak at 1629 cm21 is due to stretching of carbonyl (C@O) vibrations and broad peak at 1239 cm21 is due to CAN stretching [24].862 0.99 41. Cb is the breakthrough concentration (mg/L) and Vef is the volume of effluent that is required to attain the exhaustion of the column (L).044 0.00 62.22 H2SO4 HCl EDTA   Co 2Cb qe 5 3Vef M (4) where M is the mass of adsorbent (g).is the most predominant. and 1239.36 0.67 0.596 2.25 44. there are shiny bulky particles accumulated as a layer over the surface of adsorbents due to the presence of chromium ions. Bands at 344 July 2014 Intraparticle diffusion constants Pseudo II order 2292 and 2143 cm21 are due to the CAN stretching vibration.27 6.65 31.22 30.31 0. suggesting the coordination of CH3 groups present on the surface of metal ions. Eluant Desorption of Cr(VI) (%) at Concentration of eluant (mM) 20 min 40 min 60 min 0.45 55.63 32. of metal ion (mg/L) 100 200 300 400 500 Pseudo I order qe exp (mg/g) kI (1/min) qe cal (mg/g) R2 KII (g/mg/min) qe cal (mg/g) R2 ki (mg/g time1/2) C R2 18.50 71.2 34.45 19.27 0.54 30.0.05 0.27 8.22 47.04 33.0 and as pH increased there is a significant decrease in the removal of chromium (Figure 3).994 0. 1170 cm21.49 28.263 4. 1493.71 46. Kinetic parameters for the removal of Cr (VI) ions onto the by POC.58 56. RESULTS AND DISCUSSION Fourier Transforms Infrared Analysis To determine the surface functional groups on the adsorbent during biosorption and desorption processes of Cr(VI) onto POC.0027 0. It is seen that the maximum chromium removal is observed at a pH of 2. The validity of models was evaluated based on the regression coefficient (R2).54 25.53 24.33 0.11 0.25 30. Also.999 1.048 0. and fundamental physical properties of the given adsorbents (FEI Quanta FEG 200 High resolution SEM).491 14. in the alkaline range.89 60.05 0.65 0.01 0.0022 0. The specific surface area of the POC was determined by BET method and it is found to be 0..05 0.30 18. Fourier transform infrared (FT-IR) analysis was done (Spectrum one.25 26.892 0.075 0. and Cr4 O313.873 0.60 kg/m3.2 0. as well as the ionic form of the chromium ions during adsorption studies. At pH 2.48 50. Effect of pH pH is an important factor which influences the surface properties of the adsorbent.078 6.26 84. This is due to the fact that chromium exists as Cr2 O-7 . It is clear that.21 10. The sharp peak at 2989 cm21 is attributed to the CAH stretching. 2989.45 61.25 24.1002/ep .943 0.75 23.9 36.075 0.2) DOI 10.19 30.05 5. This may be due to the significant possibility of the chromium ions being adsorbed onto the pores and remaining trapped [25].88 33.1 0.28 0. 1563.04 22. kinetic and breakthrough data.05 7.00 0. the surface of the adsorbent will have hydroxyl groups which will not attract the chromate ions that compete with the hydroxyl ions [26]. The spectra of the dry adsorbents were measured within a range of 500– 4000 cm21.43 0.65 31.05 0. This is confirmed by the reappearance of peak at 2989 cm21 after Cr(VI) desorption from POC. After treating the adsorbent with Cr(VI) solutions at pH 2.0022 0.27 8.043 0.0046 22. 2292.1 0. Cr4 O313 . Desorption of Cr (VI) with time using different eluent.609 Table 4. Initial conc.63 0.882 0.46 0. there is disappearance.9 m2/g and its bulk density is given by 0.

whereas in higher initial metal ion concentrations this ratio is less and so the efficiency is also lesser. KTh (L/mg h) 24 1 3 10 2 3 1024 2. On the contrary. An increase in the initial metal ion concentration acts as a prime force in overcoming all the resistance to adsorption [30]. mainly due to the overlapping of adsorption sites caused by the overcrowding of the adsorbent particles or unsaturation of adsorption sites through the adsorption reaction [28].0 g/L.977 The Thomas model parameters Flow rate (ml/min) 10 15 20 Bed height (cm) 5 5 5 Figure 1. it can be concluded that the removal efficiency increased from 48 to 81% as the adsorbent dose increased but the amount of Cr(VI) ions adsorbed per unit mass decreases by increasing the biosorbent concentration. such as aggregation.61 540 960 1440 Qo (mg/g) R2 43. The removal of chromium increased with an increase in the time and reached the maximal level at 60 min with no further increase.4 3 1024 Effects of Initial Metal Ion Concentration and Contact Time The adsorption of chromium onto the POC for the different initial concentrations (100–500 mg/L) as a function of the contact time was studied.875 0. equilibrium is said to be achieved. From Figure 4. (B) FT-IR of Cr(VI) loaded POC (C) FT-IR of Cr(VI) desorbed POC. When the adsorbent surface is completely saturated with the adsorbate.Table 5.53 40.64 71. A plot between Cqee versus Ce as shown in Figure 6(a) is used to calculate the constants Qm and b. the ratio of the available surface area for adsorption to the concentration of chromium ions is higher. The Freundlich model is an empirical one.3 to 69.0 g/L did not cause any significant improvement in adsorption.5 13 19. suggesting that equilibrium has been attained. Qm is the maximum amount of the solute adsorbed per unit mass of the adsorbent to form a complete monolayer (mg/g) and b is a constant related to the affinity of the binding sites (L/mg). Another reason may be particle interactions. The Langmuir isotherm assumes that the adsorbate forms a monolayer around the homogenous surface of the adsorbent. resulting from high biosorbent concentration and such aggregation would lead to decrease in total surface area of the sorbent and an increase in diffusional path length [29]. It also provides the relationship between the amount of the metal ions adsorbed onto the surface.73 0. and the concentration of the metal ions in the aqueous solution at equilibrium condition. No.2) DOI 10. by keeping the other related parameters constant. Moreover. the removal efficiency decreased. it increases the number of collisions between the Cr(VI) ions.0 to 5. the adsorption capacity increased as the metal ion concentration increases as shown in Figure 5. However.53 58.53 37. (A) FT-IR of native POC. to design and optimize an operating procedure on a large scale. Effect of Bed height for Cr(VI) adsorption by POC using BDST and Thomas Model. the adsorption qe (mg/g) capacity decreased from 129. which assumes that adsorption takes place on a heterogeneous surface and also proposes multilayer sorption with interaction among the Environmental Progress & Sustainable Energy (Vol. and there is no interaction between the adsorbed molecules [31]. It was seen that as the metal ion concentration increased. Effect of the Adsorbent Dose The adsorbent dosage determines the capacity of an adsorbent for an adsorbate at a given initial concentration [27].857 0. Further increment in biosorbent concentration from 3.1002/ep July 2014 345 .23 as the adsorbent dose increased from 1. Ce is the concentration of the un adsorbed solute in solution (mg/L). Biosorption Isotherm Studies The adsorption isotherms are important to analyze the equilibrium data by developing a mathematical equation. This is mainly due to an increase in the number of available adsorption sites with an increase in biosorbent concentration and resulting in the increase of adsorbed metal concentration.33. This is due to the fact that when the initial metal ion concentration is low. The linear form of the Langmuir model is given by Ce 1 Ce 5 1 qe Qm b Qo (5) where qe is the amount of the solute adsorbed on the adsorbent surface at equilibrium (mg/g).5 105 195 300 43. The BDST model parameters Bed height (cm) 5 10 15 Sorbent weight (g) Breakthrough time (min) Qo (mg/g) Exhaustion time (min) 6. This is due to the binding of almost all Cr(VI) ions to the adsorbent and the establishment of equilibrium between the Cr(VI) ions bound to the sorbent and those remaining unadsorbed in the solution.

Figure 5. The effects of some indirect adsorbate/adsorbent interaction on adsorption isotherms were studied by using isotherm proposed by Temkin and Pyzhez [33] and it was found that the heat of adsorption of all the molecules in the layer decreases linearly with coverage [34]. The linearized Temkin isotherm is represented by the equation Figure 4.Figure 2. T is the absolute temperature (K). The logarithmic form of above equation can be written as 1 ln qe 5ln kf 1 ln Ce n (6) where KF is the Freundlich constant representing the bonding energy((mg/g)(L/mg)(1/n)) and n is a constant which is an indicator of the adsorption favorability.0. stirring speed 5 150 rpm. (a) SEM images of native POC (a) and (b) SEM images of Cr(VI) loaded PO. The values of KF and n are determined from the plot Figure 6.0.1002/ep . (b) between lnqe versus lnCe. Effect of initial metal ion concentration and contact time on Cr (VI) removal by POC [Adsorbent dose 5 3 g/ L. b is a constant related to the heat of adsorption. temperature 5 30 6 2 C]. stirring speed 5 150 rpm. adsorbent dose 5 3 g/L. No. contact time 5 120 min. Effect of adsorbent dose on Cr (VI) removal efficiency (%) and biosorption capacity (qe) by POC [Chromium concentration 5 500 mg/L. contact time 5 120 min. and A is the equilibrium binding constant (L/g) Environmental Progress & Sustainable Energy (Vol. pH 5 2. temperature 5 30 6 2 C].33. Figure 3. 346 July 2014 qe 5 RT RT ln A1 ln Ce b b (7) where R is the gas constant (kJ/mol).2) DOI 10. stirring speed 5 150 rpm. pH 5 2. adsorbed molecules [32]. Effect of pH on adsorption of Cr (VI) by POC [Chromium concentration 5 100 mg/L. Values of n > 1 favors adsorption. temperature 5 30 6 2 C]. contact time 5 120 min.

which determines the residence time of the sorbate at the solid–liquid interface. it is important to predict the solute uptake rate. In order to investigate the mechanism of adsorption. The values of the constants can be determined from the plot between qe and lnCe in Figure 6c. The mathematical values of these models are given in Table 3. and is expressed as   ln qe 5ln qD -2BD R2 T 2 ln 111 Ce Þ2 (8) where qD is the theoretical saturation capacity (mg/g) and BD is a constant related to the adsorption energy (mol2/kJ2).995). POC has been compared with other adsorbents based on their maximum adsorption capacity (qm) for Cr(VI) ions (Table 2).38]. Accordingly. It is calculated from the following equation 1 ED 5 pffiffiffiffiffiffiffiffiffiffiffiffi ð2BD Þ (9) According to the data from Table 1 it seems. the characteristic constants of the adsorption rate are determined using a pseudo first-order equation of Lagergren. corresponding to the maximum binding energy. Biosorption Kinetics Studies For constructing a waste water treatment plant. (c) Temkim Isotherm. and pseudo second-order equation based on solid phase adsorption. The constant BD is a representative of the mean free energy ED (kJ/mol) of the adsorption per molecule of the adsorbate. The regression coefficient of Freundlich model is found to be near unity (R2 value of 0. No. and (d) D–R isotherm. Linear isotherms for Cr (VI) removal by POC at 30 6 2 C. R is the gas constant (J/mol/K). In the present study. (a) Langmuir isotherm. that the Freundlich model fits better with the experimental data than the Langmuir model.1002/ep July 2014 347 . and an intraparticle diffusion model [37. The pseudo first order and pseudo second order kinetic models are applied to study the sorption kinetics of chromium on the POC and the extent of the uptake in the biosorption process. based on solid capacity. this data indicates that POC could be considered as promising adsorbent in comparison to other available adsorbents. The values of Bd and qD can be calculated from the slope and intercept correspondingly from the plot between lnqe and ln(1 1 1/Ce)2 as shown in Figure 6d. (b) Freundlich Isotherm. Environmental Progress & Sustainable Energy (Vol.2) DOI 10. It can be seen from Table 1 that the value of ED is 0. Another important equation for the analysis of the isotherm of a high degree of rectangularity is the Dubinin– Radush Kevich isotherm [35].33.286 kJ/mol and it is known that when ED value is lesser than 8 kJ/mol then the adsorption process follows physical adsorption [36]. and T is the temperature (K).Figure 6. The D–R isotherm model does not assume a homogenous surface.

Figure 7. and also does not pass through the origin. and qt is the amount of chromium adsorbed on the surface at any time t (mg/g). which describes the diffusion mechanism. The pseudo first order kinetic model was proposed by Lagergren [39] and is expressed as dqt 5kI ðqe -qt Þ dt (10) The integrating Eq. The pseudo second order kinetic model [40] is expressed by the equation t 1 1 5 1 t qt qe2 kII qe (12) where kII is the pseudo second order rate constant (g/mg/ min). The model is expressed as 348 July 2014 Figure 8. and the values of k1 and qe are determined from the slope and intercept.5 mM H2SO4 showed the maximum elution (84. for the desorption of Cr(VI) from a laden biosorbent.2) DOI 10. Environmental Progress & Sustainable Energy (Vol. qe is the amount of chromium adsorbed on the surface at equilibrium(mg/g). and C is a constant which gives an idea about the thickness of the boundary layer. and based on the above observation it can be concluded that the pseudo second order kinetic model fits well in this sorption study [Figures 7(a) and 7(b)]. qt 5ki t 1=2 1C (13) where ki is the intraparticle diffusion rate constant ((mg/ g)(time)1/2). Desorption Studies Desorption studies were carried out using three desorbing agents (Table 4). If this plot yields a linear graph which passes through the origin. It was seen that the qe values calculated from the pseudo first order kinetic model do not correlate well with the experimental qe values (Table 3).1002/ep .65%) of Cr(VI) in 60 min. which can be determined from the plot between t/qt versus t. then the sorption process is controlled only by intraparticle diffusion. Intraparticle diffusion plot for Cr(VI) ions removal onto the POC at 30 6 2 C. A plot is drawn between ln (qe 2 qt) versus time. gives lnðqe -qt Þ5ln qe -kI t (11) where kI is the rate constant (min21). that control the adsorption rate. Thus the adsorption of chromium ions onto the POC is presumably physisorption and the surface functional groups of the adsorbent. It was also noted that the coefficients in this model are low. respectively. Similar results have been reported in the biosorption of Cr (VI) onto the activated carbon derived from agricultural waste material [41]. Among the three agents tried. The calculated qe values from the pseudo second order kinetic model agree well with the experimental qe values. which can be calculated from the plot qt versus t1/2. No. (a) Pseudo first order and (b) second order kinetic plot (b) for Cr (VI) ions removal onto the POC at 30 6 2 C.33. while comparing the values derived from the pseudo second order kinetic model. (10) between the boundary conditions t 5 0 to t 5 t. 0. It can be seen from Figure 8 that the graph is not completely linear. It is obvious that the graph is more linear in the pseudo second order kinetic model. suggesting that there are other kinetic factors involvedapart from Intraparticle diffusion. Weber and Morris [42] proposed the intra particle diffusion model.

respectively. Co is the initial metal ion concentration which (here) is 100 mg/L. L. The time required to achieve the breakthrough concentration is called as the breakthrough time. which suggests that BDST model fits well and thus the column studies are feasible. COLUMN STUDIES Effect of The Bed Height on The Adsorption of Cr(VI) by the POC The effect of the bed height was studied by varying column height and by maintaining all other parameters. For a smaller value of Ka. The effect of bed height is explained. were calculated from the BDST plot shown in Figure 10 and were found to be 3923. pH 5 2.(Co 5 100 mg/L. which is fed into the column at the outlet of the column. The rate constant Ka. It is observed from Figure 10.33. that when the bed height increases the process becomes time consuming.46]. The time required to achieve the initial metal concentration. Z is the bed height in cm and ka is a rate constant (L/mg/min). Figure 10. the adsorption capacity is more. The BDST model is expressed as t5   No z 1 Co ln -1 Co m Ka Co Cb (14) where t is the service time that can be taken as the time (min).0 and temperature 5 30 6 2 C). From Figure 11 it can be observed that as the flow rate increases both the exhaustion time and breakthrough time decrease. as the bed height increases both the breakthrough and exhaustion time increase and also it is seen that the R2 value for the BDST plot is high. is called the exhaustion time [45. Cb is the breakthrough time taken for the outlet concentration in the column to reach 5 mg/L. pH and initial metal ion concentration and rate constant (Figure 9).2) DOI 10. The experimental and modeled breakthrough curves from Thomas Model for the adsorption of Cr(VI) onto the POC at different flow rates. a relatively longer bed is required to avoid a breakthrough. pH 5 2. BDST model for Cr(VI) adsorption by POC. Bed height 5 5 cm. It means that the adsorbent in the column cannot absorb any heavy metal beyond the exhaustion time. Adsorption was studied for various flow rates in the range of 10–20 mL/min for the initial metal ion concentration of 100 mg/L and a bed height of 5 cm. largely influences the breakthrough phenomenon in the column study. v is the velocity in cm/min. which is a measure of the rate transfer of the solute from the fluid phase to the solid phase. This value is given in Table 5 and it should also be taken into account. Effect of bed height for Cr(VI) adsorption onto the POC (flowrate 5 10 mL/min. which clearly indicates that desorption is a physic-chemical sequester on the surface [43].1002/ep July 2014 349 . Co 5 100 mg/L. where the outlet concentration of the column is 5 mg/ Figure 11. Effect of the Flow Rate on the Adsorption of Cr (VI) by POC The flow rate is one of the important characteristics in evaluating the sorbents for continuous treatment of the metal-laden effluents on an industrial scale.0 and temperature 5 30 6 2 C). whereas the breakthrough can be eliminated even in smaller bed heights when the value of Ka is high [43. The parameters of the BDST model No and the rate constant Ka. No is the adsorption capacity of the column (mg/L).46].4 mg/L and 5. The uptake values were found to be Environmental Progress & Sustainable Energy (Vol. such as the flow rate. so it is desired to perform column studies with the maximum bed height.Figure 9. using the Bed Depth Service Time (BDST) model [44].88 3 1023 L/mg/min. Bed height 5 5 cm. No. Only when the bed height is the maximum.

53. Similar trends have been observed by other researchers for various adsorbents [48. 59–71. M. Chakravarti. The Cr(VI) loaded POC was eluted with a 0.. Desorption and Column Regeneration Studies From the economic point of view. it can be inferred that the bed capacity Qo decreases with an increasing flow rate. & Polprasert. isothermal and isobaric process conditions. EPA/ 625/4-89/023.1002/ep . (1993). (1995). T. Qo is the maximum solid phase concentration of the solute (mg/g)   and V is the throughput volume (L). 34. The Thomas model is a simple and generally used model for the prediction of the concentration versus time profile. 6.J. the 0. 8. Liquid membrane multiple emulsion process of chromium(VI) separation from waste waters.73 mg/g for the flow rates 10. 62. 43.. In situ Cr(VI) reduction within coarse-textured. the Thomas model [47] can be expressed in its linear form as  ln  Co KTH Qo M KTH Co -1 5 F C F (15) where kTh is the Thomas model constant (L/mg h). Takahashi. As the adsorption and desorption cycle proceeds. 2. indicating that the surface is heterogeneous. The pseudo-second order model can be used to predict the adsorption kinetics. D. EPA/625/5-90/025. (1999). which shows the influence of the flow rate on the sorption capacity.. it can be interpreted that the efficiency of the Cr(VI) adsorption on the regenerated POC in the fourth and fifth cycle. Seaman.Manimaran. & Passino. and 20 mL/min respectively.C. A plot of ln CCo -1 against t (where t 5 V/F) for a given flow rate is used to determine the model constants. because of continuous usage..0. 1 2 3 4 5 Adsorption of Cr(VI) (%) Desorption of Cr(VI) (%) 98.. H. 115–126.5 mM H2SO4 solution through column studies. J. ACKNOWLEDGMENTS The authors (M. Korenaga. 103. P.. S. Drinking water—specification (first revision). compared with other eluant (Table 4). Recovery of chromium from tannery effluents using a redox-adsorption approach. Aravind) are thankful to the Management. After the recovery of the metal ion.. D. 33. & Mukherjee. initial chromium ions concentration and dosage concentration. American Journal of Industrial Medicine. constant column void fraction. constant physical properties of the biomass (solid-phase) and the fluid phase. From Table 5.21 75. From 350 July 2014 Table 6. G. From the FT-IR analysis it was found. and 37.12 65. Chakrabarty. and the limited diffusivity of the solute into the sorptive sites or pores of the biomass. the results showed that H2SO4 (0. of a bed height of 10 cm. 40.22 81. Environmental Protection Agency.C. 5. Lung cancer among workers in chromium chemical production. flow rate 5 10 mL/min.S. A. The adsorption is described by a pseudo second order reaction rate principle which reduces a Langmuir isotherm at equilibrium. N. L. Pinsky. Environmental Science and Technology. In our batch studies. T.C. Water Research. The amount of metal adsorbed was found to vary with the pH. A process monitoring/controlling system for the treatment of wastewater containing chromium (VI).F. 109–116. LITERATURE CITED 1. Moriwake. On the basis of the above assumption. S.. (1995). Water Science and Technology.. Therefore.. an abundant agricultural waste from biodiesel production. The reason for the decreased sorption capacity at a higher flow rate may be due to the unavailability of sufficient retention time. T. the regenerated POC was thoroughly washed with distilled water and again loaded with the Cr(VI) solution of a concentration of 100 mg/ L.Shanmugaprakash. Environmental Progress & Sustainable Energy (Vol. that the hydroxyl and CAH groups present in the surface of the adsorbent contribute to chromium adsorption. Petruzzelli. while the Thomas constants KTH increased with an increasing flow rate of 10–20 ml/min.B. X. 30–37. 38. (2000). T. B. US. O’Dwyer. 15.. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 27. Indian Standard. Adsorption and desorption efficiency of Cr(VI) ions in column studies.J.32 CONCLUSION Cr(VI) 5 100mg/L. The BDST and the Thomas Model were used to evaluate the experimental data and both the models were valid for accurate evaluation. & Rooney. 938–944. for providing the facilities to carry out this research. both the experimental and the Thomas model predicted breakthrough curves are shown in Figure 11..F.32 70. Cincinnati. This is due to the gradual deterioration of the POC. The Thomas model constants are given in Table 5 and it seen that a high correlation exists between the experimental data and the predicted value.33.5 mM) has good elution capacity. Bertsch. S. Five adsorption–desorption studies were carried out repeatedly by maintaining the same operating conditions. & Shinoda. or the breakthrough curve for the effluent with basic assumption. pH 5 2.12 40. EPA.25 82. Chakrabarty. was beginning to drop. the reusability of the adsorbent material is very important in the field of adsorption technology.. Zhou. B. Pretreatment of tannery wastewaters by an ion exchange process for Cr(III) removal and recovery..5 mM H2SO4 solution was used as the eluting agent at a constant flow rate of 10 mL/min and preloaded with Cr(VI)biomass.K. Water Science and Technology.K. (1996). P. Journal of Chemical Technology and Biotechnology. Cycle Nos. bed height 5 10 cm.Table 6. T.49]. 1049–1054. Lees. & Schwallie. Tiravanti. 36. 4. 197–207. Chromium removal by a bipolar electro-chemical precipitation process. (1997). the intraparticle diffusion and external resistance during the mass transfer processes are considered to be negligible.49 80. The present study suggests that pongamia oil cake. Coimbatore.. and reused for five adsorption–desorption studies. contact time. 7. C.33 87.22 66. Kumaraguru College of Technology. 3. No. The adsorption equilibrium data were found to fit the Freundlich isotherm. Chowdhury..43.M. the accessibility of the metal ions toward the binding sites get reduced [43]. Gibb. IS 10500. can be used as an adsorbent for the removal of chromium (VI) from aqueous solutions. 1990. P. oxide-coated soil and aquifer systems using Fe (II) solutions. 1991.. J. & Hodnett. 9. R. The breakthrough curves were analyzed at different flow rates and bed heights.2) DOI 10. Kongsricharoern. Environmental Pollution Control Alternatives.

& Garg. Bishnoi. Journal of Hazardous Materials. P. D. K.. 312–320.. & Tabrizi. Daneshvar.. Butterworth: Boston. (2002). (2011). (2004). & Martın-Lara. & Ho. Column study of chromium (VI) adsorption from electroplating industry by coconut coir pith.S. 31. 11155–11160. Kapadnis. Biosorption of zinc ions from aqueous solutions onto natural dye waste of Hibiscus rosa sinensis: Thermodynamic and kinetic studies. S. 37. B. & Masood. 44. J.P. 11. Porte. 33. J. Cr(VI) removal from synthetic wastewater using coconut shell charcoal and commercial activated carbon modified with oxidizing agents and/or chitosan. S.I. & Bishnoi. L.J.H. 34. Journal of the American Chemical Society. S. Jr. M. 24.The role of sawdust in the removal of unwanted materials from water. Journal of Hazardous Materials. 39. Equilibrium and kinetics studies for the adsorption of direct and acid dyes from aqueous solution by soy meal hull. (2008).. 40.F. and Soil Pollution. 40. J. N. H..M.. Garg. U. & Kurniawan. Bohart. an industrial solid waste.M.S. J. Bioresource Technology.1002/ep July 2014 351 . Singh.. Langmuir. M. MA. Over the adsorption in solution. Sorption potential of Haro river sand for the removal of antimony from acidic aqueous solution. Bioresource Technology.. 160. (1947). 41. 102. 18. 12. 28. 24. 83–92. 41.. Garg..S. 2218–2225. V. 98..K. D. USA. B. P.. W. & Sahu. Temkin. 185. Handlingar. Air. Bansal. (2006). Choi. Environmental Progress & Sustainable Energy (Vol... Bioresource Technology. Tenorio. Environmental Progress and Sustainable Energy. & Lele. Fauduet.A. Journal of the Sanitary Engineering Division.K. Bansal. Garg. Choong. Dubinin. 35. Kumar. E. 14–21. Singh. T. F.. 45.J.. 44.Y. V. Hasany. & Aber. Kavita. Ngabura..2) DOI 10. Nagpal. Pawar. E. Removal of Cr(VI) from aqueous solutions using pre-consumer processing agricultural waste: A case study of rice husk. (2011). (1987).M. & Sumithra.P. 15. FL. S. 576–585. N. CRC Press Boca Raton.. (2009). M. 95. N. 171–179.G.K. & Nakbanpote. V.. M. N. Industrial and Engineering Chemistry Research... 137–52.. & Yang. Environmental Progress and Sustainable Energy. Some aspects of the behavior of charcoal with respect to chlorine. Y. R.. & Keharia. R. & Pyzhev.312–320... Y. 99.. D. 3580–3585. 54. 327–356. Journal of Hazardous Materials. M. & Aydin. 25. (2005). & Radushkevich. S. C. (2012). V. 46. & Shukla. W. D. Desalination. Applied Radiation and Isotopes. Removal of Cr(VI) from aqueous solutions using pre-consumer processing agricultural waste: A case study of rice husk. Adsorption processes for water treatment.K.. M.. & Cukierman. 60–68. S.M. V. S. Zentr. H. Journal of Hazardous Materials. M. 57. (2008). 1.. (2008).. Journal of Hazardous Materials.K.Y. Shukla. 26. (2009). K. Kaur.R. (2011). D. S. Industrial and Engineering Chemistry Research.V. Chem.V. Singh. 162. Water. (1990). H. R. 36.Q. 23. 30. Zhang. & Malkoc. (2002). D. mica and platinum.. A comparative study for the removal of hexavalent chromium from aqueous solution by agriculture wastes^aeTM carbons. M. 123. Kinetics of ammonia synthesis on promoted iron catalysts. Mohan... 31–60. (2005)...S. 7– 44). G. Journal of Hazardous Materials. (1920). C. Blazquez.. 15. 38. (2006). Bulut. 35–42. (1918). 21. 1–39. U.C.. (1996)... V.. 259–267. G. T. Journal of Hazardous Materials. KungligaSvenskaVetenskapsakademiens.. 140.J.. Zurtheorie der sogenannten adsorption gel€ osterstoffe. & Zinjarde. U. H.. Garg. Chemosphere.. Khan.. Pseudo-second order model for sorption processes. Bansal. Journal of Physical Chemistry. Hong..K.M. S. Y.S.. S. & Singh. 467–471. & Liu. (1906). Removal and recovery of heavy metals by biosorption. U. Journal of Environmental Management. Bioresource Technology. Freundlich. Hernainz.W. Singh. A kinetics and thermodynamics study of methylene blue adsorption on wheat shells. & Sud. 22. Removal of lead (II) ions from synthetic and real effluents using immobilized Pinussylvestris sawdust: Adsorption on a fixed-bed column. 215.L. 207–215. Taty-Costodes. Zhu. 385–470.. 19. A. Jyoti.. 49–61. Removal of direct red 12B and methylene blue from water by adsorption onto Fe (III)/Cr (III) hydroxide. Journal of the American Chemical Society. 135. Kavitha. 47. 3600–3608. P. 89. Biosorption of Heavy Metals (pp. Lignocellulosic materials as potential biosorbents of trace toxic metals from wastewater. X. (2007). Batch and continuous packed column studies of chromium(III) biosorption by olive stone.S. (1999).. Suksabye. Journal of Hazardous Materials.J.. 951–967... Limaee. V. 17. 89–99.. (2009).. (2005).. Bioremediation Journal. No.. S. Arami. 177–188. Kinetics of adsorption on carbon from solution. (2011). M.. 162. 56–62. F. M.K. Namasivayam. G.. Bioresource Technology. Dubey. 29. & Aly. 202–208.C. S. Lagergren. Journal of hazardous materials. Cerrella. E. 194.. 42. Experimental and kinetic studies on methylene blue adsorption by coir pith carbon. Chromium adsorption and Cr(VI) reduction to trivalent chromium in aqueous solutions by soya cake. 14.. 42. & Garg. Process Biochemistry. 34. 135–144. 43. 16.. Biosorption and desorption of Nickel on oil cake: Batch and column studies. (1898). Margrave. & Moris. Gokhale. Volesky. Acta Physiochimica URSS. 218–229. 13. 31.E.P. A. Basso. Y. 135. Removal of hexavalent chromium from aqueous solution by agricultural waste biomass. & Sureshkumar.A.. Biosorption of chromium (Cr (III)/Cr (VI)) on the residual microalga Nannochlorisoculata after lipid extraction for biodiesel production. 451–465. & Adams. Y. 49–54. H. Bioresource Technology. G. 99. A. 20. & Namasivayam. Ho. The adsorption of gases on plane surfaces of glass. M. & Garg. S. (2008).33. Thiravetyan. Babel. 1. A.S. N. (2012). Bose.C. Acar. K.. K. 171. C. N. Park. Removal of hexavalent chromium from aqueous solution using lowcost activated carbons derived from agricultural waste materials and activated carbon fabric cloth. C. Salari. 94. V. 30. M. Journal of Hazardous Materials. I. P. 13–15. 523–544.D. Calero. Kim. 74. 12. (1963). Mahmoodi. Namasivayam. Weber. & Chaudhary. Faust.10.M. 27. Removal of chromium(VI) from water and wastewater using surfactant modified coconut coir pith as a biosorbent.. D. The removal of chromium(VI) from aqueous solutions by Fagusorientalis L.. 875.L. Liang. Sarswat..V. O. Equilibrium and Kinetic Studies on Biosorption of Heavy Metals by Leaf Powder of Paper Mulberry (Broussonetiapapyrifera). N. M. A. B. 32. (2002). 1361–1403. Feng. (2007).. The Suitability of Jatropha Seed Press Cake as a Biosorbent for Removal of Hexavalent Chromium from Aqueous Solutions. N. Guo. 1027–1042. E.. M. & McKay. H. (2011). (2004). Biosorption of chromium(VI) from aqueous solution and electroplating wastewater using fungal biomass.. Kinetic and equilibrium modeling of chromium (VI) biosorption on fresh and spent Spirulinaplatensis Chlorella vulgaris biomass. Y. Bankar. Chemical Engineering Journal. 94. Vankar. S. Biosorption of heavy metals from aqueous solutions by chemically modified orange peel. Equation of the characteristic curve of activated charcoal. (1940). 103.

. doi:10. H.K. Senthilkumar. (2012).C. C. 49.47.. 352 July 2014 Environmental Progress and Sustainable Energy. 29. Heterogeneous ion exchange in a flowing system. 48. M. Environmental Progress & Sustainable Energy. Environmental Progress & Sustainable Energy (Vol. K. Simultaneous adsorption and bioaccumulation: A study on continuous mass transfer in column reactor.. Vijayaraghavan. Jegan.. 1664–1666.2) DOI 10. Batch and column removal of total chromium from aqueous solution using Sargassumpolycystum.. (2010). 334– 341. Balomajumder. V.1002/ep . Mishra. & Agarwal. V. Thomas.11671.33. (1944). J. R. No.1002/ep. Journal of the American Chemical Society 66. & Velan.