Journal of Chemistry
Volume 2015 (2015), Article ID 842707, 8 pages
http://dx.doi.org/10.1155/2015/842707

Research Article

Effective Remediation of Lead Ions from Aqueous Solution by Chemically Carbonized Rubber Wood Sawdust: Equilibrium, Kinetics, and Thermodynamic Study

Swarup Biswas¹ and Umesh Mishra²

¹Department of Environmental Engineering, NIT Agartala, Tripura 799046, India
²Department of Civil Engineering, NIT Agartala, Tripura 799046, India

Received 10 June 2015; Accepted 2 August 2015

Academic Editor: Wenshan Guo

Copyright © 2015 Swarup Biswas and Umesh Mishra. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract.

Rubber wood sawdust was carbonized into charcoal by chemical treatment which was used for removal of lead ion from aqueous solution. The work involves batch experiments to investigate the pH effect, initial concentration of adsorbate, contact time, and adsorbent dose. Experimental data confirmed that the adsorption capacities increased with increasing inlet concentration and bed height and decreased with increasing flow rate. Adsorption results showed a maximum adsorption capacity of 37 mg/g at 308 K. Langmuir, Freundlich, and Temkin model adsorption isotherm models were applied to analyze the process where Temkin was found as a best fitted model for present study. Simultaneously kinetics of adsorption like pseudo-first-order, pseudo-second-order, and intraparticle diffusion models were investigated. Thermodynamic parameters were used to analyze the adsorption experiment. Fourier transform infrared spectroscopy, scanning electron microscope, and energy dispersive X-ray spectroscopy confirmed the batch adsorption of lead ion onto chemically carbonized rubber wood sawdust.

1. Introduction

Water pollution due to contamination of toxic lead ions is a serious problem for human health and environment. Lead discharged from petrochemical, organic, and inorganic fertilizer, oil refineries, and automobile industries contaminates the ground water and surface water [1, 2]. According to the US Environmental Protection Agency (EPA), World Health Organization (WHO), and Indian Standard (IS), permissible limit of lead ion in drinking water is 0.015 mg/L, 0.01 mg/L, and 0.05 mg/L, respectively. Commercial methods such as filtration, chemical oxidation/reduction, electrochemical treatment, chemical precipitation, membrane separation, and ion-exchange methods have been also utilized for the remediation of heavy metal contamination. Due to inefficiency and high operating cost these processes are not so much effective. Therefore in this study we adopted adsorption process for removal of lead ion. Many biosorbents, for example, Caulerpa lentillifera [3], sago waste [4], sawdust [5], jute [5], coir [6], algae [7], waste tea leaves [8], ground nut shell [5], rice husk ash [9], and papaya wood [10], were previously investigated by various researchers for removal of lead ions.

In this study chemically carbonized rubber wood sawdust (CCRWSD) was utilized for removal of lead ions from synthetic wastewater. The pH effect, initial concentration, contact time, and adsorbent dose in batch mode were investigated. In addition isotherm, kinetic, and thermodynamic study were carried out to compare the experimental data and to understand the adsorption behavior of lead ion onto CCRWSD.

2. Materials and Methods

2.1. Preparation of Biomass

Rubber wood sawdust was collected from rubber wood processing industry, Nagechera, Tripura, India. The carbonization and activation were done in two steps, where in first step rubber wood sawdust (10 gm) was added in concentrated sulphuric acid (11 mL, 98% m/m) for carbonization and kept for 10 minutes. Then in second step carbonized black slurry was mixed with concentrated nitric acid (6.6 mL, 65% m/m) and kept in air oven at 150°C for 24 hours. Carbonized sawdust was centrifuged with deionized water until the pH became neutral and dried in °C. Screening of the dried CCRWSD was done to get desired particle sizes ranging from 0.5 to 1 mm.

2.2. Characterization of the Adsorbent

Atomic absorption spectrophotometer (Perkin Elmer Model AAS 700) was utilized to determine the lead concentration in effluent and influent samples. Fourier transform infrared spectroscopy (FTIR) (Bruker 3000 Hyperion, Germany) was used to study the functional group present in adsorbent. Scanning electron microscope (SEM) (JELO JSM7600F) supported by EDS (energy dispersive X-ray spectroscopy) (Oxford AZtech energy system) was utilized to characterize the surface of adsorbent.

2.3. Batch Experiment

Batch experiment was carried out in a thermostatically controlled magnetic stirrer at 30°C with the speed of 120 rpm. A 0.5 g of CCRWSD was utilized at different concentration (5 mg/L to 30 mg/L) and at different pH (2.1 to 6.8). The experiment was done at different adsorbent dose (0.25 g/L to 5 g/L). For thermodynamic study the adsorption experiment was conducted in three different temperatures (303 K, 313 K, and 323 K). After completing every batch experiment the solution was filtered and sample was tested to know the residual lead concentration.

3. Results and Discussion

3.1. Characterization of the Adsorbent

Before and after adsorption functional groups were identified by using FTIR in the range of 400–4000 cm⁻¹ as shown in Figures 1 and 2. In CCRWSD the peak at 1708.58 cm⁻¹ and 1612.56 cm⁻¹ shows the presence of C=O group and –COO⁻ group. Another major peak is observed at 1162.34 cm⁻¹ which is due to C–O group. The peak at 3419 cm⁻¹ is due to O–H stretch from carboxyl group (O=C–OH and C–OH) and peak 2923.40 cm⁻¹ represents the presence of O–H stretch (hydrogen bonded –COOH). Important fact is that the shifting of peaks is observed after adsorption of lead ion which is a strong evidence of adsorption in the CCRWSD. After adsorption of lead ion, peaks are shifted because carboxyl and hydroxyl group may release proton and form new complexes with lead ion. SEM analysis (Figures 3 and 4) suggests the change in surface structure before and after adsorption of lead ion. On the other hand, EDS results also confirm the feasibility of lead adsorption process (Figures 5 and 6).

Figure 1: FTIR spectra of CCRWSD.

Figure 2: FTIR spectra of lead ion loaded CCRWSD.

Figure 3: SEM image of CCRWSD.

Figure 4: SEM image of lead ion loaded CCRWSD.

Figure 5: EDS spectra of CCRWSD.

Figure 6: EDS spectra of lead ion loaded CCRWSD.

3.2. Batch Result Analysis

Adsorption capacity is increased with the increasing of solution pH from 2.1 to 5.6 and then starts to decrease with increasing pH as shown in Figure 7. At low pH adsorption capacity is low because of higher concentration of H⁺ ion in the solution which occupies the binding sites of adsorbent.

Figure 7: Effect of pH on the adsorption of lead ions onto CCRWSD ( mg/L, dose = 0.5 g/L, contact time = 120 min, and temperature = 30°C).

Effect of contact time on adsorption of lead ion onto CCRWSD is shown in Figure 8. It is observed that the rapid adsorption is taking place in first half an hour and thereafter rate of lead ion adsorption decreases. After some time period of adsorption surface sites are occupied by lead ion and adsorption process decreases.

Figure 8: Effect of contact time on the adsorption of lead ions onto CCRWSD ( mg/L, dose = 0.5 g/L, pH = 5.6, and temperature = 30°C).

It is found that adsorption capacity increases from 9.82 to 36.4 mg/g with the increase in initial lead ion concentration from 5 to 30 mg/L. At lower concentration maximum adsorption sites are available for adsorption of lead ion. On the other hand at higher concentration many lead ions left unabsorbed in the solution as the entire binding site get saturated by lead ion.

Adsorption capacity increases from 3.96 mg/g to 37 mg/g with the decreasing of adsorbent dose from 5 g/L to 0.25 g/L. As binding sites of adsorbent increase with the increasing adsorbent amount the removal percentage increases.

3.3. Adsorption Isotherms

In batch adsorption process, Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich (D-R) isotherm models were utilized to describe the equilibrium data.

Langmuir adsorption isotherm [11] equation is expressed as

where (mg/g) is the amount of lead adsorbed at equilibrium, (mg/L) is the equilibrium concentration of lead ion in solution, (L/mg) is the Langmuir constant, and (mg/g) is the maximum adsorption amount of lead ion per unit weight of adsorbent to form a complete monolayer on the surface bound at . The values of and are calculated from the slopes and intercepts of linear plots of / versus (Figure 9) and are illustrated in Table 1.

Table 1: Parameters of Langmuir, Freundlich, and Temkin adsorption isotherm constants for adsorption of lead onto CCRWSD.

Langmuir
Freundlich
Temkin
Dubinin-Radushkevich

(mg/g)
41.15
(mg/g)
27.63

8.16
(mg/g)
32.06

(L/mg)
2.73

2.44
(J/mol)
308.76
(mol² J²)
0.0031

0.859–0.960

0.988
(L/g)
34.1
(kJ/mol)
12.70

0.992

0.993

0.954

Figure 9: Langmuir isotherm (pH = 5.6, = 5–20 mg/L, dose = 0.5 g/L, contact time = 180 min, and temperature = 30°C).

Langmuir isotherm can be checked by the value of (2) [12] as isotherm is irreversible (), favorable (), linear (), or unfavorable ():

where (mg/L) and (L/mg) are denoted by initial concentration of lead ion and Langmuir constant. In experiment values are found to be 0.859–0.960 which indicates the favorable lead adsorption.

Linear form of the Freundlich isotherm is expressed as [13]

where and are known as Freundlich coefficients, (mg/g) is the amount of lead ion adsorbed, and (mg/L) is the concentration of lead solution at equilibrium. For applying Freundlich model, is plotted against / (Figure 10) which gives the value of and . The values of the Freundlich coefficients and the correlation coefficients are explained in Table 1. The value of is 2.44 for lead adsorption on CCRWSD. As the value of lies between 1 and 10, it can be concluded that Freundlich model is favorable for lead adsorption studies.

Figure 10: Freundlich isotherm (pH = 5.6, = 5–20 mg/L, dose = 0.5 g/L, contact time = 180 min, and temperature = 30°C).

Temkin isotherm model is generally expressed as [14]

is expressed as , where (J/mol) is the Temkin constant and (K) is the absolute temperature in Kelvin. (8.314 J/mol K) is the gas constant and (L/g) is the Temkin isotherm constant. The plot of versus (Figure 11) gives the values of , , and . The values of the Temkin constants () and correlation coefficients () are shown in Table 1. Value of is greater than 0.99 which justifies that model is well fitted for adsorption of lead ion on the surface of CCRWSD.

Figure 11: Temkin isotherm (pH = 5.6, = 5–20 mg/L, dose = 0.5 g/L, contact time = 180 min, and temperature = 30°C).

Linearized form of Dubinin-Radushkevich isotherm equation [15] is expressed as

where (mg/g) is the number of lead ions adsorbed per unit weight of CCRWSD, (mg/g) is the maximum adsorption capacity, and (mol² J²) is the activity coefficient.

(kJ/mol) is the adsorption energy and is the Polanyi potential. is expressed as

where (J/mol K) and (K) are the gas constant and temperature. The plot of versus (Figure 12) gives the value of (mol²/J²) and (mg/g). The equation which is used for the calculation of adsorption energy is expressed as

Figure 12: D-R isotherm (pH = 5.6, = 5–20 mg/L, dose = 0.5 g/L, contact time = 180 min, and temperature = 30°C).

These parameters give the information about sorption mechanism, either chemical ion-exchange or physical sorption. D-R parameters are calculated from the plot of versus and listed in Table 1. From calculation it is found that the value of adsorption energy is 12.70 kJ/mol. The value of adsorption energy is greater than 8 kJ/mol and smaller than 16 kJ/mol which indicates chemisorption phenomenon [16].

After calculation of all isotherms it is observed that the value of correlation coefficients () for Temkin model is higher than the other isotherms from which it can be concluded that Temkin model is the best fitted model for this adsorption process. Langmuir, Freundlich, and Dubinin-Radushkevich are also well fitted models for the present system; hence the adsorption process can be described by these models also. In Langmuir model maximum adsorption capacity () at monolayer is measured whereas Dubinin-Radushkevich deals with the maximum adsorption capacity () at microspores volume of CCRWSD (Table 1). As a result value of the adsorption capacity from Langmuir model is higher than the Dubinin-Radushkevich model. Furthermore, high value of (L/mg) indicates that there is a strong interaction between the functional group of the adsorbent and lead ion which leads to an efficient adsorption process.

3.4. Adsorption Kinetics

Adsorption kinetic studies were conducted to have a better and broader understanding of the dynamic behaviour of lead adsorption onto CCRWS. Pseudo-first-order, pseudo-second-order, and intraparticle diffusion models are applied to study the adsorption process.

Pseudo-first-order model [17] is expressed as

where (mg/g) and (mg/g) are the amount of lead ions adsorbed at time (min) and at equilibrium per unit weight of the adsorbent. (mg/g) is the amount of lead ion adsorbed at any time and (min⁻¹) is the pseudo-first-order rate constant. The plot of versus (not shown in figure) at different concentration gives the values of and .

The values of and are shown in Table 2, where values of are quite similar with experimental data and values of are close to the unity. Similarities indicate the better agreement of pseudo-first-order model with the experimental data.

Table 2: A pseudo-first-order, pseudo-second-order, and intraparticle diffusion model parameter for adsorption of lead ion onto CCRWSD.

Constants
Initial concentration (mg/L)

5
10
15
20

(mg/g)
9.82
19.31
28.05
35.8

Pseudo-first order

     (mg/g)
7.58
16.52
27.29
31.87

     (min⁻¹)
0.0283
0.0377
0.0301
0.0458

0.991
0.995
0.984
0.990

Pseudo-second order

     (mg/g)
10.12
2.02
3.26
37.45

     (g mg⁻¹ min⁻¹)
0.016
0.600
0.199
0.004

0.998
0.995
0.988
0.998

Intraparticle diffusion

     (g mg⁻¹ min⁻¹)
0.709
1.488
2.294
2.763

0.873
0.895
0.926
0.872

Pseudo-second-order model [18] is expressed as

where (g/mg min) is the pseudo-second-order rate constant. (mg/g) and (mg/g) are the maximum capacity at equilibrium and at time (min). Values of (g/mg min) and (mg/g) are determined by using the plot of versus (Figure 13). The results are shown in Table 2 where values of theoretical adsorption capacities are not closer to the experimental data which concludes that the pseudo-second-order model is not suitable to explain the kinetics of the present adsorption system.

Figure 13: Pseudo-second-order model (pH= 5.6, dose = 0.5 g/L, contact time = 180 min, and temperature = 30°C).

Adsorption process is also checked by applying intraparticle diffusion model which is expressed as [19]

where (mg/g min) is the intraparticle diffusion constant. The plot of versus (Figure 14) gives the values of .

Figure 14: Intraparticle diffusion model (pH= 5.6, dose = 0.5 g/L, contact time = 180 min, and temperature = 30°C).

Results of the model are summarized in Table 2, where it can be seen that the values of for intraparticle diffusion model are lower than the other models. So intraparticle diffusion model is not sufficient to explain the present system.

3.5. Thermodynamic Study

Thermodynamic study of lead ion adsorption by CCRWSD was conducted in three different temperatures (303, 313, and 323 K). Gibbs free energy () (kJ/mol) of adsorption can be calculated by using (11) and (12) [20]. Enthalpy change () (kJ/mol) and entropy change () (J/K mol) are also the most important thermodynamic parameters which influence the adsorption process and they can be calculated by using (13) and (14) [20]:

where denotes gas constant, (mg/g) is the adsorption capacity at equilibrium, and (mg/L) is the concentration at equilibrium at absolute temperature (K). The slope and intercept of versus give (Figure 15) the value of and .

Figure 15: Thermodynamic plot for adsorption of lead ions onto CCRWSD (pH = 5.6, dose = 0.5 g/L, contact time = 180 min, and concentration = 20 mg/L).

A summary of calculated thermodynamic parameter is given in Table 3. The negative values of for lead ion adsorption indicate that the process is spontaneous and positive value of (+10.474 kJ/mol) is an indication of endothermic process. Positive value of (+51.332 J/K mol) reflects the randomness at solid solution interface.

Table 3: Thermodynamic parameters for lead adsorption (pH = 5.6, dose = 0.5 g/L, contact time = 180 min, and concentration = 20 mg/L).

(K)
(kJ/mol)
(J/K mol)
(kJ/mol)

303
+10.474
+51.332
−5.064

313

−5.627

323

−6.089

4. Conclusions

CCRWSD was found as a feasible adsorbent medium with maximum adsorption capacity of 37 mg/g in batch mode. The adsorption capacity is greatly affected by the pH of sample solution and its concentration. Batch experimental data shows a good agreement with Temkin isotherm model and the pseudo-first-order kinetic model. For low cost and high adsorption capacity CCRWS would be a good promising adsorbent for lead contaminated wastewater treatment.

Conflict of Interests

The authors declare that there is no conflict of interests regarding the publication of this paper.

Acknowledgment

The authors are thankful to Director of National Institute of Technology Agartala for providing necessary research facilities.

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