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Applied Surface Science 283 (2013) 856862

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Applied Surface Science


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Adsorption of heavy metal ions from aqueous solutions by bio-char, a by-product of pyrolysis
Murat Klc a, C isem Krbyk b , zge C epeliog ullar c , Ays e E. Ptn a,
a b c

Department of Chemical Engineering, Faculty of Engineering, Anadolu University, 26555 Eskis ehir, Turkey Department of Chemical Engineering, Faculty of Engineering, Selc uk University, 42075 Konya, Turkey Department of Chemical Engineering, Faculty of Chemical and Metallurgical Engineering, Istanbul Technical University, 34469 Istanbul, Turkey

a r t i c l e

i n f o

a b s t r a c t
Bio-char, a by-product of almond shell pyrolysis, was used as an alternative adsorbent precursor for the removal of heavy metal ions from aqueous solutions. The adsorption potential of almond shell bio-char for Ni(II) and Co(II) removal was investigated. Adsorption experiments were carried out by varying pH, adsorbent dosage, initial metal ion concentrations, contact time and temperature to determine the optimum conditions. To describe the equilibrium isotherms the experimental data were analyzed by the Langmuir, Freundlich, DubininRadushkevich (DR) and Temkin isotherm models. Pseudo-rst order, pseudo-second order, and intraparticle diffusion kinetic models were used to nd out the kinetic parameters and mechanism of adsorption process. The thermodynamic parameters such as G , H and S were calculated for predicting the nature of adsorption. The results showed that bio-char derived from pyrolysis of biomass can be used as a low-cost and effective adsorbent for removal of heavy metal ions from aqueous solutions. 2013 Elsevier B.V. All rights reserved.

Article history: Received 27 February 2013 Received in revised form 3 July 2013 Accepted 7 July 2013 Available online 16 July 2013 Keywords: Bio-char Adsorption Heavy metal Isotherm Kinetic Thermodynamic

1. Introduction The human health and ecological systems are threatened to get worse because abundant and harmful heavy metals can be found in the water sources due to the rapid industrial and agricultural development together with the population growth [1]. One of the most toxicological relevance presented by the industrial and agricultural efuents is the heavy metals. The pollution of water resources due to the disposal of heavy metals has been an increasing worldwide concern for the last few decades [2]. Their presence in streams and lakes has been responsible for several health problems in animals, plants, and human beings. Toxic metal compounds coming to the earths surface not only contaminate earths water (seas, lakes, ponds and reservoirs), but can also contaminate underground water in trace amounts by leaking from the soil after rain and snow. Therefore, the earths water may contain various toxic metals [3]. Thus, it is important to remove heavy metal ions from waters and wastewaters before they are released to the environment. Several technologies have been developed for the removal of heavy metal pollutants from liquid wastes where they are present in high concentrations. These include methods such as precipitation, electroplating, ion exchange and membrane processes. These

Corresponding author. Tel.: +90 0 222 321 3550x6504; fax: +90 0 222 323 9501. E-mail address: aeputun@anadolu.edu.tr (A.E. Ptn). 0169-4332/$ see front matter 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.apsusc.2013.07.033

processes are difcult to implement on large scale due to expensiveness and other shortcomings such as ineffectiveness at low concentration (<100 mg/L) and production of toxic sludge and/or other waste products that also need disposal [4,5]. Adsorption on the other hand, is one of the most important physico-chemical treatment processes that is commonly used and applied for heavy metal removal from water samples and aqueous solutions [6]. Activated carbon is one of the most widely used adsorbents due to having extensive surface area, favorable pore size distribution and high degree of surface reactivity. Despite its widespread use in industries, activated carbon remains an expensive material [7]. Activated carbons are produced from a variety of carbonaceous materials. The choice of precursor largely depends on its availability, cost, and purity, but the manufacturing process and intended applications of the product are also important considerations [8]. Great efforts have been made to use the cheapest and unconventional adsorbents to adsorb heavy metals from aqueous solutions, such as aquatic plants, plant wastes, agricultural and industrial by-products [9]. Therefore, especially evaluation of biomass is getting increased attention in all over the world as it is renewable, widely available, cheap, and environmental friendly [10]. There are a number of biomass sources, such as forest residues, low grade plants, agricultural residues and municipal solid wastes, which can be utilized for activated carbon precursor [11]. Biomass is a renewable energy resource and has a growing interest as a chemical feedstock source. There are several

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thermochemical processes for conversion of biomass into valuable products which are combustion, gasication, liquefaction and pyrolysis. Among them pyrolysis is one of the primary thermochemical conversion methods to convert organic matters into valuable products, namely; solid char (bio-char), liquid (bio-oil) and gas (bio-gas) product yields and compositions that depend on pyrolysis conditions [12]. A great number of applications have been considered for liquid product (bio-oil), but the char has not received much attention. Evaluation of bio-char as low-cost adsorbent for wastewater treatment should be taken into account. Therefore, in this study, bio-char, obtained as a by-product of almond shell pyrolysis, was used as an alternative adsorbent precursor for the removal of heavy metal ions from aqueous solutions by adsorption. 2. Experimental 2.1. Raw material The almond (Prunus dulcis), is a species of tree native to the Middle East and South Asia. Almond is also the name of the edible and widely cultivated seed of this tree. Global production of almond is nearly 2,000,000 tons/yr and Turkey is one of the major almond producer and exporter countries. Turkeys almond production is nearly 60,000 tons/yr and between 30 and 50% of almond consists of shell, thus almond shells generated from industrial usage has a major economic importance and exhibits a high afnity for heavy metals. Almond shells used in this study were obtained from Datc aMug la located in the Aegean Region in south-west Turkey. Air-dried shells were ground in a high-speed rotary cutting mill to obtain a uniform material of an average particle size (0.851.25 mm). Proximate analysis was performed to determine the amount of ash, volatile matter, moisture, and xed carbon of biomass. The weight fraction of xed carbon was calculated by the difference. Ultimate analysis was performed to determine the elemental composition. The weight fractions of carbon, hydrogen and nitrogen were determined by using elemental analyzer (Carlo Erba EA 1108). The weight fraction of oxygen was calculated by the difference. Component analysis was performed to determine the percentage distribution of cellulose, hemicellulose, and lignin structures in biomass. 2.2. Pyrolysis procedure Pyrolysis experiments of almond shells were carried out in a xed-bed Heinze retort under nitrogen (N2 ) ow of 100 cm3 /min with a heating rate of 10 C/min at 650 C to obtain porous biochars. A schematic diagram of the unit is represented in Fig. 1. The 316 stainless steel Heinze retort has a volume of 400 cm3 (70 mm ID) and is externally heated by an electrical furnace in which the temperature is measured by a thermocouple inside the bed. The connecting pipe between the reactor and the trapping system was heated to 400 C to avoid condensation of the bio-oil vapor. After reaching the nal pyrolysis temperature the reactor was set to cool to room temperature. Pyrolysis product yields were determined gravimetrically by weighing the three products. The liquid phase was collected in cold traps maintained at about 0 C using salty-ice. The traps and reactor were washed with dichloromethane solvent to obtain the liquid products. The liquid phase consisting of aqueous and oil phases were separated and weighed. Char yields were determined from the overall losses of the reactor tube. The gas yield was calculated by the difference. 2.3. Characterization of bio-char Surface area of char was calculated from N2 adsorption isotherms by BET (BrunauerEmmettTeller) method using

Table 1 Characteristics of almond shell. Proximate analysis (%) Moisture Ash Volatiles Fixed C 6.54 2.29 72.33 18.84 Ultimate analysis (%) C H N O 50.20 5.76 0.18 43.90 Structural analysis (%) Extractives Cellulose Hemicelluloses Lignin 7.52 38.62 31.23 20.34

Quantachrome Autosorb 1 analyzer. Before adsorption measurement, the samples were outgassed at 150 C for 3 h. SEM images of raw materials and char were recorded by using Zeiss EVO 50 scanning electron microscope. Samples were mounted on an aluminum stub using carbon bands and coated with a thin layer of gold-palladium in an argon atmosphere using Agar sputter coater.

2.4. Batch adsorption experiments The stock solutions were prepared by dissolving accurately weighted Ni (NO3 )2 6H2 O and Co(NO3 )2 6H2 O in distilled water to the concentration of 1000 mg/L and the concentration of experimental solutions were obtained by dilution. Double deionized water (Milli-Q Millipore 18.2 M /cm conductivity) was used for all solutions. The initial pH of each metal solution was adjusted to the required pH value by using 0.1 mol/L NaOH and 0.1 mol/L HCl solutions. Batch equilibrium adsorption experiments were performed using 50 mL of each Ni(II) and Co(II) solutions. After sorption process, the sorbent separated from the samples by ltering and the ltrate was analyzed using Varian Spectra A250 Plus model atomic adsorption spectrometer. To investigate the effects of adsorption parameters such as, pH (28), adsorbent dosage (110 g/L), initial metal ion concentration (50200 mg/L), contact time (30240 min) and temperature (2040 C) were studied in a batch mode of operation. The amount of heavy metal adsorbed per unit mass of the adsorbent (qe ) was calculated by using the following mass balance equation, qe = (Ci Ce )V W

(1)

and the percent adsorption of the metal was calculated as follows: (Ci Ce ) 100 Ci

Adsorption (%) =

(2)

where Ci is the initial metal ion concentration (mg/L), Ce is the equilibrium concentration of the metal ion (mg/L), V is the volume of solution (L), and W is the mass of biosorbent (g).

3. Results and discussion 3.1. Properties of raw material and bio-char Table 1 shows the proximate, structural and ultimate analysis results of biomass. As seen from Table 1, raw almond shell consists of 38.62% cellulose, 31.23% hemicellulose, 20.34% lignin, and 7.52% extractives. Fig. 2 shows scanning electron microscopy (SEM) images of raw almond shell and its bio-char. The escape of evolved volatile compounds from inside the particle gradually increases, when the nal temperature increases during the pyrolysis process. Therefore, porosity of bio-char and size of voids increase with increasing temperature. BET surface of bio-char was obtained as 145 m2 /g.

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Fig. 1. Schematic diagram of the xed-bed reactor.

3.2. Effect of pH on Ni(II) and Co(II) removal Since pH is one of the main variables affecting the sorption process, inuencing not only the speciation of the metal ions, but also the surface charge of the sorbent and the degree of ionization of the adsorbate during the reaction [13]. The effect of initial pH on the adsorption of Ni(II) and Co(II) was determined within the pH range of 28 and the results are given in Fig. 3. It is seen that the adsorption amount was increased as pH increased from 2 to 6 for both Ni(II) and Co(II) ions and decreased with increasing pH. As the pH increased from 2 to 6 the overall surface of the sorbents became negatively charged and this increased the Ni(II) and Co(II) interaction with binding sites. Decrease in adsorption efciency at higher pH (>6) is due to the formation of soluble hydroxylated complexes of the metal ions and their competition with the active sites, and as a consequence, the retention would decrease again [6]. Therefore, all the adsorption experiments in this study were carried out at pH 7 for both Ni(II) and Co(II) ions where the highest adsorption was obtained. 3.3. Effect of adsorbent dosage on Ni(II) and Co(II) removal Adsorbent dose is a signicant factor to be considered for effective removal as it determined sorbentsorbate equilibrium of the system [4]. In order to investigate the effect of the amount of biochar on Ni(II) and Co(II) adsorption, adsorbent dosage in the range of 110 g/L was used for the adsorption experiments and the results are given in Fig. 3 for adsorption (%) and the biosorption amount (mg/g). The adsorption amount decreases with an increase in adsorbent dosage. On the other hand, the percentage of the adsorption increased rst with an increasing amount of adsorbent and reached

saturation. The initial increase in the percentage of adsorption can be attributed to increased biosorbent surface area and the availability of more adsorption sites. The decrease in the adsorption amount may be attributed to overlapping or aggregation of adsorption sites resulting in decrease in total adsorbent surface area. According to the results for further batch equilibrium adsorption experiments 7 g/L adsorbent dose was selected for Ni(II) and 4 g/L adsorbent dose was selected for Co(II) taking into consideration of the qe value. 3.4. Effect of initial metal ion concentration and contact time on temperature-dependent adsorption The rate of adsorption is a function of the initial metal ion concentration, which makes it an important factor to be considered for effective biosorption [14]. Temperature of the medium is also an effective parameter on adsorption efciency [15]. The effects of initial metal ion concentration and contact time were determined within the range of 50200 mg/L and contact time range of 30240 min at 20, 30 and 40 C. The results are shown in Fig. 4. The adsorbed amount was increased as the initial metal concentrations and contact time increased. Large amounts of metal ions were removed within 150 min for both Ni(II) and Co(II). After that the capacity of adsorption remained constant. In general, the data revealed that sorption capacity increased with increase in initial metal ion concentrations for Ni(II) and Co(II) on adsorbent. Moreover, the experimental results showed that adsorbed amount was increased as temperature increased. The increase in adsorption with temperature may be attributed to either increase in the number of active surface sites available for adsorption on the adsorbent [16]. At higher temperatures the energy of the system seems to facilitate Ni(II) and Co(II) attachment onto the cell surface.

Fig. 2. SEM images of raw almond shell and bio-char.

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Fig. 3. Effect of pH and adsorbent dosage on Ni(II) and Co(II) sorption capacity.

Fig. 4. Effect of initial metal ion concentration and time on Ni(II) and Co(II) sorption capacity at 20, 30 and 40 C.

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Table 2 Adsorption models used in this work and their parameters. Isotherm Langmuir Equation qe =
qm KL Ce 1+ KL Ce

Linearized form
Ce qe

Parameters qe (mg/g): the amount of metal ion adsorbed at equilibrium qm (mg/g): complete monolayer adsorption capacity Ce (mg/L): the equilibrium concentration KL (L/mg): the Langmuir adsorption constant

1 qm KL

Ce qm

Freundlich

qe = KF Ce

1/n

lnqe = lnKF +

1 lnCe n

DubininRadushkevich (DR)

qe = qm exp( 2 )

ln qe = ln qm 2 = RT ln 1 +
1 E= 1 Ce

n: the empirical parameter relating the adsorption intensity, which varies with the heterogeneity of the material (dimensionless) KF ((mg/g)(L/mg) 1/n ): the Freundlich adsorption constant (mol2 /kJ2 ): the adsorption energy constant : the Polanyi potential R (8.314 J/(mol K)): the gas constant T (K): the absolute temperature E (kJ/mol): the mean free energy bT (J/mol): the Temkin constant related to the heat of adsorption KT (L/mg): the Temkin constant related to the equilibrium binding energy
k1 t 2.303

Temkin

qe = B ln (KT Ce )

qe = B ln KT + B ln Ce B=
RT bT

Pseudo-rst order

dqt dt

= k1 (qe qt )

log (qe qt ) = logqe

qe (mg/g): the adsorption capacity at equilibrium qt (mg/g): the adsorption capacity at time t t (min): contact time k1 (1/min): the rate constant of pseudo-rst order adsorption qt (mg/g): the adsorption capacity at time t k2 (g/mg min): the rate constant of pseudo-second order adsorption qt (mg/g): the adsorption capacity at time t kp (mg/g min1/2 ): the intraparticle diffusion rate constant C: the intercept

Pseudo-second order

dqt dt

= k2 (qe qt )2

t qt

1 k2 q2 e

1 qe

Intraparticle diffusion

qt = kp t1/2 + C

qt = kp t1/2 + C

Table 3 Fitting parameters for the Langmuir, Freundlich, DR and Temkin equations. Parameters T ( C) 20 C Ni(II) Langmuir qm KL R2 RL Freundlich n KF R2 D R qm E R2 Temkin KT b R2 Co(II) 30 C Ni(II) Co(II) 40 C Ni(II) Co(II)

20.00 0.094 0.989 0.096 7.092 9.299 0.907 17.62 0.00002 158 0.726 2.306 22.836 1056 0.886

28.09 0.024 1.000 0.291 3.413 5.078 0.995 23.09 0.00022 477 0.981 5.753 0.310 423 0.998

21.27 0.095 0.991 0.095 6.757 9.554 0.939 18.73 0.00001 224 0.777 2.557 16.851 985 0.920

27.86 0.028 0.996 0.259 3.610 5.669 0.948 23.79 0.00019 513 0.999 5.566 0.397 452 0.957

22.22 0.172 0.994 0.055 10.989 13.585 0.896 20.41 0.000005 316 0.713 1.773 1219.99 1467 0.876

26.95 0.041 0.997 0.197 5.155 8.749 0.990 23.59 0.00011 674 0.909 4.147 1.776 627 0.984

Table 4 Comparison of adsorption capacities of various biomass precursors. Adsorbent source Adsorption conditions: Ni(II)/Co(II) pH Daucus carota L. Cladonia furcata Seaweeds Chlorella vulgaris Garcinia mangostana Lemna minor L. Waste apricot Almond shell 5.25/5.25 5.0/ 4.5/4.0 4.5/ /4.0 5.0/ 5.0/ 7.0/7.0 Concentration (mg/L) 400/400 10/ 100/100 250/ /125 100/ 10/ 100/100 Adsorbent dosage (g/L) 5.0/ 8.0/ 4.5/4.5 1.0/ /2.0 1.25/ 25.0/ 7.0/4.0 Max. metal uptake (mg/g) Ni(II) 6.03 7.90 20.63 63.25 55.00 101.01 22.22 Co(II) 5.75 18.58 0.34 28.09 [3] [6] [28] [29] [30] [31] [32] This study Reference

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3.5. Equilibrium modeling Adsorption is a well-known equilibrium separation process for wastewater treatment. Adsorption isotherms are the equilibrium relationships between the concentrations of the adsorbed metal and the metal ion in the solution at a given temperature. In this study Langmuir [1719], Freundlich [20], DubininRadushkevich (DR) [2123] and Temkin isotherm [2426] models were used to investigate the adsorption equilibrium between the metal solution and the activated carbon phase which are described in Table 2. The Langmuir parameters can be used to predict the afnity between the adsorbate and the adsorbent using dimensionless separation factor (RL ). RL is calculated by the following equation [27]:

Table 5 Kinetic parameters obtained at different temperatures. Parameters T ( C) 20 C Ni(II) Pseudo-rst-order qe(exp) 4.61 qe 2.158 k1 0.0115 2 R 0.986 Pseudo-second-order qe 4.608 k2 0.0136 R2 0.995 Intra-particle diffusion kP 0.174 C 2.197 R
2

30 C Co(II) Ni(II) Co(II)

40 C Ni(II) Co(II)

8.64 1.841 0.0138 0.940 8.696 0.0204 0.998 0.148 6.699 0.920

4.908 2.259 0.0115 0.991 4.975 0.0131 0.996 0.186 2.410 0.999

8.895 2.014 0.0138 0.934 8.928 0.0184 0.998 0.169 6.670 0.930

5.475 2.208 0.0069 0.962 5.155 0.0156 0.962 0.169 2.845 0.964

9.768 7.161 0.0322 0.705 10.309 0.0092 0.988 0.249 6.683 0.810

1 RL = 1 + KLCo

(3)

0.992

3.7. Thermodynamic modeling where Co is the highest initial phenol concentration of the adsorbate in the solution (mg/L). The value of RL indicates the shape of the isotherm to be either unfavorable (RL > 1), linear (RL = 1), favorable (0 < RL < 1) or irreversible (RL = 0). The Langmuir, Freundlich, DubininRadushkevich (DR) and Temkin isotherm parameters for adsorption of Ni(II) and Co(II) are given in Table 3. Comparison of the R2 values shows that the Langmuir isotherm tted quite well with the experimental data. In other words, this result may be due to the homogenous distribution of active sites on the surface of the adsorbent. Maximum monolayer adsorption capacities qmax were 20.00, 21.27, 22.22 mg/g for Ni(II) and 28.09, 27.86, 26.95 mg/g for Co(II), respectively. RL values are greater than zero and less than unity, showing favorable adsorption of Ni(II) and Co(II) onto bio-char. Adsorption capacities have been compared with other reported studies from the literature and presented in Table 4. The experimental data of the present study are comparable with reported values and was found to be higher than that of many reported studies. Temperature dependence of the adsorption process is associated with several thermodynamic parameters. Thermodynamic considerations of an adsorption process are necessary to conclude whether the process is spontaneous or not. The Gibbs free energy change is an indication of spontaneity of a chemical reaction and therefore is an important criterion for spontaneity. Also, both energy and entropy factors must be considered in order to determine the Gibbs free energy of the process [38]. Thermodynamic parameters such as Gibbs free energy change ( G ), enthalpy change ( H ) and the entropy change ( S ) can be estimated using equilibrium constants changing with temperature. The Gibbs free energy change of the adsorption reaction can be determined from the following equation: G = RT lnKL (4)

where R is gas constant (8.314 J/mol K), KL is equilibrium constant and T is absolute temperature (K). The KL value was calculated using the following equation: KL = qe Ce (5)

3.6. Kinetic modeling The kinetics of adsorption is an important characteristic to dene the efciency of adsorption. In order to investigate the mechanism of adsorption and kinetic parameters sorption data was analyzed using pseudo-rst order [33,34], pseudo-second order [35,36], and intraparticle diffusion [37] models which are described in Table 2. Pseudo-rst order, pseudo-second order, and intraparticle diffusion kinetic parameters are represented in Table 5. The correlation coefcient for the pseudo-second order kinetic model was higher than the other models (R2 = 0.999) for both Ni(II) and Co(II) ions indicating that the adsorption perfectly complies with pseudosecond order reaction and the adsorption process appeared to be controlled by the chemisorption process. In addition, the theoretical qe values found from the second-order kinetic model are in accordance with the experimental qe values.
Table 6 Adsorption models used in this work and their parameters. T ( C) Ni(II) G 20 30 40 (kJ/mol) S (J/mol K) H (kJ/mol)

where qe and Ce is the equilibrium concentration of metal ions on adsorbent (mg/g) and in the solution (mg/L), respectively. Relation between G , H and S can be expressed by the following equations: G = H T S Eq. (6) can be written as
lnKL = G = H + S RT RT R

(6)

(7)

According to Eq. (7), H and S parameters can be calculated from the slope and intercept of the plot of ln KL versus 1/T, respectively [6,22,38]. The calculated values of Gibbs free energy change ( G ), enthalpy ( H ), and entropy ( S ) are given in Table 6. The negative G values indicate that the process is thermodynamically feasible, spontaneous and corresponding to a chemical

Co(II) G (kJ/mol) 9.09 9.01 8.33 S (J/mol K) H (kJ/mol)

5.76 5.92 5.58

57.375

22.805

37.388

20.145

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process of Ni(II) adsorption. Moreover, the decrease in G values with increase in temperature shows a decrease in feasibility of sorption at higher temperatures. The positive value of H indicates that the nature of adsorption process is endothermic in all cases. This behavior indicates that higher temperatures are more preferred for higher sorption. This is also supported by the increase in value of uptake capacity of the sorbent with the increase in temperature (Fig. 4). The positive value of S shows the increased randomness at the solidsolution interface during the sorption process. 4. Conclusions In this study bio-char, a by-product of pyrolysis process, was evaluated as an alternative low-cost adsorbent for removal of Ni(II) and Co(II) ions from aqueous solution. Optimum adsorption conditions were determined as a function of pH, adsorbent dosage, initial metal ion concentration, contact time and temperature of solution for Ni(II) and Co(II) removal. Langmuir adsorption isotherm model adequately described the adsorption of Ni(II) and Co(II) ions onto bio-char. The pseudo-second order kinetic model better described the sorption kinetics with high correlation coefcients. The thermodynamic parameters G , H and S show a chemically favored, spontaneous and endothermic adsorption. It can be concluded that almond shell bio-char seems an effective, alternative, and low cost sorbent precursor for the removal of heavy metals from aqueous solutions. References
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