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3 AUTHORS, INCLUDING:
Omotayo Sarafadeen Amuda
Abdur-Rahim Giwa
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Received 1 September 2006; received in revised form 11 February 2007; accepted 12 February 2007
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Abstract
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Keywords: Coconut shell; Chitosan-coated carbons; Heavy metals; Industrial wastewater; Adsorption isotherms
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The present study was undertaken to develop a cost effective biosorbent and to study the biosorption process involved in the adsorption of heavy
metal-contaminated industrial wastewater using the developed biosorbent. Coconut shell carbon was modified with chitosan and/or oxidizing agent
(phosphoric acid) to produce composite adsorbent. The adsorption efficiency of the adsorbent was evaluated by measuring the extent of adsorption
of zinc (II) in synthetic beverage industrial wastewater. Operational parameters such as pH, agitation time and adsorbent concentration, initial
ion concentration and particle size were also studied. Adsorption data fitted well with the Langmuir and Freundlich models. However, Langmuir
isotherm displayed a better fitting model than Freundlich isotherm because of the higher correlation coefficient that the former exhibited, thus,
indicating to the applicability of monolayer coverage of the zinc (II) on the surface of adsorbent.
Desorption studies were carried out with NaOH and quantitative recovery of the metal was evident. The dominant sorption mechanism is ion
exchange. The use of agricultural waste (coconut shell) and aquatic waste (chitin) to produce activated carbon potentially leads to the production
of a highly effective adsorbent generated from less expensive raw materials that are from renewable resources.
2007 Published by Elsevier B.V.
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1. Introduction
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Please cite this article in press as: O.S. Amuda et al., Removal of heavy metal from industrial wastewater using modified activated coconut shell
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2. Materials
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3. Method
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Please cite this article in press as: O.S. Amuda et al., Removal of heavy metal from industrial wastewater using modified activated coconut shell
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Table 1
The characteristics of the adsorbents
Parameters
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Adsorbents
CACSC
CCSC
ACSC
F-300
902
0.60
2.70
5.90
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670
0.49
5.62
9.60
210
668
0.52
1.45
5.50
172
628
0.47
6.53
7.40
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Ci Cf
100,
Ci
(1)
where Ci and Cf are the initial and final equilibrium concentration of Zn (II) (mg/L) in wastewater, respectively, and
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Kd =
amount of Zn in adsorbent
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(mL/g),
amount of Zn in solution
M
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100Kd
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Kd + V/m
(3)
All the experiments were duplicated to ensure accuracy, reliability and reproducibility of the collected data. Relative error
did not exceed 0.01.
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4.1.1. Effect of pH
The effect of pH on the adsorption of Zn (II) is presented
in Fig. 2. The pH of the aqueous solution is an important operational parameter in the adsorption process because it affects
the solubility of the metal ions, concentration of the counter
ions on the functional groups of the adsorbent and the degree of
ionization of the adsorbate during reaction [7]. Thus, the role of
hydrogen ion concentration was examined on the Zn (II) removal
efficiency. The pH was varied from 1 to 11, other operational
parameters (adsorbent dose, agitation time) were kept at the optimum and temperature and agitation speed were kept at 25 C and
200 rpm, respectively.
From Fig. 2, it is shown that increasing pH of the solution
from 2 to 6 caused linear increase in Zn removal efficiency. The
removal efficiency remained almost constant above pH 6. This
may be due to the formation of soluble hydroxyl complexes.
The onset of metal hydrolysis and precipitation begin at pH > 6
Please cite this article in press as: O.S. Amuda et al., Removal of heavy metal from industrial wastewater using modified activated coconut shell
carbon, Biochem. Eng. J. (2007), doi:10.1016/j.bej.2007.02.013
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Please cite this article in press as: O.S. Amuda et al., Removal of heavy metal from industrial wastewater using modified activated coconut shell
carbon, Biochem. Eng. J. (2007), doi:10.1016/j.bej.2007.02.013
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depend on the pH. They further reported amine group on chitosan is protonated to different degrees at low pH. The NH3 +
group on the chitosan is chiefly responsible for interaction with
anions and negatively charged surfaces [7]. Oxidation of nutshell carbon with mineral acids has been implicated to introduce
more acidic C O groups on the surface of nutshell carbons.
This would enhance the electrostatic interaction between chitosan and the more negatively charged CACSC, thus, preventing
agglomeration of chitosan [7]. Formation of more acidic surface
oxides on CACSC than CCSC enhanced efficient coating of chitosan, enhanced its hydrophilic character and hence improved
the hydrodynamic flow. This could be responsible for high
adsorption capacity of CACSC over CCSC. The least adsorption capacity was exhibited by ACSC. At higher pH (>5) the
presence of oxygen-containing functional groups, makes the
adsorbent surface negatively charged and hence repulsive electrostatic interaction between the adsorbent and anions occurred
[7].
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Fig. 4. Effect of agitation time on removal efficiency of Zn (II) by the adsorbents. Zn (II) dosage: 25 mg/L; agitation speed: 200 rpm; dose of each adsorbent:
30 g/L; pH of solution: 6; temperature of solution: 25 C.
Please cite this article in press as: O.S. Amuda et al., Removal of heavy metal from industrial wastewater using modified activated coconut shell
carbon, Biochem. Eng. J. (2007), doi:10.1016/j.bej.2007.02.013
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(4)
R=
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Types of isotherm
R>1
R=1
0<R<1
R<0
Unfavorable
Linear
Favorable
Irreversible
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(6)
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Values (R)
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(5)
where b is Langmuir constant (L/mg) and C0 is initial concentration (mg/L). It has been shown using mathematical calculations
that parameter R indicates the shape of the isotherms [34] as
follows:
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1
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Please cite this article in press as: O.S. Amuda et al., Removal of heavy metal from industrial wastewater using modified activated coconut shell
carbon, Biochem. Eng. J. (2007), doi:10.1016/j.bej.2007.02.013
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Table 2
Langmuir and Freundlich constants for the adsorption of Zn (II) at 25 C
CACSC
CCSC
ACSC
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Kf
1/n
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2010
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60.41
50.93
45.14
0.997
0.995
0.996
10.59
9.67
7.47
0.59
0.49
0.38
= correlation coefficient.
R2
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0.955
0.952
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R2
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qe (mg/g)
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b (L/mg)
Table 3
Comparison of the Langmuir constants for Zn adsorption onto adsorbents
Adsorbent
Mangifera indica
Coal ash
Wood ash
Natural zeolite
Fly ash
Clay mineral
CACSC
CCSC
ACSC
qe (mg/g)
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Freundlich constants
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Langmuir constants
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13.72
60.41
50.93
45.14
This isotherm does not predict any saturation of the sorbate; thus
infinite surface coverage is predicted mathematically, indicating
to multilayer adsorption on the surface [28].
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Fig. 10. Sodium hydroxide concentrationNaOH (M) as function of % desorption of Zn (II) from the adsorbents.
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References
[35]
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This study
This study
This study
Please cite this article in press as: O.S. Amuda et al., Removal of heavy metal from industrial wastewater using modified activated coconut shell
carbon, Biochem. Eng. J. (2007), doi:10.1016/j.bej.2007.02.013
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that provided chitin that was used for the preparation of chitosan;
and staff of Rotas Soilab, Ibadan were appreciated. The effort
of our students that helped during sampling cannot be under
estimated.
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Please cite this article in press as: O.S. Amuda et al., Removal of heavy metal from industrial wastewater using modified activated coconut shell
carbon, Biochem. Eng. J. (2007), doi:10.1016/j.bej.2007.02.013
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