Académique Documents
Professionnel Documents
Culture Documents
Department of Chemistry, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, 35900 Tanjung Malim, Perak, Malaysia
Nanotechnology Research Centre, Faculty of Science and Mathematics, Universiti Pendidikan Sultan Idris, Tanjung Malim, Perak, Malaysia
A R T I C L E I N F O
A B S T R A C T
Article history:
Received 26 March 2014
Accepted 17 August 2014
Available online 21 August 2014
The efcacy of coconut dregs residue, a by-product from coconut milk production factory, to adsorb
Cu(II), Ni(II) and Pb(II) ions from aqueous solutions was investigated. The effects of experimental
parameters such as solution pH, contact time and initial metal concentration on adsorption process were
examined in batch experiments. The equilibrium data were best described by the Langmuir isotherm
model, while the dynamical data followed the pseudo-second order kinetic model. The Freundlich
constant (n) and separation factor (RL) values suggest that the metal ions were favourably adsorbed onto
biosorbent. The afnity of the biosorbent for metal ion was in the order of Pb(II) > Cu(II) > Ni(II), both in
single- and multi-metal systems. The characterisation studies were carried out using scanning electron
microscope (SEM), energy dispersive X-ray spectrometer (EDX) and Fourier transform infrared
spectrometer (FTIR). Complexation between metal ions and binding sites of the biosorbents was the
main adsorption mechanism. Coconut dregs residue removed Cu(II) better than bamboo derived
activated carbon, a commercial activated carbon, from electroplating efuent.
2014 Elsevier Ltd. All rights reserved.
Keywords:
Adsorption
Characterisation
Equilibrium isotherm
Kinetics
Metal ions
Coconut dregs residue
Introduction
The release of industrial efuents containing excessive amount
of toxic metals to the environment have caused serious problems
with regards to water quality. Heavy metals such as Cr, Cu, Ni, Pb
and Zn can be found in the efuents of metal plating, battery
manufacturing, and leather nishing, mining and smelting
industries [1]. Heavy metals are non-biodegradable and carcinogenic contaminants. Therefore, their presence in the environment
can be harmful or nuisance to living organisms [2]. For example,
high intake of Cu can cause severe mucosal and central nervous
system irritation, kidney and liver dysfunction, anaemia and
gastrointestinal diseases [3]. According to Bahadori et al. [4], there
were 10 countries had serious water contamination issues in 2010.
The top 5 countries were Brazil, USA, China, Indonesia and Japan.
Due to rapid industrialisation, water pollution is becoming a
generate solid residues and suitable for a wide range of metal ion
concentrations [2,10]. Activated carbon has been widely used as an
adsorbent because it has large surface area and high adsorption
capacity [11]. In spite of its excellent ability to treat industrial
efuents, activated carbon is costly [12]. Therefore, alternative
adsorbents derived from natural materials, agricultural and
industrial wastes that are available in large quantities and cheap
need to be utilised [13,14].
Coconut dregs residue is the waste obtained from coconut milk
production and easily available at low-cost [15]. After extracting
most of the milk from the coconut, the remaining product is called
coconut dregs residue. This waste can be used to feed animal or just
let to decompose on the eld [15]. It was estimated that about
555,120 t of coconut have been produced in 2008 in Malaysia. From
this value, approximately 510,000 t of coconut has been used [16].
So, the application of coconut dregs residue for water clean-up can
offer a good solution for its disposal.
In this study, the potential of coconut dregs residue as a
biosorbent to sequester Cu(II), Ni(II) and Pb(II) ions from aqueous
solutions was evaluated. The effects of experimental parameters
such as solution pH, contact time and initial metal concentration
on metal ion adsorption were investigated. The equilibrium
adsorption data were tted with the Freundlich and Langmuir
isotherm models. The adsorption rates were determined using the
pseudo-rst order, pseudo-second order and intraparticle diffusion kinetic models. The characteristics of the biosorbents and
possible binding mechanism(s) involved were studied using SEM,
EDX and FTIR.
Materials and methods
Preparation of biosorbent
The coconut dregs residue was obtained from a coconut milk
production factory in Banting, Selangor. The residue was washed
thoroughly with deionised water and dried in an oven at 70 C for
7 days. The dried material was then ground and sieved through
150250 mm size fractions using an American Society for Testing
and Materials (ASTM) standard sieve. The ground material was
kept in self-sealing plastic bags to avoid moisture effects.
Preparation of stock solutions
The stock solutions of 1000 mg/L were prepared by dissolving
appropriate amount of Cu(NO3)22.5H2O (HmbG Reagent Chemicals), Ni(NO3)26H2O (Bendosen Laboratory Chemicals) and
Pb(NO3)2 (Bendosen Laboratory Chemicals) salts in 0.1 mol/L
KNO3. In this study, 0.1 mol/L KNO3 was used as an electrolyte
to control the ionic strength. The stock solutions were then diluted
to the required concentrations. Cu, Ni and Pb atomic absorption
spectrometer (AAS) standard calibration solutions were obtained
from Fisher Scientic. All reagents used were analytical reagent
grade, and deionised water was used throughout this study.
Characterisation studies
The surface area and pore diameter of coconut dregs residue
were determined using a Quantachrome Autosorb 1 Surface
Analyser. The surface area was determined according to the
BrunauerEmmettTeller (BET) multipoint technique [17], meanwhile the Barrett, Joyner and Halenda (BJH) technique was applied
for pore diameter analysis [18]. The surface area and pore diameter
of coconut dregs residue were measured as 0.38 m2/g and 1.83 nm,
respectively. According to the International Union of Pure and
Applied Chemistry (IUPAC) classication, the pore of the biosorbent corresponds to micropores (d < 2 nm).
1913
1914
[(Fig._2)TD$IG]
10
Effect of solution pH
The degree of ionisation of metal ions in aqueous solution and the
charge on the surface of adsorbents are greatly inuenced by the
solution pH [7]. The effects of solution pH on the adsorption of Cu(II),
Ni(II) and Pb(II) ions by coconut dregs residue were studied at an
initial pH ranged from 3.0 to 7.0 (Fig. 1). The adsorption studies were
performed within the pH range because it was observed that metal
ions formed insoluble hydroxide precipitates simultaneously at pH
value greater than 7.0. The removal of metal ions at pH value greater
than 7.0 was not solely by adsorption onto coconut dregs residue, but
due to hydroxide precipitation as well. This phenomenon leads to
inaccurate interpretation of adsorption process.
From Fig. 1, it is apparent that the amount of Cu(II), Ni(II) and
Pb(II) adsorbed by coconut dregs residue increased with increasing
the pH of the solution. This trend can be explained by the fact that
the concentration of H+ ions was high at low pH (acidic medium).
This scenario leads to competition and repulsion between H+ and
metal ions for active sites on the surface of biosorbent [8,21]. When
the pH increased, H+ ions were less available, and therefore more
metal ions can be bound to adsorption sites.
Cu(II) was the metal ion most affected by this effect, followed by
Pb(II). In contrast, Ni(II) adsorption was not really affected by
solution pH, whereby the amount of Ni(II) adsorbed was within
3.404.81 mg/g when the solution pH was adjusted from 3.0 to 7.0.
The behaviour and ability of a sorbent to adsorb contaminants from
aqueous environment can be described in terms of pH of the zero
point of charge (pHzpc). As discussed by Mall et al. [22], adsorption
of cations is favoured at pH greater than pHzpc, while adsorption of
anions is favoured at pH lesser than pHzpc. In this study, pHzpc
obtained for coconut dregs residue is 5.7. As can be seen from Fig. 1,
the maximum adsorption of Cu(II), Ni(II) and Pb(II) onto coconut
dregs residue was at pH 7.0 (higher than pHzpc value). Therefore,
pH 7.0 was chosen as the optimum pH for the adsorption process.
Effect of initial metal concentration and contact time
Fig. 2 presents the effect of initial metal concentration on the
adsorption of Cu(II), Ni(II) and Pb(II) ions by coconut dregs residue.
[(Fig._1)TD$IG]
20
40
60
80
100
120
Ni(II)
Pb(II)
From Fig. 2, it is clear that the amount of metal ion adsorbed by the
biosorbent increased when increasing the initial metal concentration. For example, the amount of Pb(II) adsorbed by coconut dregs
residue increased from 0.50 to 9.60 mg/g as the initial Pb(II)
concentration increased from 5 to 100 mg/L. High adsorption
capacity at high initial metal concentration can be related to two
main factors, namely high probability of collision between metal
ion and biosorbent, and high diffusion rate of metal ion into
biosorbent. As a result, it will increase the driving force and reduce
the mass transfer resistance [23].
In contrast to adsorption capacity, the removal percentage of
metal ion decreased signicantly when the initial metal concentration was increased (Table 1). For example, the removal
percentage of Cu(II) reduced from 86.58% to 26.64% when the
initial concentration was increased from 5 to 100 mg/L. This
observation can be explained by the fact that the ratio of metal ion
to active site was low at low initial metal concentrations and vice
versa. In other words, active sites were less available for metal ion
binding at high initial metal concentrations, reducing the
percentage of metal ion removal from aqueous solution.
The experimental data for metal ion binding by the biosorbent
with respect to contact time revealed that the adsorption process
consists of two stages. The rst stage showed a rapid adsorption
pattern, while the second stage exhibited a gradual pattern until
equilibrium has been reached. The high amount of metal ion
adsorbed at the initial stage of the adsorption process was due to
the number of active sites available on the bare surface of the
biosorbent. The actives sites were progressively occupied by
the metal ions and led to no great difference in the adsorption rate.
The adsorption of metal ions onto coconut dregs residue attained
equilibrium within 60 min.
12
Adsorption isotherms
10
Table 1
Percentage of metal ion removal by coconut dregs residue.
Removal (%)
Cu(II)
Ni(II)
Pb(II)
86.58
88.14
85.83
56.76
26.64
77.67
81.31
74.11
68.18
46.37
100
100
100
99.31
96.08
0
2
pH
Cu(II)
Ni(II)
Pb(II)
5
10
25
50
100
qe
Q Qb
(3)
1
logC e
n
(4)
1
1 bC 0
(5)
Table 2
Langmuir and Freundlich isotherm constants and correlation coefcients.
Table 3
Comparison of adsorption capacities of Cu(II), Ni(II) and Pb(II) on various
adsorbents (selected papers).
Adsorbents
Q (mg/g)
Cu(II)
Ni(II)
Pb(II)
Langmuir
Freundlich
Q (mg/g)
b (L/mg)
R2
KF (mg/g)
1/n
R2
2.76
5.86
9.74
0.4958
0.0732
13
0.9974
0.9917
0.9931
0.76
0.47
2.12
0.3595
0.6292
0.3833
0.801
0.9496
0.0777
Reference
Cu(II)
Ni(II)
Pb(II)
2.76
2.1
7.63
3.64
6.92
8.88
5.86
1.82
13.5
7.9
12.42
3.83
3.11
5.75
9.74
8.09
8.29
2.24
2.93
12.3
16.23
5.43
This study
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[38]
[39]
from the Freundlich isotherm model lie between 0 and 1 (Table 2).
This indicates that the metal ions were successfully separated from
the aqueous solutions.
The capacity of coconut dregs residue to bind Cu(II), Ni(II) and
Pb(II) ions was compared with various adsorbents (Table 3). It is
apparent that the adsorption capacity of coconut dregs residue
was comparable with other adsorbents. It is known that each
adsorbent own unique physical and chemical characteristics.
Therefore, they have different abilities to bind metal ions from
aqueous solutions.
Adsorption kinetics
From a system design viewpoint, adsorption equilibrium
studies provide insufcient information on adsorption reaction
pathways. In chemical engineering practice, kinetic study is crucial
and inevitable as it provides information on adsorption rate and
rate-limiting step during adsorbate uptake at the solid-phase
interface. In this study, the pseudo-rst order, pseudo-second
order and intraparticle diffusion kinetic models are used to
determine the rate constant and the controlling mechanism of
Cu(II), Ni(II) and Pb(II) adsorption onto coconut dregs residue. The
correlation coefcient (R2) was used to determine the best t
kinetic expression of this process.
The linear form of the pseudo-rst order equation is given as
[40]:
logqe qt logqe
k1
t
2:303
(6)
qt k2 q2e qe
(7)
(8)
0.5
Metal ion
1915
1916
Table 4
Kinetic parameters for metal ion adsorption onto coconut dregs residue.
Kinetic parameter
Cu(II)
Ni(II)
Pb(II)
qe(exp) (mg/g)
5.17
5.62
8.92
Pseudo-rst order
qe(calc) (mg/g)
k1 (min1)
R2
0.58
0.0092
0.9097
0.81
0.0023
0.3239
0.14
0.0005
0.0046
Pseudo-second order
qe(calc) (mg/g)
k2 (g/(mg min))
R2
5.18
0.0530
0.9995
5.42
0.0291
0.9927
8.86
0.1368
0.9997
Intraparticle diffusion
ki (mg/(g min0.5))
R2
0.0422
0.9477
0.0510
0.5112
0.0079
0.1003
[(Fig._3)TD$IG]
50
40
t/qt
30
20
10
0
0
50
100
150
200
250
t (min)
Cu(II)
Ni(II)
Pb(II)
Fig. 3. Test of pseudo-second order equation for adsorption of metal ion by coconut
dregs residue.
Table 5
Percentage of metal ion removal in multi-metal system.
Initial metal concentration (mg/L)
25
Removal (%)
Cu(II)
Ni(II)
Pb(II)
97.27
44.48
100
Table 6
Removal and recovery of Cu(II), Ni(II) and Pb(II) from electroplating efuent.
Adsorbent
Metal
ion
Recovery
(%)
Pb(II)
Cu(II)
Ni(II)
5.33
2.75
1.86
0.32
0.14
0.61
93.9
94.9
67.2
0.63
0.42
0.39
12.6
16.1
31.2
Pb(II)
Cu(II)
Ni(II)
5.33
2.75
1.86
0.12
0.18
0.42
97.7
93.5
77.4
0.57
0.91
0.41
10.9
35.4
28.5
The recovery of metal ions was examined using 0.5 mol/L EDTA,
and the percentage of recovery was found to be in the range of
10.931.2% (Table 6). The recovery percentage obtained was rather
low, that is less than 40% of the amount of metal ion adsorbed on
the adsorbent. This suggests that the adsorption of metal ions onto
biosorbents was chemisorption, conrming results obtained from
kinetic study. Results also show that the biosorbent had a better
performance in removing Cu(II) from industrial efuent as
compared to commercial adsorbent, and therefore its application
in industrial efuent treatment is feasible.
Characterisation study
SEM analysis
SEM analysis was performed to observe the change in the
surface morphology of the biosorbent after interaction with metal
ions. The SEM images of coconut dregs residue before and after
metal ion adsorption at 5000 magnication are shown in Fig. 4.
The coconut dregs residue displayed a dense surface morphology with grooves texture (Fig. 4a). The grooves texture remained
following interaction with Cu(II) and Ni(II) (Fig. 4b and c).
However, this texture disappeared after Pb(II) adsorption (Fig. 4d).
Interaction with Cu(II) led to formation of tiny nodules on the
surface of coconut dregs residue (Fig. 4b). Bean- and lump-like
deposits were observed on the surface of the biosorbent following
adsorption of Ni(II) and Pb(II) ions (Fig. 4c and d).
EDX analysis
The elemental composition in the coconut dregs residue and
the presence of metal features after adsorption process were
examined by EDX analysis. The EDX spectrum of coconut dregs
residue exhibits the appearance of carbon, oxygen and potassium
features at energy values of 0.277, 0.523 and 3.313 keV, respectively. The feature of platinum can be detected at 2.048 and
9.441 keV. The samples were coated with platinum prior to
1917
[(Fig._4)TD$IG]
Fig. 4. SEM images of coconut dregs residue at 5000 magnication before adsorption of metal ion (a), and after adsorption of Cu(II) (b), Ni(II) (c), and Pb(II) (d).
1918
[(Fig._5)TD$IG]
Fig. 5. EDX spectrum of coconut dregs residue after interaction with Pb(II).
[(Fig._6)TD$IG]
(a)
!
1646
1377
1711
3370
%T
(b)
2854
174
4
2923!
1457.10
1459
1065
1032
1584
1646
3365
1377
2852
1743
1711
1241
1149
2923
1064
3500
124
0
1150
3000
2500
2000
1500
1033
1000
Wavenumber (cm-1)
Fig. 6. FTIR spectra of coconut dregs residue before (a) and after adsorption of (b)
Cu(II), (c) Ni(II) and (d) Pb(II).
led to a shift in wave number from 3370 cm1 to 3365, 3378 and
3364 cm1 for OH stretching vibration. Furthermore, new
absorption bands were observed at wave numbers 1584 and
1514 cm1 after interaction with Cu(II) and Pb(II) ions (Fig. 6b and
d). These bands are related to N
H bending vibration of amine
group [50]. The absorption intensity of carbonyl group at
1742 cm1 decreased signicantly after exposure with Ni(II)
(Fig. 6c). Furthermore, the bands at 1646 and 1240 cm1 which
attributed to amine and carbonyl groups shifted to 1651 and
1246 cm1 after adsorption of Pb(II) and Ni(II), respectively
(Fig. 6c and d).
Apparently, the formation of new absorption bands, the change
in absorption intensity and the shift in wave number of the
functional groups could be due to interaction of metal ions with
active sites of coconut dregs residue through complexation. The
electron donor atoms (N and O) are involved in the binding
mechanism. It can be concluded that the main adsorption sites for
coconut dregs residue are hydroxyl, carbonyl and amine groups.
Conclusions
This study highlights the potential of coconut dregs residue, a
low-cost material, as an alternative biosorbent to treat industrial
efuent. It consists of amino, hydroxyl and carbonyl groups that
favour metal ion binding through complexation mechanism. The
selectivity of the biosorbent was in the order of Pb(II) > Cu(II) >
Ni(II), which was consistent in both single- and multi-metal
systems. Several fundamental aspects of chemical engineering
1919
[31] K.S. Low, C.K. Lee, S.Y. Wong, P.L. Tang, Metal adsorption enhancement of
rice hull through chemical modication, Environ. Technol. 21 (2001) 1239
1244.
[32] T. Vaughan, C.W. Seo, W.E. Marshall, Removal of selected metal ions from
aqueous solution using modied corncobs, Bioresour. Technol. 78 (2001) 133
139, doi:http://dx.doi.org/10.1016/S0960-8524(01)00007-4. 11333031.
[33] S. Guo, W. Li, L. Zhang, J. Peng, H. Xia, S. Zhang, Kinetics and equilibrium
adsorption study of lead(II) onto the low cost adsorbentEupatorium
adenophorum spreng, Process Saf. Environ. Prot. 87 (2009) 343351, doi:
http://dx.doi.org/10.1016/j.psep.2009.06.003.
[34] J.W. Choi, S.G. Chung, S.W. Hong, D.J. Kim, S.H. Lee, Development of an
environmentally friendly adsorbent for the removal of toxic heavy metals from
aqueous solution, Water Air Soil Pollut. 223 (2012) 18371846, doi:http://dx.
doi.org/10.1007/s11270-011-0988-1.
[35] M.
ciban, M. Klasnja, B. krbi
c, Modied softwood sawdust as adsorbent of
heavy metal ions from water, J. Hazard. Mater. 136 (2006) 266271, doi:http://
dx.doi.org/10.1016/j.jhazmat.2005.12.009. 16426747.
[36] A. Sar, M. Tuzen, .D. Uluzl, M. Soylak, Biosorption of Pb(II) and Ni(II) from
aqueous solution by lichen (Cladonia furcata) biomass, Biochem. Eng. J. 37
(2007) 151158.
[37] E. Malkoc, Ni(II) removal from aqueous solutions using cone biomass of Thuja
orientalis, J. Hazard. Mater. 137 (2006) 899908, doi:http://dx.doi.org/10.1016/
j.jhazmat.2006.03.004. 16621254.
[38] Y. Bulut, Z. Tez, Adsorption studies on ground shells of hazelnut and almond, J.
Hazard. Mater. 149 (2007) 3541, doi:http://dx.doi.org/10.1016/j.jhazmat.2007.03.044. 17467899.
[39] F. Gzel, H. Yakut, G. Topal, Determination of kinetic and equilibrium
parameters of the batch adsorption of Mn(II), Co(II), Ni(II) and Cu(II) from
aqueous solution by black carrot (Daucus carota L.) residues, J. Hazard. Mater.
153 (2008) 12751287, doi:http://dx.doi.org/10.1016/j.jhazmat.2007.09.087.
17980960.
[40] S. Lagergren, Zur theorie der sogenannten adsorption gelster stoffe, K. Sven.
Vetenskapsakad. Handl. 24 (1898) 139.
[41] Y.S. Ho, G. McKay, The kinetics of sorption of divalent metal ions onto
Sphagnum moss peat, Water Res. 34 (2000) 735742, doi:http://dx.doi.org/
10.1016/S0043-1354(99)00232-8.
[42] W.J. Weber, J.C. Morris, Kinetics of adsorption of carbon from solution, J.
Sanitary Eng. Div. 89 (1963) 3159.
[43] K. Banerjee, S.T. Ramesh, R. Gandhimathi, P.V. Nidheesh, K.S. Bharathi, A novel
agricultural waste adsorbent, watermelon shell for the removal of copper from
aqueous solutions, Iranica J. Energy Environ. 3 (2012) 143156.
[44] Y. Kalmykova, A.M. Strmvall, B.M. Steenari, Adsorption of Cd, Cu, Ni, Pb and Zn
on Sphagnum peat from solutions with low metal concentrations, J. Hazard.
Mater.
152
(2008)
885891,
doi:http://dx.doi.org/10.1016/j.jhazmat.2007.07.062. 17765394.
, Y. Aktay, Mass transfer and equilibrium studies for the sorption of
[45] Y. Sag
chromium ions onto chitin, Process Biochem. 36 (2000) 157173, doi:http://
dx.doi.org/10.1016/S0032-9592(00)00200-4.
[46] P. Miretzky, A. Saralegui, A.F. Fernndez Cirelli, Simultaneous heavy metal
removal mechanism by dead macrophytes, Chemosphere 62 (2006) 247254,
doi:http://dx.doi.org/10.1016/j.chemosphere.2005.05.010. 15990152.
[47] B.C. Qi, C. Aldrich, Biosorption of heavy metals from aqueous solutions with
tobacco dust, Bioresour. Technol. 99 (2008) 55955601, doi:http://dx.doi.org/
10.1016/j.biortech.2007.10.042. 18096382.
[48] Department of Environment Malaysia (DOE), Environmental Quality Act 1974
(Act 127), 1974.
[49] J.R. Mohrig, C.N. Hammond, P.F. Schatz, Techniques in Organic Chemistry,
second ed., W.H. Freeman, USA, 2006.
[50] D.H. Williams, I. Flemming, Spectroscopic Methods in Organic Chemistry, fth
ed., The McGraw-Hill Companies, London, UK, 1995.