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Abstract
The performance of a commercially available palm shell based activated carbon to remove lead ions from aqueous solutions by
adsorption was evaluated. The adsorption experiments were carried out at pH 3.0 and 5.0. The eect of malonic and boric acid presence
on the adsorption of lead ions was also studied. Palm shell activated carbon showed high adsorption capacity for lead ions, especially at
pH 5 with an ultimate uptake of 95.2 mg/g. This high uptake showed palm shell activated carbon as amongst the best adsorbents for lead
ions. Boric acid presence did not aect signicantly lead uptake, whereas malonic acid decreased it. The diuse layer surface complexation model was applied to predict the extent of adsorption. The model prediction was found to be in concordance with the experimental
values.
2005 Elsevier Ltd. All rights reserved.
Keywords: Adsorption; Lead; Malonic acid; Boric acid; Modeling; Palm shell carbon
1. Introduction
The use of activated carbon to remove heavy metal ions
from wastewater by adsorption is a well-established process. The economics of this process depends mainly on
the cost of the adsorbent material. As such, low cost adsorbents are becoming the focus of many investigations. Low
cost adsorbents could be produced from many raw materials such as agriculture and industrial wastes. In Malaysia,
the palm oil industry generates huge amounts of palm shell.
Some of this solid waste is usually used as fuel to produce
process steam and/or electricity in palm oil mills. However,
a large portion of it is either burned in open air or dumped
in areas adjacent to the mill, which creates huge environmental and disposal problems. In recent years the interest
to palm shell has increased mainly due to the fact that
this material was shown to be an excellent source of high
quality and low cost activated carbon. However, most of
the research on palm shell carbon is focused on the
*
Corresponding author. Tel.: +60(3) 7967 5313; fax: +60(3) 7967 5319.
E-mail address: mk_aroua@um.edu.my (M.K. Aroua).
0960-8524/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2005.10.023
2351
the speciation diagrams for single lead and lead with complexing agents systems.
3. Results and discussion
2. Methods
Commercial granular palm shell activated carbon
(PSAC) was provided by Pacic Activated Carbon a local
manufacturer in Johor Bahru, Malaysia. Activated carbon
granules with particle size ranging from 0.8 to 1.0 mm were
used throughout the experiments. NaNO3 and Pb(NO3)2
from Merck were used as the background electrolyte and
lead ions source, respectively. All solutions were prepared
in deionized water and the pH was adjusted by adding
small amounts of 0.1 M NaOH and HCl solutions. Malonic and boric acids stock solutions of 0.1 M were used to
adjust the proportion of ligand to the metal ion to a value
of 10:1 on a molar basis.
In a typical adsorption run, 500 mg of activated carbon
was equilibrated with 100 ml of lead ion solution at a constant temperature of 27 C. The equilibrated solution was
then subjected to ICP-AES (Varian, Liberty 200) analysis
in order to determine the concentration of residual lead
ion. The amount of lead ion adsorbed was calculated as
the dierence between the initial and nal lead concentration. The adsorption isotherm was obtained by varying
the initial concentration of lead ions from 10 to
700 ppm. The BET surface area of the activated carbon
was determined from N2 adsorption isotherm at 77 K
using BrunauerEmmetTeller equation. The N2 adsorption isotherm was determined using Micrometric ASAP
2010 system. Determination of the total acidity of PSAC
was carried out using Boehm method (Boehm, 1994). pH
of point of zero charge was determined using the pH
drift method (Lopez-Ramon et al., 1999; Mullet et al.,
1999).
The potentiometric titration experiments were carried
out in a glass cell at 25 C, under a OFN gas ow to prevent CO2 dissolution. In these experiments, 500 mg of activated carbon was placed in a ask containing 100 mL of
0.15 M NaNO3, and placed on a shaker at 27 C and
150 rpm for 48 h. Then the solution was titrated with
0.1 M HCl and/or NaOH. The titration was monitored
with a glass electrode paired with an internal Ag/AgCl/
KCl 3 M reference system. The electrode was calibrated
with buers at pH 4, 7 and 10 prior to the potentiometric
measurements. The equipment used included a microprocessor controlled burette and pH meter Metrohm 716
DMS Titrino controlled with a computer using TiNet 2.4
software. The potentiometric titration data were used to
obtain the pKa values of PSAC via application of the computer software Fiteql 4.0 (Herbelin and Westall, 1999).
Modeling on adsorption data was carried out using diffuse layer surface complexation model (Chen et al., 1996;
Faur-Brasquet et al., 2002; Borretzen and Salbu, 2003).
This model is incorporated in the VMinteq 2.15 software
(Gustafsson, 2003). The same software was used to obtain
ACCs (Faur-Brasquet
et al., 2002)
PSAC
CS-1501
RS-1301
957.04
1680
1460
1.51
2.63
0
0
4.14
2.605
1.43
7.386
12.24
0.60
0.10
0.40
0
1.10
0.25
0.15
0.40
0
0.80
7.50
6.26
9.33
9.53
3.90
11.90
1
C, %
40
20
0
0
10
12
14
Pb(NO3)2 (aq)
PbNO3+
Pb(OH)2 (aq)
Pb(OH)3-
Pb(OH)2 [s]
PbOH+
100
80
60
40
20
0
0
8
pH
10
12
14
Pb2+
PbNO3+
Pb(NO3)2 (aq)
Pb-Malonate (aq)
PbOH+
Pb(OH)2 (aq)
Pb(OH)3-
Pb(OH)2 [s]
16
a Ce
;
1 b Ce
100
80
C, %
Pb2+
pH
C, %
2352
60
40
20
0
0
10
12
pH
Pb2+
PbNO3+
Pb(NO3)2 (aq)
Pb(OH)2 (aq)
Pb(OH)3-
Pb(OH)2 [s]
PbOH+
14
2353
Table 2
Langmuir parameters for the adsorption of lead
pH
Variant
qm (mg/g)
qm (mmol/g)
SSE
R2
5
5
5
Pb
Pb + MA
Pb + BA
10.6
8.9
9.1
1.12
0.28
0.08
95.2
31.5
22.0
0.46
0.15
0.59
0.19
0.48
0.13
0.99
0.99
0.99
3
3
3
Pb
Pb + BA
Pb + MA
13.3
15.9
0.34
0.16
0.24
0.02
82.0
67.1
16.0
0.39
0.32
0.08
0.17
0.05
0.33
0.99
0.99
0.99
This was possible in view of the reported ndings of Rajakovic and Ristic (1996) who determined that 1.4 mg/g of
boric acid from potable water was adsorbed on the activated carbon. Rajakovic and Ristic (1996) also showed
that activated carbon had higher sorption anity towards
monomeric, univalent ions than towards polyvalent structures of boric acid that were present in aqueous solutions.
The activated carbon maintained its adsorptive functions
in the presence of boric acid and the principal ion
BOH
4 in borax solution did not demonstrate anity
towards complex formation (Rajakovic and Ristic, 1996).
Furthermore, the ineectiveness of boric acid on adsorption of lead at pH 3.0 could be associated with its weak
electrolytic properties and slow dissociation, especially in
the acidic aqueous solutions (Cotton and Wilkinson,
1966).
Malonic acid had a deteriorating aect on the adsorption of lead compared to the two previous systems. The
uptake of lead was signicantly lower: 31.5 and 16.0 mg
Pb2+/g AC at pH 5.0 and 3.0, respectively, compared to
95.2 and 82.0 mg Pb2+/g AC for single lead system. However, the same trend was observed with the eect of pH as
the amount of lead removed at pH 5.0 was higher than at
pH 3.0. The speciation diagram for lead with malonic acid
identied formation of leadmalonate (aq) complex in pH
range 310, with a peak concentration at pH 6.5. The formation of this complex could be responsible for the substantial decrease of lead adsorption on PSAC.
Table 3
Adsorption capacities (mg/g) of lead by various adsorbents
Adsorbent
Natural ferric oxide
Tea leaves
Clay
Groundnut husk
Sphagnum moss peat
Olive mill residue
Sago waste
ACC
Carex peat
Cocoa shells
Bone powder
Active carbon
Nile rose plant powder
Commercial carbon
Palm shell activated carbon
pH
Lead (II)
References
5.6
25.5
210
7.8
2
3 and
3 and
3 and
3 and
3 and
230.0
78.7
0.12
39.3
30.7
21.56
46.64
30.45
83%
6.2
29.5 and 55.3
32.7 and 41
19.7 and 27.4
9.8 and 27.3
82.0 and 95.2
5
5
5
5
5
In order to assess the performance of palm shell activated carbon as adsorbent for lead ions, a comparison with
other types of adsorbents was made (Table 3). All adsorbents showed lower lead uptake than PSAC, except the
natural mineral ferric oxide, which was characterized by
a capacity three times higher than PSAC. Such high uptake
for ferric oxide was expected since this solid was characterized by high number of surface hydroxide groups that
exhibited high anity for heavy metals. The capacities of
other carbonaceous materials of plant origins were considerably lower compared to the PSAC capacity. This could
be due to the smaller surface area that these adsorbents
possessed. Due to the lack of information on the surface
areas of most of these adsorbents, it was dicult to conrm
the eect of the surface area on the adsorption capacity.
Nevertheless, a rigorous comparison could be made with
ACC. As shown in Table 3, PSAC was characterized by
a capacity, which was more than a double of that of
ACC despite the higher surface area of the later. This result
indicated that the concentration of surface acidic groups
was more important in this adsorption process than the
overall surface area.
Table 4
Surface complexation constants values calculated for PSAC using DLM
Initial conc. Pb2+
Log K int
SOM
Log K int
SOM
128.7
153.6
229.2
258.7
273.8
294.0
6.4
6.2
5.8
5.7
5.6
5.5
315.8
337.0
394.4
424.7
485.0
511.0
541.6
5.5
5.4
5.3
5.2
5.0
5.0
4.9
100
80
mod %
2354
60
40
20
0
0
4.00E-02
exp
model
3.00E-02
[H+]
2.50E-02
2.00E-02
1.50E-02
1.00E-02
5.00E-03
0.00E+00
0
40
60
80
100
exp %
3.50E-02
20
10
pH
Fig. 4. Acidbase titration curves for Pacic palm shell activated carbon.
Acknowledgements
We would like to thank the Ministry of Science, Technology and Innovation, Malaysia for the IRPA Research
Grant; the Institute for Postgraduate Studies and Research
(IPSP), University Malaya for nancing VotF 159/2003A
research project; and Pacic Activated Carbon Company,
Johor Baru, Malaysia for the generous provision of palm
shell activated carbon for our research.
References
Abdel-Halim, S.H., Shehata, A.M.A., El-Shahat, M.F., 2003. Removal of
lead ions from industrial waste water by dierent types of natural
materials. Water Res. 37, 16781683.
Abu Bakar, N., 1999. Adsorption studies of phenols in aqueous solution
using activated carbon prepared from several part of oil palm tree.
M.Sc. Thesis. Faculty of Science and Environmental studies. University Putra Malaysia, Malaysia.
Boehm, H.P., 1994. Some aspects of the surface chemistry of carbon
blacks and other carbons. Carbon 32 (5), 759769.
Borretzen, P., Salbu, B., 2003. Geochemical Models for sediment
seawater interactions. Laboratory for Analytical Chemistry Institute
for Chemistry and Biotechnology. Agricultural University of Norway.
1432 As, Norway.
Chen, J.P., Lin, M.S., 2001. Equilibrium and kinetics metal ion adsorption
onto a commercial H-type granular activated carbon: experimental
and modeling studies. Water Res. 2 (35), 23852394.
Chen, J.P., Wang, X., 2002. Removing copper, zinc, and lead ion by
granular activated carbon in pretreated xed-bed columns. Sep. Purif.
Technol. 19, 157167.
Chen, J., Yiacoumi, S., Blaydes, T.G., 1996. Equilibrium and kinetic
studies of copper adsorption by activated carbon. Sep. Technol. 6,
133146.
Chen, J.P., Hong, L., Wu, S.N., Wang, L., 2002. Elucidation of
interactions between metal ions and Ca-alginate based ion exchange
resin by spectroscopic analysis and modelling simulation. Langmuir 18
(24), 94139421.
Chen, J.P., Wu, Sh., Chong, K.-H., 2003. Surface modication of a
granular activated carbon by citric acid for enhancement of copper
adsorption. Carbon 41, 19791986.
Chu, K.H., Hashim, M.A., 2002a. Adsorption characteristics of trivalent
chromium on palm oil fuel ash. Clean Technol. Environ. Policy 4, 8
15.
Chu, K.H., Hashim, M.A., 2002b. Adsorption and desorption characteristics of zinc on ash particles derived from oil palm waste. J. Chem.
Technol. Biotechnol. 77, 685693.
Corapcioglu, M.O., Huang, C.P., 1987. The adsorption of heavy metals
onto hydrous activated carbon. Water Res. 21, 10311044.
Cotton, F.A., Wilkinson, G., 1966. Advanced Inorganic Chemistry,
second ed. Interscience, NY.
Dastgheib, S.A., Rockstraw, D.A., 2002. A model for the adsorption of
single metal ion solutes in aqueous solution onto activated carbon
produced from pecan shells. Carbon 40, 18431851.
Daud, W.M.A.W., Ali, W.S.W., 2004. Comparison on pore development
of activated carbon produced from palm shell and coconut shell.
Biores. Technol. 93, 6369.
Daud, W.M.A.W., Ali, W.S.W., Sulaiman, M.Z., 2002. Eect of activation temperature on pore development in activated carbon produced
from palm shell. J. Chem. Technol. Biotechnol. 78, 15.
Department of Environment (DOE), Malaysia Environmental Quality
Report, 2002. Ministry of Science, Technology and the Environment,
Malaysia. ISSN 0127-6433.
Donnet, J.B., 1968. Carbon 6, 161.
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