J. Anal. Appl.

Pyrolysis 87 (2010) 188–193

Contents lists available at ScienceDirect

Journal of Analytical and Applied Pyrolysis

journal homepage: www.elsevier.com/locate/jaap

Adsorption of copper from aqueous solution by activated carbons obtained

by pyrolysis of cassava peel
J.C. Moreno-Piraján a,*, L. Giraldo b
a
Departamento de Quı´mica, Facultad de Ciencias, Universidad de Los Andes, Grupo de Investigación en Sólidos Porosos y Calorimetrı´a, Bogotá, Colombia
b
Departamento de Quı´mica, Universidad Nacional de Colombia, Bogotá, Colombia

A R T I C L E I N F O A B S T R A C T

Article history: Activated carbons (ACs) were prepared by pyrolysis of cassava peel in presence of chloride zinc (chemical
Received 29 October 2009 activities). Cassava peel from Colombian cassava cultives were impregnated with aqueous solutions of
Accepted 14 December 2009 ZnCl2 following a variant of the incipient wetness method. Different concentrations were used to
Available online 22 December 2009
produce impregnation ratios of 40, 70, 110 and 160 wt.%. Activation was carried out under argon flow by
heating to 823 K with 1 h soaking time. The porous texture of the obtained ACs was characterized by
Keywords: physical adsorptions of N2 at 77 K and CO2 at 273 K. The impregnation ration had a strong influence on
Cassava peel
the pore structure of these ACs, which could be easily controlled by simply varying the proportion of
Adsorption
ZnCl2 used in the activation. Thus, low impregnation ratio led to essentially microporous ACs. At
Surface area
Activated carbon intermediate impregnation ratios, ACs with wider pore size distribution (from micropores to mesopores)
Langmuir were obtained. Finally, high impregnation ratios yielded essentially mesoporous carbons with high
Prausnitz–Radlke surface area and pore volume. The four best-fit three-parameter isotherms Sips, Toth, Radke–Prausnitz
and Vieth–Sladek suggests that the sorption capacity of activated carbon of cassava peel to uptake
copper ions to be 55 mg/g.
ß 2009 Elsevier B.V. All rights reserved.

1. Introduction
Activated carbons are materials having complex porous
structures with associated energetic as well chemical inhomoge-
neities. Their structural heterogeneity is a result of existence of
micropores, mesopores and macropores of different sizes and
shapes. Activated carbon is one of the most important adsorbents
from an industrial view point. The main application of this
adsorbent is for separation and purification of gaseous and liquid
phase mixtures [1–7].
There are two processes for preparation of activated carbon:
chemical activation and physical activation. Chemical activation is
known as a single step method of preparation of activated carbon
in the presence of chemical agents. Physical activation involves
carbonization of a carbonaceous materials followed by activation
of the resulting char in the presence of activating agents such as
CO2 or steam. The chemical activation usually takes place at a
temperature lower than that used in physical activation, therefore
it can improve the pore development in the carbon structure
because of the effect of chemicals. The carbon yields of chemical
activation are higher than physical one [6,8]. Cassava is one of the
most important foods in Colombia, an agricultural country.
Cassava is one of the primary foods in our country and usually
used for traditional food, cake, etc. The cassava production in
Colombia is very huge and only small amounts are utilized by
traditional food industries, and the rest are used as the raw
material for cassava starch industries. Cassava starch making
operation produces a large amount of solid wastes (cassava peel),
and direct discharge of this solid wastes will cause the
environmental problems. Here we report on the porous texture
characteristics of ACs prepared by ZnCl2 activation of cassava peel,
i.e. the shells covering cassava. These constitute a by-product from
cassava processing following harvest with few practical applica-
tions and whose uncontrolled spill (e.g. in rivers) causes some
environmental concern. In fact, applications of cassava peel are
limited to use as fuel or as feedstock to obtain food for animal. We
will show that carbon adsorbents with high surface areas and pore
volumes can be obtained from this material, and that development
of the porous structure can be modulated by changing the relative
proportions of feedstock and ZnCl2.
2. Experimental
2.1. Reagents

* Corresponding author. Tel.: +57 13394949; fax: +57 13324366. All chemicals were of reagents grade, purchased Merck and
E-mail address: jumoreno@uniandes.edu.co (J.C. Moreno-Piraján). cassava peel were obtained from cultives Colombian.

0165-2370/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2009.12.004
 J.C. Moreno-Piraján, L. Giraldo / J. Anal. Appl. Pyrolysis 87 (2010) 188–193
Fig. 1. Furnace vertical to obtain activated carbon from cassava peel.
2.2. Treatment and preparation of sample
Prior to the use, the cassava peel was repeatedly washed with
distilled water in order to remove dust and other inorganic
impurities, then oven-dried for 24 h at 393 K to reduce the
moisture content. Peel from Colombian cassava was impregnated
with aqueous solutions of chloride zinc following a variant of the
incipient wetness method; similar cases have been described in
the literature [9,10]. This consists of adding dropwise (while
stirring the solid, to facilitate homogeneous absorption of liquid)
the amount of aqueous solution (2.0 mL g1 cassava peel)
necessary to produce swelling until incipient wetness. Different
concentrations of ZnCl2 in aqueous solution were used to vary the
content of impregnation agent, which will be expressed as
impregnation ratio (Xp, wt.%), defined as (gram ZnCl2 per g cassava
peel)  100. Impregnation ratios of 40, 70, 110 and 160 wt.% were
used. After impregnation, the samples were dried for 8 h at 383 K
in air. Pyrolysis treatments (activations) were carried out in a
vertical tubular reactor made of quartz in furnace CarboliteTM,
Fig. 1, using in all cases 25 g of impregnated and dried material.
All treatments were done at a constant heating rate of
10 K min1 and with an argon (99.999% pure) flow of
30 STP cm3 min1, which was kept during heating and cooling.
An activation temperature of 823 K and a soaking time of 4 h were
used. After cooling the solid pyrolysis residue to room temperature
it was washed with milli-Q distilled water until lowering the
conductivity of the washing liquids to <5 mS cm1 (measured with
a pH/conductivity meter HP, model MARK 602). The resulting ACs
were dried at 383 K for 24 h in a vacuum furnace. The activated
carbon were labeled here as: CP40, CP70, CP110 and CP160,
according to their impregnation ratios with ZnCl2.
2.3. Pore structure characterization
The porous texture of ACs was characterized by physical
adsorption of nitrogen at 77 K (using an automatic volumetric
adsorption apparatus, AUTOSORB 3B from Quantachrome instru-
ments) and carbon dioxide at 273 K (using a automatic volumetric
adsorption apparatus, AUTOSORB 3B from Quantachrome instru-
ments). In either case the samples were degassed overnight at
573 K before every adsorption measurement. Gases used had
minimum purities of 99.999% (N2) and 99.98% (CO2). N2 adsorption
data were analyzed by means of the BET and Dubinin–Radushke-
vich (DR) equations, the aS method (using Spheron-6 carbon black
as reference material) and the density functional theory (DFT). CO2
189
adsorption data were analyzed by the Dubinin–Radushkevich–
Kaganer (DRK) equation.
2.4. Study of pH and determination of isotherms of
adsorption from aqueous solution
Batch adsorption experiments were carried out in a series of
stoppered reagent bottles. 100 mL of CuSO4 solution with
predetermined initial concentration of 10, 20, 30, 40, 50–
100 mg/L was put inside the 30 mL stoppered reagent bottles,
which contained 0.5 g using the activated carbon of mayor area
(CP160). Prior to that, the pH solution was adjusted to the desired
values by adding HNO3 or NaOH. The reagent bottles with
activated carbon–CuSO4 mixture were shaken using an orbital
incubator shaker, which operated at 100 rpm and 298 K (1 K) for
8 h to attain the equilibrium condition. Blank solutions were treated
similarly without the adsorbent, and the recorded concentrations at
the end of each operation were taken as the initial. The final
concentrations of the solution were then determined from a
calibration curve. The solutions were continuously agitated for at
least 8 days, which is the maximum contact time to reach equilibrium
with this sorbent and particle size (according to previous studies with
many other metals). Blank samples were also processed in the
absence of sorbent to check for sorption on the experimental
equipment (flasks, filtration units, etc.) and the absence of
precipitation phenomena. Samples were finally collected and filtered
using 1.2 mm pore size filter membranes. Metal content in the filtrate
was measured using atomic emission spectrometry (AES) (Perkin
Elmer AAnalyst 300, US). The mass balance equation was used to
calculate the amount of copper at equilibrium. Therefore, the sorption
capacity q (mg Cu g1) was obtained from:
VðC o  C eq Þ
q¼
m
where V is the volume of the solution (l), m is the amount of sorbent
(g), Co and Ceq are the initial and equilibrium concentration in the
solution (Cu, mg L1).
3. Results and disscusion
3.1. Physical properties of activated carbons obtained
Fig. 2 shows adsorption–desorption isotherms of N2 at 77 K on
ACs from cassava peels impregnated with different amounts of
ZnCl2. The isotherms are type Ia for the AC with Xp = 40 wt.%
190 J.C. Moreno-Piraján, L. Giraldo / J. Anal. Appl. Pyrolysis 87 (2010) 188–193

Fig. 2. N2 adsorption–desorption isotherms at 77 K on ACs prepared at different Fig. 3. PSDs obtained by applying the DFT theory to N2 adsorption data at 77 K.
impregnation ratios. Empty symbols, adsorption; full symbols, desorption.

(typical of microporous materials where micropore filling may
take place by primary filling at very low p/p0) [10] with a small
development of mesopores, and type Ib when Xp = 70 wt.% (typical
of microporous materials where micropore filling may take place
by co-operative filling in wider micropores over a range of higher
p/p0 than in type Ia) [10]. The AC prepared by impregnation at
Xp = 110 wt.% gives a type Ib isotherm, but in this case a plateau is
not clearly reached, indicating widening of pores; this isotherm
exhibits a type H4 hysteresis loop, characteristic of slit-shaped
pores. Finally, the AC prepared by impregnation with 160 wt.%
chloride zinc yields a type IIb isotherm but with an important
adsorption at low p/p0, indicative of simultaneous presence of
micro- and mesopores. Similar evolutions from type I to type II
isotherms with increasing amount, but with phosphoric acid have
been reported by other authors [1–3].
Table 1 reports textural parameters deduced from N2 and CO2
adsorption isotherms. The BET (SBET) and micropore [Smicrop. (DR,
N2)] surface areas increase with increasing Xp, sharply from
Xp = 100–160 wt.% and less markedly above the latter impregna-
tion ratio (40–70 wt.%). The micropore surface areas deduced from
CO2 isotherms [Smicrop. (DRK, CO2)] go through a maximum at
160 wt.%. The external surface area [Sext (aS, N2)] increases with
increasing Xp, slightly at low impregnation ratios and more steeply
above 110 wt.% ZnCl2, as could be expected from the shape of the
isotherms.
The total pore volume, Vp (N2) (calculated from N2 adsorption
data as volume of liquid N2 at a relative pressure of 0.975) increases
continuously with increasing impregnation ratio as does the
mesopore volume, Vmp (DFT, N2) (volume of pores with widths
between 2 and 50 nm). The ultramicropore volume, Vumicrop. (DFT,
N2) (volume corresponding to pores of width <0.7 nm) follows the
opposite trend.
Let us examine now the variation of the micropore volume as a
function of Xp. Parameters such as Vmicrop. (DRK, CO2) and Vmicrop.
(DFT, N2) (the latter being calculated as the volume of pores of
width <2 nm) go through a maximum at Xp = 70 wt.%. The
alternative parameter Vmicrop. (DR, N2) increases with increasing
Xp over the entire range of impregnation ratios studied, albeit the
increase is small above Xp = 70 wt.%. Vmicrop. (DRK, CO2) is always
smaller than Vmicrop. (DFT, N2) and Vmicrop. (DR, N2), this being
attributable to the presence of wide micropores that are not filled
with CO2 at the low relative pressures (<0.03) attained at 273 K; it
is well-known that, under these conditions, CO2 only measures
narrow microporosity [11]. The differences between Vmicrop. (DFT,
N2) and Vmicrop. (DR, N2) are ascribable to the artifactual minimum
around 1 nm that arises systematically in DFT calculations. This
minimum, introduced by modelling assumptions [12,13], certainly
contributes to underestimate the micropore volume as calculated
by this method.
Fig. 3 shows pore size distributions (PSDs) calculated by means
of the DFT method from N2 adsorption data. Values below 1 nm can
be noticed in all cases. The width of the distribution increases with
increasing Xp. The AC prepared at Xp = 40 wt.% exhibits a maximum
at 0.50 nm, which becomes displaced towards larger pore sizes

Table 1
Textural parameters deduced from N2 adsorption at 77 K and CO2 adsorption at 273 K on ACs prepared at different impregnation ratios (Xp).

Xp (wt.%) N2 CO2

SBET Sext Vp DFT-method DR-method DRK-method

Vumicrop. Vmicrop. Vmp. Smicrop. Vmicrop. Smicrop. Vmicrop.

40 834 7 0.33 0.12 0.24 0.03 876 0.30 650 0.23

70 945 12 0.57 0.10 0.32 0.22 965 0.47 660 0.31
110 1276 17 0.91 0.09 0.33 0.45 1289 0.48 698 0.25
160 1567 143 1.18 0.06 0.25 0.87 1560 0.62 723 0.24

Surface areas in m2 g1 and pore volumes in cm3 g1.

 J.C. Moreno-Piraján, L. Giraldo / J. Anal. Appl. Pyrolysis 87 (2010) 188–193 191

(0.80 nm) at higher Xp values. For all samples this is the maximum. Table 2
Isotherms and the parameters involved in the different equilibrium sorption
An increase in the pore volume and a displacement towards higher
isotherms.
pore sizes can be clearly noticed as the impregnation ratio
increases. Finally, the mesopore volume also increases with Isotherm Expression Parameters
increasing Xp; for instance, mesopores only represent 21% of the Freundlich [15] qe ¼ K F Ce
1=nF
K F, nF
total pore volume of the AC prepared at an Xp = 40 wt.%, whereas qm K L C e
Langmuir [16] qe ¼ 1þK L C e KL, qm
they amount to 56% for the sample prepared at Xp = 160 wt.%.
AC e
From the above results one can deduce that the ACs obtained at Redlich–Peterson [17] qc ¼ 1þB Ce
g A, B, g
low impregnation ratios are essentially microporous. As the Toth [18] qe ¼ qm C e ðbT þ Ce T Þ
n 1=nT
bT, nT, qm
amount of ZnCl2 increases, pores with a wide range of sizes are K RP qm C e
Radke–Prausnitz [19] qe ¼ ð1þK RP C e ÞmRP
KRP, qm, mRP
developed so that at high Xp the ACs become predominantly
K q C
FS m e
mesoporous. Similar effects of the amount but with using Fritz–Schluender [20] qe ¼ 1þq Cm
KFS, qm, mFS
m e

phosphoric acid on porosity development have been reported qm ðK S C e ÞmS

for other lignocellulosic precursors [1,2,4,5]. It is generally
accepted that the porosity is generated with phosphoric acid
remaining intercalated in the internal structure of lignocellulosic
materials. As the amount of ZnCl2 used increases, the volume filled
by it and various polyphosphates will increase, resulting in larger
pore volume and pore size.
3.2. Effect of initial pH and isotherm from aqueous solution
The acidity of solution pH is one of the most important
parameters controlling the uptake of heavy metals from waste-
water and aqueous solutions. The uptake and percentage removal
of copper from the aqueous solution are strongly affected by the pH
of the solution as illustrated in Fig. 4. The uptake of copper
increases from 0.20 to 1.43 mg/g when the pH increases from pH 1
to pH 5. Copper sorption is noted to increase significantly at pH 3
with 0.40 and 1.43 mg/g adsorption capacity at pH 5 respectively.
After that the capacity of adsorption decreases slightly in pH range
of 6–10. The minimum adsorption observed at low pH (pH 1) may
be due to the fact that the higher concentration and higher
mobility of H+ ions present favored the preferential adsorption of
hydrogen ions compared to Cu(II) ions. It would be plausible to
suggest that at lower pH value, the surface of the adsorbent is
surrounded by hydronium ions (H+), thereby preventing the metal
ions from approaching the binding sites of the sorbent. This means
that at higher H+ concentration, the biosorbent surface becomes
more positively charged such that the attraction between biomass
and metal cations is reduced.
In contrast, as the pH increases, more negatively charged
surface becomes available thus facilitating greater copper removal.
It is commonly agreed that the sorption of metal cations increases
with increasing pH as the metal ionic species become less stable in
the solution. However, at higher pH values (pH 6, pH 7, pH 8, pH 9
Sips [21] qe ¼ 1þðK S C e ÞmS
KS, qm, mS
m bC e
Vieth and Sladek [22] qe ¼ K VS C e þ q1þ bC e  q KVS, qm, b
and pH 10) there is a decrease in the adsorption capacity. This is
due to the occurrence of copper precipitation. At pH 6 there are
three species present in solution as suggested by Elliot and Huang
[4], Cu2+ in very small quantities and Cu(OH)+ and Cu(OH)2 in large
quantities. Three species are adsorbed at the surface of adsorbent
by ion exchange mechanism with the functional groups present in
adsorbent or by hydrogen bonding.
3.3. Adsorption isotherm of copper from aqueous solution
The capacity of the adsorption isotherm is fundamental, and
plays an important role in the determination of the maximum
capacity of adsorption. It also provides a panorama of the course
taken by the system under study in a concise form, indicating how
efficiently a carbon will adsorb and allows an estimate of the
economic viability of the carbons commercial applications for the
specified solute. In order to adapt for the considered system, an
adequate model that can reproduce the experimental results
obtained, equations of Langmuir, Freundlich, Redlich–Peterson,
Toth, Vieth–Sladek, Fritz–Schluender, Radke–Prausnitz and Tem-
kin have been considered. Thus, the non-linearized forms of the
different isotherm models were shown in Table 2. Fig. 5 shows the
adsorption of ions copper adjusted of Lagmuir model.
Experiments were performed at controlled pH using sodium
hydroxide and sulfuric. The pH of the solutions was regularly
checked and the pH was controlled when the variation was 0.1.

Fig. 5. Adsorption of copper. Model Langmuir. Conditions: pH: 5.0, temperature:

Fig. 4. Effect of pH on adsorption capacity of copper ions on activated carbon CP160. 298 K.
192 J.C. Moreno-Piraján, L. Giraldo / J. Anal. Appl. Pyrolysis 87 (2010) 188–193

Table 3 Table 4
Isotherm parameters for copper ions onto activated carbon CP160 Sorption capacities of several adsorbents for the uptake of ions copper from its
from cassava peel obtained by non-linear method at 298 K. aqueous solutions.

Langmuir Freundlich Sorbent Sorption capacity Reference

qm (mg/g) = 56.17016779 KF = 7.476458 Bark pine pulp 45.2 [23]

KL = 0.061459875 1/nF = 0.436197
r2 = 0.989458796 r2 = 0.949785
Redlich–Peterson Toth isotherm
A = 1.985288877 m (mg/g) = 52.96222
B = 0.0678388877 bT = 17.24579
g=1 nT = 1
r2 = 0.989824598 r2 = 0.978278
Radke–Prasunitz Fritz–Schluender
qm (mg/g) = 54.96344751 qm (mg/g) = 71.00181
KRP = 0.072145873 KFS = 8.548796
mRP = 1 mFS = 0.72458
r2 = 0.978123 r2 = 0.965785
Sips Vieth–Sladek
qm (mg/g) = 53.54032617 qm (mg/g) = 52.96357
KS = 0.086478964 KVS = 0
mS = 1 b = 0.075486
r2 = 0.997698745 r2 = 0.978315
We have followed the same treatment for our adsorption data from
aqueous solution suggested in [14]. For non-linear method, a trial and
error procedure, which is applicable to computer operation is
developed using solver add-in, Microsoft spreadsheet, Microsoft
Excel [14–22] shows the calculated isotherm parameters and their
corresponding coefficient of determination, r2, values were shown in
Table 3. From this table, it was observed that the higher r2 values for
the three-parameter Sips, Redlich–Peterson and the two-parameter
Langmuir isotherms suggests the applicability of these models to
represent the equilibrium sorption of copper ions by activated carbon
of cassava peel particles. In addition to Sips, Langmuir and Redlich–
Peterson isotherm the equilibrium copper ions uptake by activated
carbon of cassava peel particles was reasonably well represented by
Toth, Radke–Prausnitz and Vieth–Sladek isotherms with r2 values of
0.978. The value of Sips isotherm constant mS and the Redlich–
Peterson isotherm constant g equal to unity suggests that the
isotherm is approaching the Langmuir isotherm and not Freundlich
isotherm. The lower r2 values for Freundlich and Fritz–Schluender
isotherm shows it is not appropriate to use these models to represent
the uptake of copper ions by activated carbon of cassava at
equilibrium. From data of Table 2, it was observed that the Langmuir
isotherm have the same coefficient correlation that Redlich–Peterson
isotherm have so it is possible that these isotherms overlapped by
plot. Thus Langmuir is a special case of Redlich–Peterson when the
constant g equals unity. Similarly from Table 2, it was observed that
the three-parameter isotherms Toth, Radke–Prausnitz and Vieth–
Sladek isotherms overlapped to plotting because each one have the
same r2. This suggests Toth, Radke–Prausnitz and Vieth–Sladek are
the same when the Toth isotherm constant, nT, Radke–Prausnitz
isotherm constant, mRP, equals unity and the Vieth–Sladek isotherm
constant, KVS equals zero. The four best-fit three-parameter isotherms
Sips, Toth, Radke–Prausnitz and Vieth–Sladek suggests that the
sorption capacity of activated carbon of cassava peel to uptake copper
ions to be 55 mg/g. Table 3 shows the sorption capacity of other
lignocellulosic material to uptake copper ions from aqueous solutions
for comparison. From the same Table 4, it was observed that copper
ions sorption capacity of activated carbon of cassava peel was found
to be major adsorption capacity than the other low ligcellulosic
materials. Thus the low cost of waste of cassava peel can be used as an
adsorbent for the removal of ions of heavy metals bearing waste-
waters.
Manganese nodule power 40.0 mg/g [24]
Tourmaline 30.0 mg/g [25]
Bamboo 15.0 mg/g [26]
Humic acids from Fluka AG and Aldrich 51.47 mg/g [27]
Activated charcoal 10.20 mg/g [28]
Zeolite 5.0 mg/g [29]
Fungal mycelium pellets of Aspergillus niger 4.5 mg/g [30]
Alumina 15.0 mg/g [31]
Clay 18.0 mg/g [32]
Activated carbon of cassava peel 52 mg/g This study
4. Conclusion
In summary, pyrolysis of cassava peel impregnated with
chloride zinc produces materials with a well-developed pore
structure and high adsorption capacities, making possible to attain
surface areas as high as 1567 m2 g1 and pore volumes as large as
1.18 cm3 g1. The impregnation ratio has a strong influence on the
pore structure of these ACs, which can be easily controlled by
simply varying the proportion of chloride zinc used in the
activation. Thus, low impregnation ratios lead to microporous
ACs with almost no mesopores. At intermediate impregnation
ratios, ACs with wide PSDs (from micropores to mesopores) are
obtained. At high impregnation ratios one obtains essentially
mesoporous carbons with a high pore volume. Finally, the four
best-fit three-parameter isotherms Sips, Toth, Radke–Prausnitz
and Vieth–Sladek suggest that the sorption capacity of activated
carbon of cassava peel to uptake copper ions to be 55 mg/g.
Acknowledgements
The authors would like to thank the Departments of Chemistry
of the Universidad Nacional de Colombia and of the Universidad de
Los Andes (Colombia) and the Master Agreement established
between these two institutions. Special gratitude to the Fondo
Especial de Investigaciones de la Facultad de Ciencias de la
Universidad de Los Andes (Colombia) for its partial financing of
these research.
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