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Journal of Environmental Chemical Engineering 2 (2014) 22802288

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Journal of Environmental Chemical Engineering


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

Comparative cadmium adsorption study on activated carbon prepared


from aguaje (Mauritia exuosa) and olive fruit stones (Olea europaea L.)
Daniel Obregn-Valencia a , Mara del Rosario Sun-Kou b, *
a
b

Instituto de Corrosin y Proteccin, Ponticia Universidad Catlica del Per, Av. Universitaria 1801, Lima 32, Peru
Seccin Qumica, Departamento de Ciencias, Ponticia Universidad Catlica del Per, Av. Universitaria 1801, Lima 32, Peru

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 5 June 2014
Accepted 5 October 2014

This study assesses the capacity of activated carbons, prepared from Mauritia exuosa (AG series) and
Olea europaea L. (OL series) fruit stones, to adsorb cadmium ions. These carbons were activated
chemically through phosphoric acid solution, using impregnation ratios of 0.75, 1.0,
and 1:5gH3 PO4 =gprecursor . The impregnated precursor material was subsequently activated at 400,
500 and 600  C. The physicochemical characteristics of precursors and activated carbons were analyzed
by thermogravimetric analysis (TGA), nitrogen adsorptiondesorption isotherm (SBET), Boehms titration,
and scanning electron microscopy (SEM). Kinetic assays were evaluated from solutions containing
10 ppm of cadmium (Cd(II)). Within each series, the activated carbons with higher adsorption capacity
turned out to be AG0.75_600 and OL1_600 with 8.14 and 9.01 mg g1, respectively at pH 2. Among
26.33 and 24.83 mg g1, respectively at pH 5. Both activated carbons were characterized by the highest
mesoporous area and acidic surface functional group compared to other activated carbons (of each
series). The obtained isotherm correlations t better according to a Langmuir model and this was
conrmed with a RedlichPeterson model (with G values close to 1). The adsorption process of cadmium
ions took place mostly in adsorption sites of uniform energies.
2014 Elsevier Ltd. All rights reserved.

Keywords:
Adsorption
Cadmium
Aguaje stones
Activated carbons
Olive stones
Adsorption of heavy metals

Introduction
Cadmium is one of the most prevailing heavy metals with one of
the highest environmental toxicities [1]. Cadmium enters soil,
water, and air from mining, industry, and burning coal and
household waste. Fish, plants, and animals take up cadmium from
the environment [2].
Among the techniques that can currently be applied to remove
heavy metals from aqueous solutions, there are chemical precipitation, conventional coagulation, reverse osmosis, ion-exchange,
ultraltration, and adsorption, among others [3]. In industry, the
adsorption process is widely adopted for water purication because
of its efciency, versatility, and ease of implementation. Activated
carbon (AC) is a carbonaceous material and it is one of the most
applied adsorption materials due to its high surface area and
chemical reactivity [4]. It can be prepared from renewable and low
cost sources (precursors) such as lignocellulosic materials which can
be obtained from agroindustrial waste (fruit stones and peels)
[510]. The main object of this study is to analyze and compare the AC
adsorption capacity prepared from two different precursors: aguaje

* Corresponding author. Tel.: +51 1 626 2000; fax: +51 1 6262853.


E-mail address: msun@pucp.edu.pe (M.d.R. Sun-Kou).
http://dx.doi.org/10.1016/j.jece.2014.10.004
2213-3437/ 2014 Elsevier Ltd. All rights reserved.

(Mauritia exuosa) and olive (Olea europaea L.) fruit stones in order
to set the inuence of precursor nature and preparation conditions
on the adsorbent properties of the activated carbons.
Materials and methods
Activated carbon preparation
Aguaje and olive fruit stones from the Peruvian provinces of
Ucayali and Arequipa were used as precursor materials. These
materials were previously washed until all organic residues were
eliminated, oven-dried at 80  C and grounded until less than
10 mm particles were obtained.
The sample (50 g) was mixed with a particular concentration of
phosphoric acid solution (initial concentration H3PO4 85%, Merck)
in order to obtain three impregnation ratios of 0.75, 1.0, and
1.5 calculated as gram weight ratio of phosphoric acid per gram of
precursor. First, this mixture was vacuum dried and then
oven-dried at 85  C for 24 h.
The impregnated and dried material was later carbonized in a
stainless steel tubular reactor, which was placed in an oven at a
heating speed of 10  C min1 until the set activation temperature
was reached. Three different activation temperatures (400  C,

D. Obregn-Valencia, M.R. Sun-Kou / Journal of Environmental Chemical Engineering 2 (2014) 22802288

500  C, and 600  C) were considered and these were maintained for
60 min. During the activation process, a 100 cm3 min1 nitrogen
ow was used through the reactor to create an inert atmosphere
and to remove the formed vapor by entrainment.
In this study the sample nomenclature assigned is as follows:
AG = aguaje stones and OL = olive stones, follow by the impregnation ratio, and the activation temperature in Celsius degree ( C).
For example, the sample AG0.75_600 was prepared from aguaje
stones, with an acid impregnation ratio of 0:75gH3 PO4 =gprecursor , and
an activation temperature of 600  C.
Characterization
Thermogravimetric analyses (TGA) and differential thermal
analyses (DTA) of starting materials (precursor material) were
performed in a thermogravimetric analyzer (LINSEIS STA-PT model
1600) under an argon ow. For this analysis 25 mg of each material
were weighted. They were heated at a rate of 5  C min1 until
550  C were reached in an argon atmosphere with 4 L h1 ow.
The textural properties were studied by N2 adsorption
measurements at liquid nitrogen temperature using Micromeritics
GEMINI VII, model 2390t equipment. Prior to adsorption experiments, samples were degassed in vacuum at 250  C for 2 h. The
range of relative pressures used was from 0.013 to 0.99. The specic
surface area was calculated according to the BET method.
Microporous surface was calculated by the t-plot method.
Mesoporous area was evaluated by the difference of the total
area and microporous area.
The quantitative determination of the acidic surface groups was
done according to Boehms method. About 25 mg of activated
carbon was added to 50 mL solutions of NaOH 0.1 N standard and
was shaken at room temperature for 24 h. Then, the activated
carbon samples were separated by ltration. The quantity of acidic
surface group on AC samples was determined by back titration of
ltered solutions with HCl 0.1 N standard.
The activated carbons were characterized with an electronic
microscope of scanning (SEM) Phillips model 505DX. In order to
appreciate the morphology with more clarity all samples were re-

155

307

AGUAJE
STONE

40
20
0

150

155

300
T (C)

450

307
380

-20

qe

C o  C e V
W

(1)

where Co and Ce are the respective initial and equilibrium


concentration of cadmium ions (mg L1); V is the volume of
aqueous phase (L); and W is the weight of the activated carbon (g).
The cadmium ion concentration was analyzed using a PerkinElmer
model 3110 spectrophotometer with acetylene ame at a
wavelength of 228.8 nm.
Results and discussion
TGA and DTA curves for both precursors show four different
stages of weight loss (Fig. 1). For both precursors, the rst stage

100

155 257 333


380

80

40
20
0

DTA

150

155

-20

-40
-60

AGUAJE
STONE

-80
0

150

300
T (C)

450

600

TGA
OLIVE
STONE

60

600

dm/dt

dm/dt

Adsorption equilibrium information is the most important to


understand an adsorption process. Kinetics tests were conducted
at room temperature (20  C) with a cadmium solution with an
initial concentration of 10 ppm and pH 2 (which was adjusted
using 0.1 N HCl and 0.1 N NaOH). About 15 mg of activated carbon
were added to different vials with 20 mL of the aqueous solution
and kept under agitation. The contact time in each vial was
different (between 5 min and 180 min). The amount of cadmium
ions adsorbed increases sharply during the rst 30 min., and it
reaches its equilibrium value within 1 h. The activated carbons
prepared with an activation temperature of 600  C reach their
highest adsorption capacity within each series.
Adsorption isotherms were determined using a series of solutions
of cadmium in which the initial concentration was increased from
2 to 80 ppm using the activated carbons prepared with an activation
temperature of 600  C. The adsorbentadsorbate time of contact was
4 h in order to ensure stationary conditions. The adsorption capacity
is the amount of cadmium ions adsorbed at equilibrium, qe (mg g1),
and it was calculated according to Eq. (1):

TGA

60

-100

Adsorption measurements

380

80

covered with a gold lm to provide the sample of electrical


conductivity.

Mass loss (%)

Mass loss (%)

100

2281

300
T (C)

450

257 333
380

600

DTA

-40
-60

OLIVE
STONE

-80
-100

150

300
T (C)

450

Fig. 1. Thermogravimetric analysis and differential thermal analysis of aguaje and olive stones.

600

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D. Obregn-Valencia, M.R. Sun-Kou / Journal of Environmental Chemical Engineering 2 (2014) 22802288

appears by 40163  C, with a weight loss about of 12% of the initial


weight. This stage is associated with the loss of water physisorbed
on the precursors. The second stage for the aguaje stones extends
by 163307  C with a weight loss of about 47%, due mainly to
hemicelluloses degradation (Fig. 1 left). The olive stones (Fig. 1
right) showed consecutive weight losses by 155257  C and
257333  C of about 11 and 22%, respectively, attributed to
hemicelluloses and lignin degradation. In DTA curves for olive
stones, the inexion point at 257  C shows a sharp exothermic peak
due to volatile evolution (CO2, CH4 and some hydrocarbon) from
biopolymer degradation of hemicelluloses and lignin. These values
are signicantly higher compared to aguaje stones, which indicates
that there is a high content of these biopolymers in the o
lives stones.
The third stage for the aguaje stones shows up by 307377  C
with a weight loss of about 12%. At this stage the cellulose is mainly
degraded. The olive stones were degraded at 334380  C with a
weight loss of about 7%.
Lignin degradation occurred in a wide temperature range (100
900  C) due to its structure. The last stage is attributed to lignin
degradation. The aguaje stones showed a weight loss by
391570  C of about 13.83% with a remainder weight of 14.36%,
and the olive stones showed a weight loss by 380570  C of about
14% with a remainder weight of 31%. This difference is due to the
higher lignin content in olive stones, a fact which agrees with the
lignin content of 6.5% for aguaje stone and 19.5% for olive stone, as
determined by adapting the analysis method from ASTM D1106-96
(2007) [11]. The thermogravimetric results were compared with
Yang et al. [12] who made a thermogravimetric study of the
cellulose, hemicelluloses and lignin, and establishing thereby the
temperature degradation range for each biopolymer.
The results for the surface area, mesoporous distribution,
surface acidity, and adsorption capacity are shown in Table 1 [13].
In both series, the surface area decreases as the pyrolysis
temperature is increased, due to a thermal contraction effect on
the porous structure. The same behavior was observed by others
authors [1416]. This contraction is more evident in the AG series
and it affects its micro and mesoporous areas as well.
Both series of activated carbons with an activation temperature
of 600  C show that while the surface area increases with the
impregnation ratio, its mesoporous area decreases. This holds true
for both series and especially for the AG series. As for the OL series,
an exception is found for sample OL0.75, given that its mesoporous
area is lower than that of the rest of the OL series. The increase in
surface area is attributed to phosphoric acid decomposition
(Eq. (2)) [1417] which favors the formation of water and enhances
the formation of various gaseous compounds, such as CO2(g), CO(g),
H2(g) (Eqs. (3) and (4). These compounds are released from the
precursor forming the porous structure of the activated carbon
[17].

H3PO4 ! P2O5(S) + 3H2O(g)(2)

(2)

C(S) + H2O(g) ! H2(g) + CO(g)(3)

(3)

CO(g) + H2O(g) ! H2(g) + CO2(g)(4)

(4)

Acidic surface groups were determined by Boehms method.


The increase in activation temperature generated the increase in
surface acidity (Table 1); this property is closely related to
absorbentadsorbate interactions that take place on the carbon
surface. Puziy et al. [18] found that, as the activation temperature is
increased, the surface enrichment with oxygen progressively
expands to deeper layers of carbon due to the action of phosphoric
acid as an oxidizing agent. In both series, the sample with higher
impregnation ratio (AG1.5_600 and OL1.5_600) showed a low
acidic surface. Thus, although phosphoric acid favors the formation
of carbonoxygen bonds, in large quantity the phosphorous
compounds avoid the formation of oxygen-containing functional
groups on the carbon surface. This behavior was observed in
studies on AC prepared from cellulose, hemicelluloses, and lignin
[1921]. For OL series the surface acidity is very similar between
OL1_600 and OL0.75_600 decreasing signicantly in OL1.5_600.
Fig. 2 shows the SEM micrographs of the four activated carbons
with higher adsorption capacity at a magnication of 1010X. In AG
series, the sample AG0.75_600 (Fig. 2 top-left) shows pores with an
average size of 8 mm on the surface of the activated carbon. Sample
AG1_600 (Fig. 2 top-right) shows pores with an average size of
5 mm. OL series show more compact bers, furthermore, the
porous structure is not so developed as in AG series. The sample
OL0.75_600 (Fig. 2 bottom-left) shows pores with an average size
of 3.5 mm. Finally, the sample AC1_600 (Fig. 2 top-right) shows an
irregular surface with pore sizes from 2 to 0.5 mm.
Adsorption capacity
For both series of activated carbons, the capacity for cadmium
ion adsorption increases with higher activation temperature, as
shown in Table 1. Furthermore, the adsorption capacity decreases
with the increase of impregnation ratio. The higher adsorption
capacities in samples AG0.75_600 and OL1_600 were associated to
their high surface acidity and high mesoporous area (Table 1). Both
AC samples with high adsorption capacity (AG0.75_600 and
OL1_600) differ in their impregnation ratio. This fact is attributed
to differences in their precursor source. The higher lignin content
and compact bers in olive stones required a high ratio of
impregnation in order to get a high supercial acidity and suitable
mesoporous structures in favor of cadmium ion adsorption.

Table 1
Characterization and adsorption capacities of the activated carbon.
Sample

Surface area
(m2 g1)
Total

Mesoporous

AG1_400
AG1_500
AG1_600
AG0.75_600
AG1.5_600
OL1_400
OL1_500
OL1_600
OL0.75_600
OL1.5_600

1202
1077
1014
906
1623
1283
1242
1169
800
1565

109
36
77
140
32
145
135
125
10
75

Surface acidity
(mmol H+ g1)

Adsorption capacity
(mg g1)

Removal efciency
(%)

1.42
1.98
2.24
2.43
1.40
1.44
1.80
2.37
2.36
0.54

0.60
2.92
7.28
8.14
4.11
0.68
3.03
9.01
3.00
2.66

5
22
55
61
31
5
23
68
23
20

D. Obregn-Valencia, M.R. Sun-Kou / Journal of Environmental Chemical Engineering 2 (2014) 22802288

2283

Fig. 2. SEM micrographs of activated carbons at a magnication of 1010X.

On the other hand, while sample OL0.75_600 shows a similar


surface acidity as OL1_600, its surface area was not completely
developed and its low mesoporous area was unfavorable to the
adsorption capacity (3 mg g1).

In accordance with the results, the surface acidity and the


surface area developed (high mesoporous structure) were the
main important factors in the adsorption capacity of cadmium.

Fig. 3. Effect of contact time on the removal of cadmium ion from different AC prepared with an activation temperature of 600  C.

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D. Obregn-Valencia, M.R. Sun-Kou / Journal of Environmental Chemical Engineering 2 (2014) 22802288

Table 2
Pseudo rst order, pseudo second order and Elovich parameters.
Sample

AG1_400
AG1_500
AG1_600
AG0.75_600
AG1.5_600
OL1_400
OL1_500
OL1_600
OL0.75_600
OL1.5_600

Pseudo rst order

Pseudo second order


2

qe
(mg g1)

k1
(min1)

0.25
0.52
1.45
2.58
0.56
0.20
0.82
3.53
0.93
1.60

0.03
0.01
0.03
0.03
0.05
0.02
0.02
0.07
0.02
0.06

0.69
0.64
0.78
0.91
0.80
0.87
0.86
0.98
0.94
0.84

Elovichs model
2

qe
(mg g1)

k2
(g mg1 min1)

0.63
2.88
7.38
8.35
4.15
0.70
3.04
9.22
3.06
2.84

0.20
0.10
0.06
0.03
0.21
0.36
0.07
0.04
0.08
0.05

0.99
0.99
1.00
1.00
1.00
0.99
0.99
1.00
0.99
0.99

Kinetic studies
The adsorption kinetic describes the rate at which Cd(II) is
adsorbed onto the activated carbon surface and the time required
to reach its equilibrium. The results were assessed with pseudo
rst and second order models, and the Elovich equation described
by:
Pseudo rst order [22]:


k1
(5)
t
logqe  qt logqe 
2:303

Dqe (%)

(1/b) ln (ab)
(mg g1)

1/b
(mg g1)

r2

11.08
12.91
2.53
2.29
2.27
3.68
13.85
17.70
23.75
14.84

0.09
2.12
4.21
3.77
3.06
0.32
1.90
5.67
1.52
0.45

0.11
0.13
0.19
0.97
0.24
0.08
0.20
0.75
0.31
0.51

0.84
0.64
0.83
0.89
0.77
0.89
0.84
0.97
0.95
0.92

are shown in Table 2. The kinetic curves tted better with pseudo
second order model with r2 values as 0.99 which means that
adsorption occurred by two mechanisms: physical and chemical
absorption over the activated carbon surface.
A similar behavior was established by other authors [2527]. The
rate constant, k2, is lower in the AC with higher adsorption capacity.
It can be established that if the diffusion rate is higher in other AC, it
does determine the adsorption capacity. Furthermore, the Elovich
parameters show that adsorption capacity is proportional to the
available areas according to 1/b (mg g1) values.
Adsorption mechanism

Pseudo second order [23]:


t
1
1

t
qt k2 q2e qe

(6)

where k1 (min1) and k2 (g mg1 min1) are the rst and second
rate constant of adsorption respectively, qe and qt (mg g1) are the
amount adsorbed at equilibrium and the amount adsorbed at time
t. A linear plot of log(qe  qt) vs. t and t/qt vs. t is used to calculated
k1 and 1/qe (slops) and log (qe) and 1/kqe2 (intercepts), respectively.
Elovichs model [24]:
 
1
1
(7)
lnab lnt
qt
b
b
where a is considered the initial adsorption rate (mg g1 min1)
and b is related to the area of surface coverage and activation
energy for chemisorptions (g mg1). A linear plot of qt vs. ln (t) is
used to calculated 1/b (slope) and (1/b)ln (ab) (intercept). The 1/b
values are related to the vacancy sites available on the AC surface
and (1/b)ln (ab) values are related to the adsorption amount at zero
time.
All kinetics curves of activated carbon with an activation
temperature of 600  C are shown in Fig. 3. The equilibrium state
was reached within the rst hour. The kinetic model parameters

The intraparticle diffusion model was also evaluated to identify


the mechanism of adsorption based on Weber and Morriss theory
[28]. They established that the adsorption mechanism depends on
the physicochemical characteristics of the adsorbents as well as on
the mass transport or diffusion. The intraparticle diffusion
coefcient, kdiff, is given by:
qt kdiff t0:5 C

(8)

1

where qt (mg g ) is the adsorption capacity at time t (min), kdiff


(mg g1 min0.5) is the intraparticle diffusion constant and C
(mg g1) is related to the thickness of boundary layer.
The intraparticle parameters are shown in Table 3. The
intraparticle diffusion constant values decrease from the rst
stage, or external surface adsorption, to the second stage where
intraparticle diffusion is the limiting rate. Comparing the
parameters on the second stage, in both series the higher values
were found in AG0.75_600, AG1_600 and OL1_600. None linear
portion of second and third stage are extrapolated through the
origin, this indicates that particle diffusion is involved but is not
the only limiting rate mechanism (Fig. 4).
In brief, kinetic curves tted in pseudo second order model with
major inuence of intraparticle diffusion, which leads to establish

Table 3
Comparison of intraparticle diffusion constants from activated carbon.
Sample

AG1_400
AG1_500
AG1_600
AG0.75_600
AG1.5_600
OL1_400
OL1_500
OL1_600
OL0.75_600
OL1.5_600

Intraparticle diffusion model


kdiff1
(mg g1 min0.5)

kdiff2
(mg g1 min0.5)

kdiff3
(mg g1 min0.5)

C1

C2

C3

r12

r22

r 32

0.09
1.05
2.15
2.14
1.43
0.18
1.03
3.06
0.85
0.49

0.07
0.04
0.51
0.61
0.17
0.05
0.06
0.44
0.17
0.33

0.02
0.07
0.07
0.15
0.02
0.01
0.11
0.07
0.08
0.04

0
0
0
0
0
0
0
0
0
0

0.11
2.29
4.11
3.95
3.04
0.35
2.18
5.90
1.67
0.48

0.41
2.04
6.52
6.52
3.94
0.52
1.82
8.27
2.16
2.26

1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00

0.69
0.41
0.78
0.77
0.68
0.75
0.98
1.00
0.80
0.91

0.71
0.74
0.99
0.91
0.65
0.96
0.94
0.67
1.00
0.61

D. Obregn-Valencia, M.R. Sun-Kou / Journal of Environmental Chemical Engineering 2 (2014) 22802288

12

12

AG0.75_600
AG1.5_600

OL1_600
OL1_500
OL1_400

qt (mg g )

kdiff3

kdiff1

-1

-1

qt (mg g )

AG1_600
AG1_500
AG1_400
9 k
kdiff2
diff1
6

2285

OL0.75_600
OL1.5_600

kdiff2

kdiff3

0
0

6
1/2

10

12

1/2

6
1/2

(min )

10

12

1/2

(min )

Fig. 4. Intraparticle diffusion model plot for the adsorption of cadmium ion from different activated carbons.

that ion cadmium adsorption is governed by two types of


interactions, physical and chemical, over the activated carbon
surface.
Adsorption isotherms
An adsorption isotherm curve describes the phenomenon
governing the retention or mobility of a substance from the
aqueous solution to a solid-phase at a constant temperature (20  C)
and pH 2. The experimental values are related to the following
equilibrium isotherm models: Langmuir, Freundlich, Redlich
Peterson, DubininRadushkevich and Temkin [29].
Langmuir isotherm model can be represented as:
Ce
1
ce

qe K L qmax qmax

(9)

Freundlich isotherm model can be represented as:


1
logqe logK F logC e
n

(10)

where qe (mg g1) is the adsorption capacity at equilibrium and Ce


(mg L1) is the solute concentration in the solution at equilibrium.
The KL (L mg1) constant is related to the adsorption heat and the
KF (mg1 1/n L1/n g1) constant is a parameter related to the
adsorption capacity. The maximum capacity value is represented
by qmax (mg g1) and 1/n value (dimensionless) represents the
adsorption intensity.

where qe (mg g1) is the adsorption capacity at equilibrium, Ce (mg


L1) is the solute concentration present in the solution at
equilibrium; ARP,BRP and G (heterogeneity grade) are Redlich
Peterson parameters. In the limit, it approaches Freundlich
isotherms model at high concentration (as G values tend to 0)
and is in accordance with the low concentration limit of the ideal
Langmuir condition (as G values are all close to 1).
DubininRadushkevich (DR) isotherm assumes that there is a
surface area in which the adsorption energy is homogeneous. The
DR isotherm is expressed as:
lnqe lnqs  K ad e2

1
E p
2K ad

(13)

OL1_600
12

10

10

OL0.75_600

OL1.5_600

qe (mg g-1)

12

AG0.75_600

AG1_600

AG1.5_600

4
2

2
0

(12)

where e = RTln [1 + 1/Ce], qs is the theoretical isotherm saturation


capacity (mg g1), Kad is related to the mean free energy of sorption
per mole of the adsorbate when it is transferred to the surface of
the solid from the solution and this energy can be computed using
the following relationship:

14

14

qe (mg g-1)

The RedlichPeterson isotherm [30] is an empirical isotherm. It


combines elements from both the Langmuir and Freundlich
equations and the mechanism of adsorption is a hybrid. Therefore
it can be applied either to homogeneous or heterogeneous
systems. The linearized equation is expressed as:


Ce
(11)
ln ARP  1 GlnC e lnBRP
qe

20

40
60
-1
Ce (mg L)

80

20

40
-1
Ce (mg L)

60

80

Fig. 5. Adsorption isotherms of cadmium ion from different activated carbons prepared with an activation temperature of 600  C.

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D. Obregn-Valencia, M.R. Sun-Kou / Journal of Environmental Chemical Engineering 2 (2014) 22802288

Table 4
Comparison of Frendlich, Langmuir, RedlichPeterson, DubininRadushkevich, and Temkin model adsorption parameters at pH 2.
Model

Sample
AG0.75_600

Freundlich
KF (mg g1)
1/n
r2
Dqe (%)

AG1_600

AG1.5_600

OL0.75_600

OL1_600

OL1.5_600

6.08
0.18
0.81
1.52

3.83
0.23
0.80
5.92

1.90
0.32
0.88
2.94

1.70
0.30
0.98
158.24

5.78
0.20
0.76
17.03

2.29
0.22
0.92
3.69

11.87
0.74
1.00
0.03

9.47
0.48
0.99
3.56

6.76
0.23
1.00
0.76

6.87
0.14
0.99
3.87

11.86
0.83
0.99
10.40

6.57
0.11
0.97
1.39

0.77
0.99
1.00
0.03

0.98
0.97
0.99
0.72

0.98
0.95
0.99
0.39

0.43
0.96
0.99
1.08

2.34
0.98
1.00
5.36

0.25
0.97
0.99
0.62

DubininRadushkevich
Qm (mg g1)
Kad
E (kJ mol1)
r2
Dqe (%)

11.1
0.29
1.32
0.96
0.03

8.1
0.15
1.80
0.95
0.72

5.2
0.52
0.98
0.90
0.39

4.7
0.53
0.97
0.80
1.08

10.0
0.05
3.06
0.96
5.36

5.1
3.62
0.37
0.61
0.62

Temkin
A (L g1)
B (kJ mol1)
r2
Dqe (%)

69.79
1.67
0.87
1.13

31.73
1.98
0.93
4.39

4.56
2.12
0.98
1.07

3.54
2.32
0.97
0.50

142.84
1.83
0.90
5.98

4.10
2.41
0.88
0.39

Langmuir
qmax (mg g1)
KL (L mg1)
r2
Dqe (%)
RedlichPeterson
BRP (L mg1)G
G
r2
Dqe (%)

The Temkin isotherm assumes that the decrease in the heat of


adsorption is linear rather than logarithmic, as implied in the
Freundlich equation. It is expressed as:
qe

RT
RT
lnAT lnC e
b
b

(14)

where constant RT/b is related to the heat of adsorption, R the


universal gas constant (J mol1 K1), T the temperature (K), b the
variation of adsorption energy (J mol1) and AT is the equilibrium
binding constant (L mg1) corresponding to the maximum binding
energy.
The isotherms curves are shown in Fig. 5. All activated carbons,
except for AG1_600 and OL1_600, are concave type and are similar
to curve L type according to Giless classication [31], meanwhile,
AG1_600 and OL1_600 are similar to H type curve. This type of
curve represents a strong adsorption of the adsorbate which is
reected in the high initial slope. In all cases, except for
AG0.75_600, there is a progressive increase of adsorption capacity
as the equilibrium concentration increases.
The correlation of the experimental values with the mathematical
isotherm models are shown in Table 4. The isotherm constants for
RedlichPeterson were evaluated using a trial-and-error optimization method to calculate the isotherm constants through maximization of the coefcient of determination (r2). Both activated carbon
series (AG and OL) isotherm curves t the Langmuir and Redlich
Peterson isotherm models (r2  0.99 for all the tested samples. The
normalized standard deviation values were calculated by [32]:
s
X qeexp  qepred =qepred 2
(15)
Dqe % 100 
N
where qe(exp) is the experimental qe and qe(pred) is the corresponding predicted qe according to the equation under study with best
tted parameters, N is the number of measurements.

The G value close to 1 in RedlichPeterson model conrms that


the adsorption process corresponds to a Langmuir model.
The Langmuir isotherm model shows that the monolayer
adsorption value (qmax) decreases with high impregnation rates. In
AG series, these values decrease from 11.87 to 6.76 mg g1. In OL
series, the maximum adsorption capacity is obtained for
OL1_600 and the least for OL1.5_600 with 11.86 and 6.57 mg g1,
respectively.
Furthermore, the adsorption constant, KL, is higher in the
activated carbons with higher adsorption capacities in both series;
this means that adsorption process requires a high energy to retain
the cadmium ion over the carbon surface. This can be explained by
pH solution condition (pH 2) which can produce a competitive
effect between cadmium ions and protons H+ in the solution.
Table 5
Comparison of Frendlich, Langmuir, RedlichPeterson, DubininRadushkevich, and
Temkin model adsorption parameters at pH 5.
Model

Sample
AG0.75_600

OL1_600

Freundlich
KF (mg g1)
1/n
r2
Dqe (%)

12.03
0.19
0.95
0.73

12.59
0.18
0.91
1.85

Langmuir
qmax (mg g1)
KL (L mg1)
r2
Dqe (%)

26.33
0.46
0.99
8.27

24.83
0.78
1.00
14.50

1.69
1.00
1.00
1.22

3.17
1.00
1.00
76.13

RedlichPeterson
BRP (L mg1)G
G
r2
Dqe (%)

D. Obregn-Valencia, M.R. Sun-Kou / Journal of Environmental Chemical Engineering 2 (2014) 22802288

Furthermore, the total surface charge will be on average positive


[4] in a solution with pH lower than the point zero charge (pHPZC)
of the adsorbent (in previous work, it was found that pHPZC was on
average 2.55) which generates electrostatic repulsion between the
AC surface charge and the cadmium ion.
The adsorption capacity of Cd increased at pH 5 (Table 5), for
example, according with Langmuir model, the sample AG0,75 _600
reached a qmax = 26.33 mg g1 and OL1_600 a qmax = 24.83 mg g1.
These results were compared with Rao et al. [33] which obtained a
qmax = 19.59 mg g1. At this pH, the carbon surface is negatively
charged, it gets more nucleophile and this allows a greater
attraction of the adsorbate to the surface of the adsorbent. This
indicates that the adsorption process would be associated with an
electrostatic interaction.
Conclusions
The parameters with greater inuence in the adsorption
properties of the activated carbons are the precursor nature, the
activation temperature, and the impregnation ratio. Aguaje stones
offer a promising raw material for the production of activated
carbon for water treatment purposes.
The activated carbon chemical and textural characteristics are
highly related to the precursor nature and generate different
adsorption capacities, although both precursors (aguaje and olive
fruit stones) were prepared under the same conditions.
The activated carbons with the highest adsorption capacities
were: from AG series, AG0.75_600 (26.33 mg g1) and from OL
series OL1_600 (24.83 mg g1) at pH 5. Both activated carbons
presented a high developed mesoporous area (140 y 125 m2 g1,
respectively) and a high supercial acidity (2.43 y 2.37 mmol
H+ g1, respectively). The high lignin content and natural ber
compaction in olive stones required a higher impregnation ratio to
get a suitable supercial acidity and mesoporous area to increase
the cadmium ion adsorption.
The kinetic curve tted suitably to pseudo second order model,
which allows to establish that the adsorption process is the result
of two types of interactions, chemical and physical, between the
metal ion and the activated carbon surface.
The isotherm model ts suitably to Langmuir model. In
accordance with RedlichPetersons G parameter near to 1, the
adsorption process mostly takes place in homogeneous active sites
over the activated carbon surface.
Conicts of interest
The authors declared that there is no conict of interest.
Acknowledgement
The authors thank Vicerrectorado de Investigacin (VRI-PUCP)
for the partial support under Proyecto Interdisciplinario DGI 20100099.
References
[1] Agency for Toxic Substances and Disease Registry, [Internet]. Toxicological
Prole for Cadmium. [updated 03.04.11; cited 23.08.13]. Available from: http://
www.atsdr.cdc.gov/toxproles/tp5-c6.pdf.
[2] Agency for Toxic Substances and Disease, [Internet]. The Priority List of
Hazardous Substances That Will Be the Subject of Toxicological Proles: the
ATSDR 2011 Substance Priority List [updated 25.10.11; cited 23.08.13].
Available from: http://www.atsdr.cdc.gov/SPL/index.html.
[3] F. Fu, Q. Wang, Removal of heavy metal ions from wastewaters: a review, J.
Environ. Manage. 92 (3) (2011) 407418, doi:http://dx.doi.org/10.1016/j.
jenvman.2010.11.011. 21138785.

2287

[4] R.C. Bansal, M. Goyal, Activated Carbon Adsorption, CRC Press, Boca Ratn, U.S.
A, 2005.
[5] N. Yaln, V. Sevin, Studies of the surface area and porosity of activated
carbons prepared from rice husks, Carbon 38 (14) (2000) 19431945, doi:
http://dx.doi.org/10.1016/S0008-6223(00)00029-4.
[6] W.T. Tsai, C.Y. Chang, S.L. Lee, Preparation and characterization of activated
carbons from corn cob, Carbon 35 (8) (1997) 11981200, doi:http://dx.doi.org/
10.1016/S0008-6223(97)84654-4.
[7] B.S. Girgis, S.S. Yunis, A.M. Soliman, Characteristics of activated carbon from
peanut hulls in relation to conditions of preparation, Mater. Lett. 57 (1) (2002)
164172.
[8] A. Aygn, S. Yenisoy-Karaka, I. Duman, Production of granular activated
carbon from fruit stones and nutshells and evaluation of their physical,
chemical and adsorption properties, Microporous Mesoporous Mater. 66 (23)
(2003) 189195, doi:http://dx.doi.org/10.1016/j.micromeso.2003.08.028.
[9] G. Duman, Y. Onal, C. Okutucu, S. Onenc, J. Yanik, Production of activated
carbon from pine cone and evaluation of its physical, chemical, and adsorption
properties, Energy Fuels 23 (4) (2009) 21972204, doi:http://dx.doi.org/
10.1021/ef800510m.
[10] M. Olivares-Marn, C. Fernndez-Gonzlez, A. Macas-Garca, V. GmezSerrano, Porous structure of activated carbon prepared from Cherry stones by
chemical activation with phosphoric acid, Energy Fuels 21 (5) (2007) 2942
2949, doi:http://dx.doi.org/10.1021/ef060652u.
[11] American Society for Testing and Materials, ASTM D1106-96(2007). Standard
Test Method for Acid-Insoluble Lignin in Wood, ASTM International, West
Conshohocken, PA, 2007.
[12] H. Yang, R. Yan, H. Chen, D.H. Lee, C. Zheng, Characteristics of hemicellulose,
cellulose and lignin pyrolysis, Fuel 86 (1213) (2007) 17811788, doi:http://
dx.doi.org/10.1016/j.fuel.2006.12.013.
[13] D.C. Obregn-Valencia, Comparative Cadmium Adsorption Study on Activated
Carbon Prepared from Aguaje and Olive Stones (Lic thesis), Ponticia
Universidad Catlica del Per, Peru, 2012.
[14] W.M. Daud, W.S. Ali, Comparison on pore development of activated carbon
produced from palm shell and coconut shell, Bioresour. Technol. 93 (1) (2004)
6369, doi:http://dx.doi.org/10.1016/j.biortech.2003.09.015. 14987722.
[15] M. Molina-Sabio, F. Rodrguez-Reinoso, Role of chemical activation in the
development of carbon porosity, Colloids Surf. A 241 (13) (2004) 1525, doi:
http://dx.doi.org/10.1016/j.colsurfa.2004.04.007.
[16] M. Molina-Sabio, F. Rodrguez-Reinoso, F. Caturla, M.J. Sells, Porosity in
granular carbons activated with phosphoric acid, Carbon 33 (8) (1995) 1105
1113, doi:http://dx.doi.org/10.1016/0008-6223(95)00059-M.
[17] M. Jagtoyen, F. Derbyshire, Activated carbons from yellow poplar and white
oak by H3PO4 activation, Carbon 36 (78) (1998) 10851097, doi:http://dx.doi.
org/10.1016/S0008-6223(98)00082-7.
[18] A.M. Puziy, O.I. Poddubnaya, R.P. Socha, J. Gurgul, M. Wisniewski, XPS and NMR
studies of phosphoric acid activated carbons, Carbon 46 (15) (2008) 2113
2123, doi:http://dx.doi.org/10.1016/j.carbon.2008.09.010.
[19] Y. Guo, D.A. Rockstraw, Physical and chemical properties of carbons
synthesized from xylan, cellulose, and kraft lignin by H3PO4 activation,
Carbon 44 (8) (2006) 14641475, doi:http://dx.doi.org/10.1016/j.carbon.2005.12.002.
[20] A.M. Puziy, O.I. Poddubnaya, A. Martnez-Alonso, F. Surez-Garca, J.M.D.
Tascn, Surface chemistry of phosphorus-containing carbons of lignocellulosic
origin, Carbon 43 (14) (2005) 28572868, doi:http://dx.doi.org/10.1016/j.
carbon.2005.06.014.
[21] B. Jibril, O. Houache, R. Al-Maamari, B. Al-Rashidi, Effects of H3PO4 and KOH in
carbonization of lignocellulosic material, J. Anal. Appl. Pyrol. 83 (2) (2008)
151156, doi:http://dx.doi.org/10.1016/j.jaap.2008.07.003.
[22] M.H. Kalavathy, T. Karthikeyan, S. Rajgopal, L.R. Miranda, Kinetic and isotherm
studies of Cu(II) adsorption onto H3PO4-activated rubber wood sawdust, J.
Colloid Interface Sci. 292 (2) (2005) 354362, doi:http://dx.doi.org/10.1016/j.
jcis.2005.05.087. 16040040.
[23] Y.S. Ho, G. McKay, Pseudo-second order model for sorption processes, Process
Biochem. 34 (5) (1999) 451465, doi:http://dx.doi.org/10.1016/S0032-9592
(98)00112-5.
[24] M.K. Aroua, S.P. Leong, L.Y. Teo, C.Y. Yin, W.M. Daud, Real-time determination of
kinetics of adsorption of lead(II) onto palm shell-based activated carbon using
ion selective electrode, Bioresour. Technol. 99 (13) (2008) 57865792, doi:
http://dx.doi.org/10.1016/j.biortech.2007.10.010. 18023577.
[25] F. Bouhamed, Z. Elouear, J. Bouzid, Adsorptive removal of copper(II) from
aqueous solutions on activated carbon prepared from Tunisian date stones:
equilibrium, kinetics and thermodynamics, J. Taiwan Inst. Chem. Eng. 43 (5)
(2012) 741749, doi:http://dx.doi.org/10.1016/j.jtice.2012.02.011.
[26] T.S. Anirudhan, S.S. Sreekumari, Adsorptive removal of heavy metal ions from
industrial efuents using activated carbon derived from waste coconut
buttons, J. Environ. Sci. 23 (12) (2011) 19891998, doi:http://dx.doi.org/
10.1016/S1001-0742(10)60515-3. 22432329.
[27] L. Wang, J. Zhang, R. Zhao, Y. Li, C. Li, C. Zhang, Adsorption of Pb(II) on activated
carbon prepared from Polygonum orientale Linn.: Kinetics, isotherms, pH, and
ionic strength studies, Bioresour. Technol. 101 (15) (2010) 58085814, doi:
http://dx.doi.org/10.1016/j.biortech.2010.02.099. 20362430.
[28] W.J. Weber, J.C. Morris, Kinetics of adsorption on carbon from solution, J.
Sanitary Eng. Div. 89 (2) (1963) 3160.
[29] K.Y. Foo, B.H. Hameed, Insights into the modeling of adsorption isotherm
systems, Chem. Eng. J. 156 (1) (2010) 210, doi:http://dx.doi.org/10.1016/j.
cej.2009.09.013.

2288

D. Obregn-Valencia, M.R. Sun-Kou / Journal of Environmental Chemical Engineering 2 (2014) 22802288

[30] O. Redlich, D.L. Peterson, A useful adsorption isotherm, J. Phys. Chem. 63 (6)
(1959) 1024, doi:http://dx.doi.org/10.1021/j150576a611.
[31] C.H. Giles, D. Smith, A. Huitson, A general treatment and classication of
the solute adsorption isotherm. I. Theoretical, J. Colloid Interface Sci. 47
(3) (1974) 755765, doi:http://dx.doi.org/10.1016/0021-9797(74)90252-5.
[32] R.K. Singh, S. Kumar, S. Kumar, A. Kumar, Development of parthenium based
activated carbon and its utilization for adsorptive removal of p-cresol from

aqueous solution, J. Hazard. Mater. 155 (3) (2008) 523535, doi:http://dx.doi.


org/10.1016/j.jhazmat.2007.11.117. 18207322.
[33] M.M. Rao, A. Ramesh, G.P. Rao, K. Seshaiah, Removal of copper and cadmium
from the aqueous solutions by activated carbon derived from Ceiba pentandra
hulls, J. Hazard. Mater. 129 (13) (2006) 123129, doi:http://dx.doi.org/
10.1016/j.jhazmat.2005.08.018. 16191464.