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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
(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,
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)
100
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
TGA
60
-100
Adsorption measurements
380
80
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
2282
(2)
(3)
(4)
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
2283
Fig. 3. Effect of contact time on the removal of cadmium ion from different AC prepared with an activation temperature of 600 C.
2284
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
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
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
(8)
1
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
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
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.
qe K L qmax qmax
(9)
(10)
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)
14
14
qe (mg g-1)
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.
2286
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 (%)
RT
RT
lnAT lnC e
b
b
(14)
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 (%)
2287
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