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Chemical Engineering Journal 174 (2011) 117125

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Chemical Engineering Journal


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NaOH-activated carbon of high surface area produced from coconut shell:


Kinetics and equilibrium studies from the methylene blue adsorption
Andr L. Cazetta a , Alexandro M.M. Vargas a , Eurica M. Nogami a , Marcos H. Kunita a ,
Marcos R. Guilherme a , Alessandro C. Martins a , Tais L. Silva b , Juliana C.G. Moraes a , Vitor C. Almeida a,
a
Department of Chemistry, Universidade Estadual de Maring, Av. Colombo 5790, CEP 87020-900, Maring, Paran, Brazil
b
Department of Civil Engineering, Universidade Estadual de Maring, Av. Colombo 5790, CEP 87020-900, Maring, Paran, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Activated carbons (ACs) of coconut shell produced by NaOH activation at impregnation ratios of
Received 5 July 2011 NaOH:char (w/w) equal to 1:1 (AC-1), 2:1 (AC-2) and 3:1 (AC-3) were prepared. The properties of these
Received in revised form 20 August 2011 carbons, including BET surface area, pore volume, pore size distribution, and pore diameter, were char-
Accepted 22 August 2011
acterized from N2 adsorption isotherms. It was found that the ACs are essentially microporous and that
the BET surface area was in order of 783 m2 g1 for AC-1, 1842 m2 g1 for AC-2, and 2825 m2 g1 for
Keywords:
AC-3. Scanning electron microscopy images showed a high pore development while Boehm method and
NaOH-activated carbon
Fourier-transform infrared spectroscopy spectra indicated the presence of acid functional groups which
Coconut shell
Methylene blue
was conrmed by pH drift method. The adsorption equilibrium and kinetics of methylene blue (MB) onto
Adsorption AC-3 were carried out. Experimental data were tted to the four isotherm models (Langmuir, Freundlich,
Toth and RedlichPeterson), and was found that Langmuir model presented the best t, showing maxi-
mum monolayer adsorption capacity of 916 mg g1 . The kinetic studies showed that experimental data
follow pseudo-second-order model. The mechanism of the adsorption process was described from the
intraparticle diffusion model. The AC-3 has a high surface area and showed to be an efcient adsorbent
for removal of MB from aqueous solutions.
2011 Elsevier B.V. All rights reserved.

1. Introduction production of ACs from cheap and renewable precursors, such as


olive husk [3], coffee endocarp [4], cotton stalks [5], plum kernels
The impacts caused by a variety of industrial pollutants and [6], r wood [7,8], pistachio shell [8], olive stone [9], bamboo [10]
growing concern for environmental issues have led to the search and amboyant pods [11].
for new methods of treatment, and development of new materials The coconut shell is a potential precursor for the production of
that are able to reduce these environmental problems. Among the ACs, because it corresponds to 35% of the fruit mass. Brazil is the
various types of existing efuent treatment, the adsorption pro- fourth largest producer of coconut in the world: its current produc-
cess using activated carbon is of easy application, good efciency tion is equivalent to 6% of world, which generates a large amount
and economically viable [1]. of waste from this fruit. The use of coconut shell for the production
Activated carbons (ACs) are porous materials that have a high of ACs has been studied by some researchers, which reported the
surface area and high adsorption capacity, which can remove a chemical activation of the material from chemical reagents, such
wide variety of pollutants such as dyes, heavy metals, pesticides as KOH [1214], H3 PO4 NaHCO3 [15] and ZnCl2 [16]. The produc-
and gases. Due to its adsorptive properties, the ACs are used to tion of ACs from coconut shell by chemical activation with NaOH,
purify, detoxify, deodorize, lter, discolor or alter the concentra- so far, has not been reported in the literature yet. NaOH has been
tion of many liquid and gaseous materials. These applications are used in studies for production of ACs with high surfacial area from
of great interest in various industrial sectors such as food, phar- r wood [17], plum kernels [6] and amboyant pods [18]. Among
maceutical, chemical, oil, mining, and especially in treatment of the basic reagents, Tseng [19] reported that NaOH activation in
drinking water [2]. comparison with KOH activation has advantages such as: (i) lower
Because of the high cost and non-renewable source of commer- dosage (weight measurement), (ii) cheaper, (iii) more environmen-
cially available AC, in recent years, researchers have studied the tally friendly, and (iv) less corrosive.
Methylene blue (MB) is a cationic dye that is most com-
monly used for coloring. It is generally used for dyeing cotton,
Corresponding author. Tel.: +55 44 3261 3678; fax: +55 3261 4334. wool, and silk. MB can cause eye burns in humans and animals,
E-mail address: vcalmeida@uem.br (V.C. Almeida). methemoglobinemia, cyanosis, convulsions, tachycardia, dyspnea,

1385-8947/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.08.058
118 A.L. Cazetta et al. / Chemical Engineering Journal 174 (2011) 117125

irritation to the skin, and if ingested, irritation to the gastrointesti- microscopy (SEM) analysis (Shimadzu, model SS 550) was carried
nal tract, nausea, vomiting, and diarrhea [20]. This dye has been out for raw material, AC-1, AC-2 and AC-3 to study the development
studied because of its known strong adsorption onto solids, and it of porosity.
often serves as a model compound for removing organic contami- The surfaces of ACs were chemically characterized by Boehm
nants and colored bodies from aqueous solutions [10]. titration [23] and pH drift method [24]. The surface organic struc-
The focus of this research was to prepare ACs from coconut shell tures of the raw material and AC were studied by FT-IR spectra
by NaOH activation and evaluate its potential for adsorption in recorded at 4 cm1 of resolution and 20 scans min1 between 4000
removal of MB from the aqueous solution. The textural and chem- and 400 cm1 using a Bomem MB-100 spectrometer.
ical characterizations of the ACs were also performed. In order to
establish the removal capacity of this adsorbent, different models of 2.3. Batch adsorption studies
isotherms and adsorption kinetics were tted to the experimental
data. The cationic dye, MB or Basic Blue 9 (B. Herzog, Germany), was
used as an adsorbate. It has the molecular formula C16 H18 N3 SCl and
2. Materials and methods the molecular weight of 319.85 g mol1 .
A stock solution of 1.0 g L1 was prepared by dissolving the
2.1. Raw material appropriate amount of MB in 100 mL and completing the volume of
1000 mL with distilled water. Batch adsorption was performed in
Coconuts used for preparation of AC were obtained from local a set of 50 mL plastic asks containing 25 mL of MB solutions with
market in Maring, Paran, Brazil. The fruits were washed with dis- various initial concentrations (1001000 mg L1 ). The amount of
tilled water, and subsequently dried at 110 C for 48 h. After that, 0.025 g of AC was added to each ask and kept at 25 C on a shaker.
the shells were removed from the fruits, dried at 110 C for 48 h, For equilibrium studies, the experiment was carried out for 2.5 h
ground and granulometrically separated. The proximate analysis of to ensure equilibrium was reached. Previous tests were performed
the raw material used in this study by ASTM-D1762 Standards [21] varying the solution pH from 2 to 10 and the MB removal of approx-
revealed moisture, ash, volatile matter, and xed carbon content imately 90% in all pH range was determined. Therefore, the pH 6.5
values of 3.52, 1.28, 74.60, and 20.60%, respectively. was selected because it favors the adsorption system MB-AC-3. All
samples were ltered prior to analysis (using 0.45-m membrane
2.2. Preparation and characterization of activated carbon lters) in order to minimize the interference of small particles of the
activated carbon. The MB concentrations in the supernatant solu-
The raw material, which had particle size between 250 m tions before and after adsorption were determined using a UVvis
and 425 m, was placed in a horizontal stainless steel reactor and spectrophotometer (Varian Cary 50 UV/Vis) at its maximum wave-
heated in a furnace at the rate of 20 C min1 from room temper- length () of 664 nm. The MB concentration was determined by
ature to 500 C, and maintained at this temperature for 2.0 h. The comparing absorbance to a calibration curve previously obtained.
obtained char was mixed with varying amounts of NaOH pellets All experiments were duplicated and only the mean values were
and 10 mL of water, at the ratios of 1:1, 2:1, and 3:1 (NaOH:char) in reported. The amount of MB adsorbed onto AC, qe (mg g1 ) was
a vertical stainless steel reactor under magnetic stirring for 2 h and calculated by Eq. (2):
then dried at 130 C for 4 h. The reactor containing the dry mixture
(C0 Ce )V
was set into a furnace under N2 ow of 100 cm3 min1 , and heated qe = (2)
W
at the rate of 20 C min1 to the nal temperature of 700 C, which
was maintained for 1.5 h. After cooling, the resulting mixture was where C0 and Ce (mg L1 ) are the initial and equilibrium liquid-
washed with a 0.1 M solution of HCl followed by hot distilled water phase concentrations of MB, respectively, V (L) is the volume of the
until pH 6.5 to eliminate activating agent residues and other inor- solution, and W (g) is the mass of dry adsorbent used. For batch
ganic species formed during the process. In the washing step, the kinetic studies, the same procedure was followed, but the aqueous
activated carbon was separated using 0.45-m membrane lters. samples were taken at preset time intervals. The concentrations of
The carbon obtained was dried at 110 C for 24 h and kept in tightly MB were similarly measured. The amount of MB adsorbed at any
closed bottles for further analysis. The prepared activated carbon time, qt (mg g1 ), was calculated by Eq. (3):
at NaOH:char ratios of 1:1, 2:1, and 3:1 were labeled as AC-1, AC-2,
(C0 Ct )V
and AC-3, respectively. qt = (3)
W
The activated carbon yield was dened as the nal weight of
product after activation, washing, and drying. The percent yield where Ct (mg L1 ) is the liquid-phase concentration of MB at any
was determined from the relation: time. Initial concentrations of 800, 900, and 1000 mg L1 of the dye
wc and an adsorption time of 150 min were studied.
Yield (%) = 100 (1)
wo
where wc and wo are the nal activated carbon dry weight (g) and 2.4. Adsorption isotherm and kinetic models
the precursor dry weight (g), respectively.
Textural characterization of the ACs was carried out by N2 The application of adsorption isotherms is very useful to
adsorption at 77 K using QuantaChrome Nova 1200 surface area describe the interaction between the adsorbate and the adsorbent
analyzer. The surface area, SBET , was determined from isotherms of any system. The parameters obtained from the different mod-
using the BrunauerEmmettTeller equation (BET). The total pore els provide important information on the sorption mechanisms
volume, VT , was dened as the volume of liquid nitrogen cor- and the surface properties and afnities of the adsorbents. There
responding to the amount adsorbed at a relative pressure of are several equations for analyzing experimental adsorption equi-
P/P0 = 0.99 [22]. The micropore volume, V , was determined with librium data. The Langmuir and Freundlich models are the most
the DubinineRadushkevich equation and the mesopore volume, accepted surface adsorption model for single solute systems. On
Vm , was calculated as the difference between VT and V . The aver- the other hand, an interesting trend in the isotherm modeling is
age pore diameter, Dp , was calculated using the relation 4VT /SBET , the derivation in more than one approach, thus directing to the dif-
and the pore size distribution, by the BJH method. Scanning electron ference in the physical interpretation. In this study, the isotherms of
A.L. Cazetta et al. / Chemical Engineering Journal 174 (2011) 117125 119

Table 1
Non-linear forms of kinetic and isotherm models, and intraparticle diffusion model.
a 1000
Models Names Expression 900

Adsorbed Volume at STP (cm g )


-1
AC-3
qe = Qm Ka Ce 800

3
Isotherm Langmuir 1+Ka Ce

Freundlich RL = 1 700
1+Ka Ce

qe = KF Ce1/nF 600
RedlichPeterson qe =
ARP Ce 500 AC-2
g
1+BRP Ce
Qmax bT Cf 400
Toth Q = nT
[1+(bT Cf )1/nT ]
300
Kinetic Pseudo-rst order qt = qe [1 eK1 t ] 200
AC-1
h0 = K1 qe 100
K2 q2 t
Pseudo-second order qt = e
1+K2 qe t
0
0.2 0.4 0.6 0.8 1.0
h0 = K2 q2e 0
Relative Pressure (P/P )
Intraparticle diffusion qt = kid t0.5 + C

Qm = maximum adsorption capacity; Ka = Langmuir constant; RL = separation factor; b


KF and nF = Freundlich constants; ARP , BRP and g = RedlichPeterson constants, bT 0.9
and nT = Toth constants, K1 and K2 = rate constants for the pseudo-rst and pseudo- AC-1
second order adsorption, respectively; h0 = initial adsorption rate; kid = intraparticle 0.8 AC-2
diffusion constant; C = intercept. AC-3
0.7
0.6

P / n (P - P)
two parameters (Langmuir and Freundlich [25]) and three param-
eters (RedlichPeterson [26] and Toth [27]) were applied. Table 1 0.5

0
shows the equations and parameters of such isotherms.
a
0.4
The kinetic models such as pseudo-rst order [28], pseudo-
0.3
second order [29] and intraparticle diffusion model [25] were used
to understand the adsorption dynamics in relation to time for the 0.2
MB-AC-3 system. The equation and parameters of these models are
0.1
shown in Table 1.
Both adsorption isotherms and kinetic models of pseudo-rst 0.03 0.06 0.09 0.12 0.15 0.18 0.21
0
and pseudo-second order were tted employing the non-linear t- Relative Pressure (P/P )
ting method, using the software Origin 6.0. The theoretical models
most appropriate that describe the experimental data of MB-AC-3 Fig. 1. N2 adsorption (closed symbols) and desorption (open symbols) isotherms at
77 K (a) and linear ts for the adsorption isotherms (b) of the AC-1, AC-2 and AC-3.
system were chosen from the correlation coefcient (R2 ). Addition-
ally, the normalized standard deviation, qe (%), was calculated for
kinetic studies by Eq. (4).
the N2 volume was observed for whole range of relative pressure,

 [(qe,exp qe,cal )/qe,exp ]2 and that the higher initial volume was shown for AC-3. According to
qe (%) = 100 (4) IUPAC, the isotherms that show reversibility are classied as type I,
N1 which also are known as Langmuir. This type of isotherm indicates
where N is the number of data points, qe,exp and qe,cal (mg g1 ) are that the adsorbate and adsorbent have a high afnity, and that the
the experimental and calculated equilibrium adsorption capacity material in question consists mostly of micropores [30].
value, respectively. The BET equation requires a linear t that relates P/na (P0 P)
and P/P0 , where na is the amount in moles adsorbed at the relative
3. Results and discussions pressure P/P0 . Fig. 1(b) shows the linear ts for the isotherms of AC-
1, AC-2 and AC-3. The values of correlation coefcients obtained, R2 ,
3.1. Yield were 0.9999, 0.9992 and 0.9998 for AC-1, AC-2 and AC-3, respec-
tively.
The yield values based on the original weight of the raw material The pore size distributions of the prepared ACs are shown in
were of 33.80% for the char and of 28.94%, 23.26% and 18.80% for Fig. 2. An increase in pore volume was observed for the ACs. Addi-
the AC-1, AC-2 and AC-3, respectively. According to the results, the tionally, the most of the pores had sizes smaller than 2.5 nm (25 A),
increase in the impregnation ratio (NaOH:char) caused a decrease indicating a development of microporosity of the material
in the yield values. The decrease in the yield for ACs is justied by Table 2 lists the physical properties of activated carbon derived
action of the dehydrating reagent (NaOH), which provided elimi- from coconut shell by NaOH activation. The data show that the
nation and dehydration reactions, breaking the bonds COC and SBET of the ACs increased from 783 m2 g1 to 2825 m2 g1 when the
CC of the raw material [22]. Tseng and co-workers [7] report that NaOH:char ratio increased from 1 to 3. The differences between the
the activation mechanism with NaOH is according to the following SBET values of AC-1 and AC-2, AC-2 and AC-3 were of approximately
reaction: 1000 m2 g1 , showing a linear relationship of SBET with increasing
of the NaOH:char ratio. As can be observed, the increase in the
6NaOH + 2C  2Na + 2Na2 CO3 + 3H2 (5) NaOH:char promotes an increase of the SBET and a decrease in the
AC yields. Researches, which used the r wood [17] and Siberian
3.2. Textural characterization anthracite [31] as a raw material, also showed that the increase of
the NaOH:char promoted and increase in the SBET value.
Fig. 1(a) shows the N2 adsorption isotherms obtained for AC-1, As can be observed in Table 2, as well as the value of SBET , the val-
AC-2 and AC-3. According to the gure, a progressive increase in ues of VT , V and Vm increased with the NaOH:char. VT is directly
120 A.L. Cazetta et al. / Chemical Engineering Journal 174 (2011) 117125

Table 2
Textural characteristics of the activated carbons in the NaOH:char ratio of 1:1 (AC-1), 2:1 (AC-2) and 3:1 (AC-3).

SBET (m2 g1 ) VT (cm3 g1 ) V (cm3 g1 ) Vm (cm3 g1 ) V /VT (%) Dp (nm) Yield (%)

AC-1 783 0.378 0.356 0.022 94.2 1.63 28.9


AC-2 1842 0.927 0.775 0.152 83.6 1.80 23.4
AC-3 2825 1.498 1.143 0.355 76.3 2.27 18.8

SBET = BET surface area; VT = total pore volume; V = micropore volume; Vm = mesopore volume; V /VT = percentage of micropores, Dp = average pore diameter.

0.024
Incremental Pore Volume (cm g )
-1

0.021 AC-1
3

AC-2
0.018 AC-3
0.015
0.012
0.009
0.006
0.003
0.000
15 20 25 30 35 40 45 50 55 60
Diameter ()

Fig. 2. Pore size distribution of AC-1, AC-2 and AC-3.

related to the development of porosity of the material. The acti-


vation process rearranges the carbon structure producing a more
ordered structural skeleton. The pore development occurs from
four stages: (i) opening of previously inaccessibly pores, (ii) cre-
ation of new pores, (iii) widening of the existing pores and (iv)
merger of the existing pores due to pore wall breakage [32].
The values of Vm and Dp for AC-1, AC-2 and AC-3 were
0.022 cm3 g1 , 0.152 cm3 g1 and 0.355 cm3 g1 and 1.63 nm,
1.80 nm and 2.27 nm, respectively (Table 2). According to the
results, there was a tendency of increase of Vm and Dp with the
increase of NaOH:char. This tendency can be justied by the micro-
pore merge and collapse, which occurred when large amounts of
NaOH were used [3]. The micropores were the responsible for
the increase of VT . In addition, the increase of NaOH:char pro-
moted a development of mesopore and consequently a decrease
in the micropore percentages (V /Vt (%)). The values of V /Vt (%)
were 94.2, 83.6 and 76.3 for the AC-1, AC-2 and AC-3, respectively.
The presence of mesopores and micropores in AC enhances their
adsorption capacities, especially for large molecules of adsorbates
as dye molecules [33].
Fig. 3(ac) shows the SEM images for the ACs. The activation
method with NaOH provided the development of many pores with
varying sizes and materials of high surface area.

3.3. Chemical surface characterization

The method described by Boehm [23] was used in chemical


surface characterization of the prepared ACs. The methodology
consists of a series of titrations in which it is possible to quan-
Fig. 3. SEM images of the AC-1, AC-2 and AC-3.
tify chemical groups such as carboxyls, lactones and phenolics. The
Boehm method results are shown in Table 3.

Table 3
Results of the Boehm and pH drift methods for the AC-1, AC-2 and AC-3.

Carboxylic (mmol g1 ) Lactonic (mmol g1 ) Phenolic (mmol g1 ) Acid (mmol g1 ) Basic (mmol g1 ) Total (mmol g1 ) pH drift

AC-1 0.37 0 0.38 0.75 0.73 1.47 6.00


AC-2 0.62 0 0.88 1.5 0.75 2.25 5.09
AC-3 0.75 0 1.00 1.75 0.75 2.50 5.01
A.L. Cazetta et al. / Chemical Engineering Journal 174 (2011) 117125 121

a 32 b 20.0

31
19.5
30 Coconut shell AC-3
Transmitance (%)

Transmitance (%)
29 19.0

28 18.5
27 AC-1
18.0
26

25 17.5 AC-2

4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500
-1 -1
Wavenumber (cm ) Wavenumber (cm )

Fig. 4. FT-IR spectra for the raw material (a) and ACs (b).

As can be observed in Table 3, there was a gradual increase in decrease in the functionality of the raw material. Montes-Morn
the amount of acid groups (carboxylic and phenolic) for ACs, which et al. [42] reported that the bands which were observed in the
consequently caused an increase in the amount of total groups. The region between 1700 cm1 and 1500 cm1 are attributed to C C
lactonic groups have not been detected and basic groups had values symmetrical stretching of pyrone groups and C O of carboxylic
of approximately 0.75 mmol g1 for prepared ACs. Additionally, it groups. The spectra shown in Fig. 4(b) are similar to those reported
can be seen that acid characteristics are more evident for AC-2 and by Vargas et al. [18], which produced activated carbons from am-
AC-3. boyant pods.
The use of chemical reagents in the activation process provides
an increase in the amount of acid groups present in the ACs surface, 3.4. Adsorption isotherms
as observed in other studies [18,34]. On the other hand, the basic
character is presented for materials produced from thermal treat- The adsorption isotherms describe how the adsorbate molecules
ment. The basicity is due to Lewis basic sites, oxygen free, on the are distributed between the liquid phase and solid phase when the
graphene layer, and from some surface groups containing oxygen system reaches the equilibrium [43]. The analysis of isotherm data
such as carbonyls, pyrone, and chromene type structures [35]. by tting them to different models is important to nd a sustainable
The pH drift method provides important information about the model that can be used [44].
characteristics of acidity and basicity of activated carbons, as the In order to optimize the design of an adsorption system of
pHpzc value, which has helped in the understanding of the adsorp- MB-AC-3, four adsorption isotherm models namely the Langmuir,
tion mechanism. According to Table 3, the pHpzc value of 6.0 for the Freundlich, RedlichPeterson and Toth isotherms in their non-
AC-1 was lower than for AC-2 (5.09) and AC-3 (5.01), respectively. linear forms, were applied to the equilibrium data, and are shown
The acid characteristic of the ACs agrees with the results obtained in Fig. 5. The Langmuir and Freundlich isotherms are known as
by Boehm method and by other researchers which produced ACs two-parameter models, which provide information on the adsorp-
from a chemical activation [36,37]. tion capacity and constants related to the activation energy. The
The FT-IR spectra were obtained to evaluate qualitatively the RedlichPeterson isotherm is known as three-parameter model,
chemical structures of the raw material and ACs. The spectra are which incorporates the factors of Langmuir and Freundlich equa-
shown in Fig. 4. Fig. 4(a) shows the FT-IR spectrum of the raw tion in a single. The Toth isotherm is of three-parameters and was
material, which indicated various surface functional groups. The developed to explain adsorption process in heterogeneous sys-
broad band at around 3404 cm1 is typically attributed to hydroxyl tems; it resembles the empirical proposal, which was developed
groups. The band located at around 2900 cm1 corresponds to by Freundlich to explain the adsorption phenomenon of these sys-
CH stretching vibration. The region of the spectrum of 1612 cm1 tems [27]. The values of the maximum adsorption capacity (Qm ),
is attributed to axial deformation of carbonyl groups (C O). The correlation coefcient (R2 ), and other constants obtained for the
stretching vibration of the molecular plane of C C bonds, char- models from experimental data are shown in Table 4.
acteristics of aromatic rings appear in the region of 1465 cm1 The Langmuir model assumes that the adsorption is a process
[38]. Axial and angular deformation of ketones arises in the region which occurs in a homogeneous surface, in which the molecules
of 1300 cm1 and 1100 cm1 . The broad band at 1058 cm1 is form a monolayer of adsorbate on the surface of the mate-
attributed to the angular deformation symmetrical of ethers [39]. rial, saturating the pores and preventing the transmigration [45].
The band caused by OH out-of-plane bending vibrations band is According to the results presented in Table 4, the Qm and R2 val-
located at 580 cm1 [40]. The presence of hydroxyl groups, car- ues obtained from Langmuir isotherms were of 916.26 mg g1 and
bonyl group, ethers and aromatic compounds is an evidence of the 0.8805, respectively. The Qm is close to the experimental value of
lignocellulosic structure of coconut shell as also observed in oth- Qm that is equal to 955.25 mg g1 . The separation factor (RL ) dened
ers materials such as Tunisian olive-waste cakes [41], jackfruit peel by Weber and Chakkravorti [46] is an important parameter of the
waste [24], and cotton stalks [5]. Langmuir isotherm that can be used to verify if the adsorption in the
The FT-IR spectra of the ACs obtained are shown in Fig. 4(b). system is unfavorable (RL > 1), linear (RL = 1), favorable (0 < RL < 1)
According to the results, it can be observed that there was dis- or irreversible (RL = 0). For the value range of concentrations stud-
appearance of bands when comparing the raw material spectrum ied (1001000 mg L1 ), the RL values decreased from 5.52 103
with the ACs spectra, indicating that the chemical bonds were to 5.55 105 , indicating that the MB-AC-3 system is favorable.
broken during the carbonization process followed by the activa- The Freundlich model is an empirical equation based on the
tion. In addition, other bands decreased drastically, indicating a adsorption on heterogeneous surface [47]. The heterogeneity fac-
122 A.L. Cazetta et al. / Chemical Engineering Journal 174 (2011) 117125

Table 4
Langmuir, Freundlich, RedlichPeterson and Toth isotherm model parameters and correlation coefcients for adsorption of MB on activated carbon.

Langmuir Freundlich Toth RedlichPeterson

Qm = 916.26 mg g1 KF = 747.32 mg g1 Qm = 720.81 mg g1 ARP = 24.47 103 (L mg1 )g


Ka = 1.80 L mg1 nF = 20.08 bT = 0.031 BRP = 32.35 L g1
R2 = 0.8805 R2 = 0.8796 nT = 0.95 g = 0.95
R2 = 0.8796 R2 = 0.8796

a 1000 data t preferentially the Langmuir isotherm. The R2 value for the
Freundlich model was 0.8796.
900 The Toth model is a combination of the characteristics of
800 the Langmuir and Freundlich isotherms [45]. The Toth equation
(Table 1) reduces to Langmuir for nT = 1. In the present study,
700
nT = 0.95 is close to the unit value, which reduces the Langmuir
Experimental values
600 equation. Additionally, the model provided values of Qm and R2
qe (mg g )

Toth
equals to 720.32 mg g1 and 0.8796, respectively.
-1

500 Langmuir
RedlichPeterson model is used as a compromise between Lang-
400
muir and Freundlich models [49]. The parameter g in the equation
300 indicates which of the two models, Freundlich or Langmuir, bet-
200 ter ts the experimental data. For g = 1, the Langmuir isotherm
is favored, and g = 0 the equation of Freundlich is favored. In this
100
study, the g value is close to unity, which means that the isotherms
0 conform to Langmuir model better than Freundlich model.
0 10 20 30 40 50 60 70 80 Comparing the R2 values (Table 4), it can be observed that the
-1
Ce (mg L ) Langmuir model yielded the best t with the highest R2 value. The
suitability of the Langmuir model to experimental data was con-
rmed by the constant RedlichPeterson model and the value 1/n
b 1000 described by the Freundlich model. The t of the experimental data
to the Langmuir model indicates a homogeneous nature of the AC-
900 3 surface. Additionally, it describes the formation of monolayer
800 coverage of dye molecule at the outer surface of the AC-3 [50].
The Qm value of 916.26 mg g1 describes the high adsorption
700
capacity of the AC-3, which is directly related to high surface are
600 Experimental values (SBET ) and the average pore diameter (Dp ). Considering that width of
qe (mg g )

Freundlich
-1

500 the MB molecules is 1.42 nm [25], and the Dp of AC-3 is 2.27 nm, the
Redlich-Peterson MB molecules can diffuse from solution into the AC, which justies
400
the high value of Qm . In addition, the adsorption is favored due to
300 the acid characteristics of the AC-3 surface, which was described by
200 Boehm and pH drift methods. The negative surface of AC-3 interacts
effectively with the MB, due to cationic property of the dye.
100 Table 5 lists a comparison of the surface area (SBET ) and maxi-
0 mum adsorption capacity (Qm ) of ACs from coconut shell produced
0 10 20 30 40 50 60 70 80 from various activation methods. The NaOH-activated carbon pre-
-1
Ce (mg L ) pared in this work presented a high surface area (SBET ), which was
proven by the high adsorption capacity of the MB dye.
Fig. 5. Non-linear ts of the isotherm models. Langmuir and Toth (a),
RedlichPeterson and Freundlich (b). 3.5. Kinetic studies

tor (nF ) indicates whether the adsorption process is linear (nF = 1), Kinetic studies are important to understand the dynamic of the
chemical (nF < 1) and or physical (nF > 1). Additionally, the value reaction in terms of order of the rate constant. Since the kinetics
of 1/nF < 1 indicates a normal Langmuir isotherm while 1/nF > 1 parameters provide information for designing and modeling the
is an indicative of cooperative adsorption [48]. According to the adsorption process. The data of adsorption kinetics for the AC-3-MB
results shown in Table 4, the values of nF = 20.08 and 1/nF = 0.050 system were analyzed by non-linear tting of two different kinetic
indicate that the adsorption is physical, and that the experimental models: pseudo-rst order and pseudo-second order, which are

Table 5
The BET surface area (SBET ) and maximum adsorption capacity values (Qm ) of coconut activated carbons produced from various activation methods.

Activation methods SBET (m2 g1 ) Adsorbate Qm (mg g1 ) Reference

H3 PO4 902 Zinc 60.41 [15]


KOH/CO2 2,4,6-Trichlorophenol 191.73 [13]
KOH/CO2 1940 Methylene blue 434.78 [50]
KOH/CO2 1026 Phenol 205.8 [12]
ZnCl2 /steam 2114 Methane 122.85 [51]
ZnCl2 /CO2 1884 Methylene blue 14.36 [52]
Steam Methylene blue 277.90 [53]
NaOH 2885 Methylene blue 916.26 This work
A.L. Cazetta et al. / Chemical Engineering Journal 174 (2011) 117125 123

a 1000 1000

800 800

600 600
Experimental values

qt (mg g )
qt (mg g )

Experimental values

-1
-1

Pseudo-first order Pseudo-first order


400 Pseudo-second order 400 Pseudo-second order

200 200

0 0
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
Time (min) Time (min)

c 1000

800

600 Experimental values


qt (mg g )

Pseudo-first order
-1

Pseudo-second order
400

200

0
0 20 40 60 80 100 120 140 160
Time (min)

Fig. 6. Non-linear ts of pseudo-rst order and pseudo-second order kinetics for the MB concentration of 800 (a), 900 (b) and 1000 (c) mg L1 .

shown in Fig. 6. According to Fig. 6, the AC-3-MB system reached adsorption process is preferably controlled by chemisorption; as
the equilibrium after 30 min, suggesting that interactions between also reported by Tan et al. [50] which studied the methylene blue
the adsorbent and adsorbate were favorable. adsorption onto KOH/CO2 -activated carbon from coconut.
Table 6 shows the parameters obtained from the ts of the To identify the diffusion mechanism, the intraparticle diffusion
adsorption kinetic models. The correlation coefcients (R2 ) for model based on the theory proposed by Weber and Morris [54] was
all models were greater than 0.9705 in different concentrations, applied to the AC-3-MB system.
being that the highest values were observed for the pseudo-second Fig. 7 shows the plots of qt versus t1/2 . The value of the slope cor-
kinetic model. The applicability of the pseudo-second-order kinetic responds to intraparticle diffusion constant, kdi , and the intercept
model was conrmed by the low value of normalized standard value, Ci , at an approximate value of the thickness of bound-
deviation (qe = 2.59%). Additionally, the qe values obtained by the ary layer. The data from the three different initial concentrations
tting agreed with qe,exp values. This suggests that the rate of the showed two stages of linearity, being the rst stage was completed

Table 6
Pseudo-rst order and pseudo-second order kinetic model parameters for different initial MB concentrations.

C0 (mg L1 ) qe,exp (mg g1 ) Pseudo-rst order Pseudo-second order


1
800 795.15 qe = 774.54 (mg g ) qe = 802.14 (mg g1 )
K1 = 0.43 (min1 ) K2 = 0.00097 (g g1 min1 )
h0 = 333.05 (mg g1 min1 ) h0 = 624.13 ((mg g1 ) min1 )
R2 = 0.9909 R2 = 0.9998

900 868.50 qe = 826.39 (mg g1 ) qe = 856.64 (mg g1 )


K1 = 0.50 (min1 ) K2 = 0.00104 (g g1 min1 )
h0 = 413.20 (mg g1 min1 ) h0 = 763.18 ((mg g1 ) min1 )
R2 = 0.9745 R2 = 0.9932

1000 911.30 qe = 867.96 (mg g1 ) qe = 900.69 (mg g1 )


K1 = 0.47 (min1 ) K2 = 0.00092 (g g1 min1 )
h0 = 407.94 (mg g1 min1 ) h0 = 746.34 ((mg g1 ) min1 )
R2 = 0.9758 R2 = 0.9959
qe (%) = 5.79 qe (%) = 2.59
124 A.L. Cazetta et al. / Chemical Engineering Journal 174 (2011) 117125

Table 7
Intraparticle diffusion model constants and correlation coefcients for adsorption MB on prepared activated carbon.

C0 (mg L1 ) Intraparticle diffusion model

kdi1 (mg g1 min1/2 ) kdi2 (mg g1 min1/2 ) C1 (mg g1 ) C2 (mg g1 ) R12 R22

800 119.09 4.97 345.14 739.37 0.9865 0.9087


900 89.07 12.59 471.86 730.79 0.9834 0.9070
1000 104.57 10.08 463.74 795.71 0.9995 0.9112

1000 Acknowledgement
900
The authors acknowledge Fundaco Araucria and CAPES for the
800
nancial support.
700
600 -1
800 mg L References
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900 mg L
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