You are on page 1of 8

Journal of Environmental Chemical Engineering 1 (2013) 496503

Contents lists available at SciVerse ScienceDirect

Journal of Environmental Chemical Engineering


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

Adsorption kinetics of some textile dyes onto granular activated carbon


Kumar Djamel Belaid a, Smal Kacha a,*, Mostefa Kameche b, Zoubir Derriche b
a
Laboratory of Materials and Reactive Systems (LMRS), Djillali Liabes University of Sidi Bel-Abbes, P.O. Box 89, 22000 Sidi Bel-Abbes, Algeria
b
Laboratory of Physical-Chemistry of Materials, Faculty of Sciences, University of Sciences and Technology of Oran, MNouar 1505, 31000 Oran, Algeria

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

Article history: Adsorption kinetics of Acid Blue 113 (AB), Basic Red 5 (BR) and Reactive Yellow 81 (RY) textile dyes were
Received 5 March 2013 studied. The investigations were essentially conducted to determine the inuence of the initial dye
Received in revised form 2 May 2013 concentration of aqueous solutions on the adsorption kinetics. The experiments, carried out in a batch
Accepted 7 May 2013
reactor, allowed the determination of the equilibrium times (1 h for RY and AB and 4 h for BR). The
experimental data were analyzed according to the surface reaction and intra-particle models. In effect,
Keywords: the adsorption results were perfectly tted to the pseudo-second order, with very high regression
Textile dyes
coefcients (r2), predicting a signicant intra-particle diffusion stage in the controlling of the adsorption
Aqueous solutions
process. Moreover, the tting to Elovich equation, conrms that the process is ensured by chemisorption
Granular activated carbon
Adsorption on a highly heterogeneous material.
Kinetics 2013 Elsevier Ltd. All rights reserved.

Introduction to their solubility in water [8]. Acid, basic, reactive and direct dyes
are soluble dyes, while dispersed pigments and oxidized dyes are
The wastewater treatment is required by various obligations insoluble in water.
which are environmental or concerning with public health. Dye Adsorption kinetics describe the reduction of the aqueous
wastewaters represent the most amounts of the discharged adsorbate concentration from solution according to the reaction
industrial water [1]. The test, application and development of time variation. During the adsorption process, four distinct stages
many treatment methods were the essential subjects of many are considered. The transport of the aqueous adsorbate until the
articles. They can be physical, chemical or biological [24]. lm surrounds the particle surface of the adsorbent (this rst stage
Biodegradation and adsorption were the two treatments widely can be neglected if the system is perfectly stirred); the external
used in the purication of waters [5,6]. The treatment by diffusion (the second stage); the intra-particle diffusion (the third
adsorption consists of the retention of dyes onto a solid material stage) and the physical or chemical surface reactions (the fourth
called adsorbent by chemical or/and physical bonding. Several stage). These stages can be compared to a succession of resistance
solid adsorbent materials such as activated carbon [7], clays [8], phenomenon to the mass transfer of the adsorbate from the
zeolite [9], biomasses [10], and industrial waste products [11] are solution medium until the adsorption sites of the adsorbent
able to remove efciently color from water. (Fig. 1). One or two of these stages can be kinetically determining.
Commercial activated carbons are the most adsorbent materials Ho and McKay [20] consider that only the external and intra-
used in the water treatment [12]. They are obtained from various particle lm diffusions control the kinetics of adsorption.
resources, including rattan sawdust [13], coconut husk [14], cattail Although the adsorption of dye removal from solutions was
[15], etc. They are physically or chemically activated at high sufciently studied by many authors, it was observed that the
temperature [16] in order to confer them porous structure, several studies were devoted for one type of dyes. Nandi et al. [1]
chemical surface function and important adsorption properties studied the removal of cationic dyes from aqueous solutions by
[17]. kaolin. Shi et al. [3] studied the removal of direct dyes by
Textile dyes are the essential cause of color in the discharged preformed polymeric aluminum species. Kacha et al. [8] studied
wastewaters [18]. Dye molecules present a considerable structural the equilibrium and kinetics of color removal from acid dye
diversity, allowing them to be classied by several manners [19]: solutions with bentonite and polyaluminum hydroxide. Orfao et al.
either according to their chemical structures or their applications [17] studied the adsorption of a reactive dye on chemically
with suitable type of ber. They can also be classied with respect modied activated carbons. It is, thus, interesting to check the
behavior of structurally different dyes belonging to various groups
with the same adsorbent material. In this work, a commercial
* Corresponding author. Tel.: +213 567 577; fax: +213 544 344. granular activated carbon was used as adsorbent to remove from
E-mail address: smail_k@yahoo.fr (S. Kacha). water three textile dyes namely Acid Blue 113, Basic Red 5 and

2213-3437/$ see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jece.2013.05.003
K.D. Belaid et al. / Journal of Environmental Chemical Engineering 1 (2013) 496503 497

Nomenclature

b coefcient related to the extension of covered


surface and chemi-sorption activation energy
(g mg1)
a rate of chemi-sorption (mg g1 min1)
k1 pseudo-rst order rate constant (min1)
C0 initial dye concentration (mg/L)
Ce equilibrium dye concentration in liquid phase (mg/
L)
C a constant
De diffusivity of aqueous salt (m2/s)
F(t) fraction of salt on adsorbent
H initial sorption rate (mg g1 min1)
k2 pseudo-second order rate constant (g mg1 min1)
kF external coefcient of mass transfer (m min1)
kid intra-particle diffusion rate constant
kL Langmuir equilibrium constant for carbon/dye
system (L mg1)
m mass of the used carbon (g)
Fig. 1. External and intra-particle diffusion of adsorbates onto porous adsorbents.
ms adsorbent dosage (=m/V)
q0 initial dye concentration present on solid phase
(mg/g) cotton using simple exhaustive techniques. They are mixtures of
qe adsorption capacity at equilibrium (mg/L) molecule dyes (5098%) and several substrates used as additives.
qt adsorption capacity at time t (mg/L) The basic dye possesses a small molecule (M = 288.8 g mol1)
R adsorbent particles ray (m) compared to the two others (M = 681.65 and 1631 g mol1,
SS specic particles area during external mass trans- respectively) and has a different behavior in an aqueous solution.
fer (cm1) Physicalchemical specications concerning the dyes (i.e. purity
V volume of sample (L) degree and developed chemical formulae) are sometimes not
communicated by manufacturers. The main characteristics of the
studied dyes are presented in Table 2.
Reactive Yellow 81. The study was particularly focused on the
inuence of the initial dye concentration on the adsorption Methods
kinetics.
Dye solutions
Materials and methods The dyes were used as provided by the manufacturer, without
any preliminary purication. The acidic (AB) and basic (BR) dye
Materials solutions were prepared by dissolving 400 mg of dye powder in 1 L
of distilled water. For the reactive dye (RY) existing in a hydrolyzed
Commercially available granular activated carbon (GAC) form in the textile efuents [21], a dye solution of 600 mg/L was
purchased from Cheminova International (Spain) was used. The prepared by the same method described by Pereira et al. [22]. The
BET surface area, mean particle size and main characteristics of this dye was hydrolyzed by increasing the temperature to 50 8C, and
granular activated carbon are listed in Table 1. The mean diameter adding some salts with sodium hydroxide until the nal pH of the
of its particles is higher than 2 mm. A quantity of this coal was solution became 12. All solutions with different initial dye
initially crushed in a laboratory mortar, then separated by sifting in concentrations were prepared from the three indicated solutions
order to obtain the fraction of diameter ranging between 1 and by adding distilled water.
2 mm, washed with distilled water and dried during 48 h in a
drying oven at 383 K, and nally stocked in a desiccator for future Adsorption kinetics
uses. Adsorption batch experiments were carried out from 1.7 L of
Two anionic dyes (Acid Blue 113 and Reactive Yellow 81) and dye solution in a 3-L beaker. The solutions of dyes, used as aqueous
one cationic (Basic Red 5) were considered in this study. These adsorbates, were stirred during 35 h at 550 rpm. In order to
three soluble dyes can be applied to most synthetic bers and investigate the effect of the initial dye concentration on the
adsorption kinetics, the following concentrations were used: 20,
40, 60 and 80 mg/L (AB and BR); and 32, 65, 95 and 123 mg/L (RY).
Table 1 The activated carbon amounts were added to prepared solutions.
Physicochemical characteristics of granular activated carbon (GAC).
They were well stirred and kept at 294 K with an air-bath. The
Origin Charcoal, vegetal activated equilibrium was normally reached during 1 h for AB and RY, whilst
Mean particle size (mm) 3 4 h for BR. The optimal mass of 3.4 g of the adsorbent (2.0 g L1)
Surface area (m2/g) 1100 determined separately, the diameters of the particles (1 = 1
Bulk density (cm3/g) 0.425 2 mm) and the temperature of the bath (294 K) were kept constant
Iodine value 1050 during all the experiments. The initial pHs (67) of the basic
Ashes (%) <12
H2O (%) <10
solutions of BR and RY, were adjusted by adding sulfuric acid
solution 0.1 N. This pH range was chosen so that the charge point
498 K.D. Belaid et al. / Journal of Environmental Chemical Engineering 1 (2013) 496503

Table 2
Main characteristics of dyes used with different forms.

Dye Acidic Basic Reactive

Symbol AB BR RY
Commercial name Acid Blue 113 Neutral Red Reactive Yellow 81
Generic name C.I. Basic Red 5
IUPAC name Disodium8-anilino-5-[[4-(3-sulfonatophenyl)azo-1- Chlorure de 3-amino-7-dimethylamino-2-methylphenazine
naphthyl]azo]naphthalene-1-sulfonate
C.I. number 26360 50040 CI 2630
CA.S. number 3351-05-1 553-24-2 59112-78-6
Dye composition 50% 98%
Linear formula C32H21N5O6S22Na C15H16N4HCl C52H34Cl2N18O20S66Na
Molecular weight 681.65 288.8 1631
UVvis (lmax) 565 nm 462 350a
a
Hydrolized dye.

vanished. In effect, for the activated carbon used the pH was 6.7. Pseudo-second order equation. The most mentioned formula to
This value was determined by the same method cited by Crini [6]. express the pseudo-second order was indicated by Ho and McKay
Samples of each solution were taken at regular intervals of time, [25] by the following expression (Eq. (3)):
then ltered by glass lters (diameter of pores 0.45 mm) and    
analyzed to determine their concentration. t 1 1
2
t (3)
The equilibrium dye concentration of solutions were measured qt k2 qe qe
from their absorbances at the maximum absorption wavelength of
with k2 the pseudo-second order constant (g mg1 min1) and
each dye, by UVvis spectrophotometer (Ficher Bioblock Scientic 2
k q2e h the initial sorption rate (mg g1 min1).
1100, Germany), with retro enlightened LCD screen, equipped by
The constants of this equation can be determined by plotting
10 mm tubular cell (Table 1).
the straight line 1/qt versus t.
In order to quantify the sorbed amounts of dyes onto solid
In this case, the pseudo-second order kinetics for the whole
phase (GAC), being determined from measured concentrations, the
adsorption reaction, it may be accepted a two-partial order with
adsorption capacities qe (mg/g) were calculated using (Eq. (1)):
respect to the free sites concentration and a zero partial with
  respect to the solute in the solution.
V In order to obtain better results in terms of regression
qe  C 0  C e q0 (1)
m coefcient and comparison between theoretical and experimental
values, certain authors showed that (Eq. (3)) can be exploited
where V is the volume of the dye solution (L), m the mass of used differently with some rearrangements [26].
GAC (g), C0 and Ce the initial and the equilibrium concentrations of
dye in the liquid phase (mg/L) and q0 is the concentration of dye Elovich equation. Namasivayam and Sangeetha [11] indicated that
initially present on the solid phase (mg/L). the Elovich expression (Eq. (4)) was initially used to describe the
The pH of the dye solutions was measured using a pH-meter chemisorption kinetics of gases onto solids [27]. In spite of this, it
(InoLab pH Level 1, D-82362 Weillheim, Germany). was widely used and cited in case of chemisorption kinetics of
solid/liquid systems [28]. Currently, Elovich equation has been
Theoretical models generalized and frequently used in the sorption studies of many
pollutants in aqueous solution [29]:
The results were tted to surface reaction and intra-particle    
models. 1 1
qt  lnab  lnt (4)
b b
Surface reaction where a is the chemi-sorption rate (mg g1 min1) and b is a
coefcient in relation with the extension of covered surface and
Pseudo-rst order equation. The pseudo-rst order was often
activation energy of chemi-sorption (g mg1).
expressed by Lagergren equation [23] being the most cited
The equation constants are tabulated from the plot of the
formula [24] (Eq. (2)):
straight line qt versus ln t.
 
k1 Diffusion models
logqe  qt logqe  t (2)
2:303
External diffusion equation. The kinetic equation presented by
with qe the adsorption capacity at equilibrium (mg/L), qt the McKay and Allen [30] is often applied to model the external
0
adsorption capacity at time t (mg/L) and k1 the pseudo-rst order diffusion, during the migration of aqueous adsorbates from a liquid
constant (min1). phase to the solid adsorbent (Eq. (5)):
The slope of the linear t of log(qe  qt) versus t allows to    0   
Ct A k f  Ss
determine the value of (k1/2.303). The intercept of the straight- ln  ln A0  0 t (5)
C0 ms K L A
line gives the value of log(qe).
Lagergren equation represents the pseudo-rst order kinetics with KL the Langmuir constant for carbon/dye system (L mg1), Kf
for the whole adsorption reaction, with a one-partial order with the coefcient of external mass transfer (m min1), Ss the specic
respect to the free concentration sites and a zero-partial order with surface of particles during external mass transfer (cm1), ms the
respect to the solute in the solution. concentration of adsorbent in liquid phase: ms = m/V, with
K.D. Belaid et al. / Journal of Environmental Chemical Engineering 1 (2013) 496503 499

50
ms  K L
A0
1 ms  K L
40
By plotting ln[(Ct/C0)  (A0 /msKL)] versus time, it is possible to
know if the external diffusion stage is (or not) determinant for the
adsorption process.
30

q e (mg/g)
Intra-particle diffusion equation. According to Hamdaoui [29], any
kinetic approach of the intra-particle diffusion may be deduced
20
successively from works of Weber et al. [31] and Boyd et al. [32]. As
proved recently [33,34], in order to appreciate the role of the intra-
particle diffusion in the adsorption process, the following kinetic
expression is used (Eq. (6) or (7)): 10

qt kid  t 1=2 (6)


0
or 0 20 40 60 80 100 120 140 160 180 200 220 240
Time (min)
qt kid  t 1=2 C st (7)
Fig. 3. Effect of initial Basic Red concentration on adsorption capacity of granular
where qt is the sorbed amount of adsorbate per unit of mass of activated carbon. VS = 1.7 L; mad = 3.4 g; 1p = (12 mm); stirring = 500 rpm; pH 6
adsorbent (adsorption capacity at the time t) (mg/L) and kid is the 7; T = 294 K.
intra-particle diffusion constant.
80 mg/L) were found equal to 2.5, 4.0, 5.7 and 7.6 mg/g,
Results and discussion respectively.

Adsorption of the acid dye (AB) Adsorption of the basic dye (BR)

Fig. 2 shows the effect of the initial dye concentration on the The adsorption kinetics of BR on the GAC was studied using the
retention rate of AB onto GAC at increasing contact time. The same conditions applied in the case of AB; the results concerning
variation of extracted dye amounts per unit of mass of adsorbent with the variation of qt according to the reaction time are
(qt) according to the reaction time was mentioned. For the four presented in Fig. 3. The equilibrium of the sorption process is
used concentrations, the rate of retention increases with the gradually reached once again, in agreement with the fact that the
increasing reaction time, but it follows two different slopes. The activated carbon has a porous structure [35,36]. The pseudo-
rst, ranging between 20 and 60 min, is fast, whilst the second is equilibrium time in the case of high dye concentrations was longer
slow. This is explained by the availability of adsorption sites than that of low concentrations, and required more than 2 h of
initially free, which become saturated as time increases. The reaction. When the initial dye concentration increases from 20 to
retention is, thus, limited. It is known that the equilibrium of 80 mg/L, the percentage of dye elimination remains almost
adsorption process in case of porous adsorbents is gradually constant around 63% except for 20 mg/L (69%). The amounts of
reached [35]. According to the obtained results, it may be noticed the sorbed dye (qe), for the used concentrations (20, 40, 60 and
that the elimination rate of dyes slightly decreases with the 80 mg/L) are found 6.7, 12.5, 18.9 and 25.1 mg/g, respectively. The
increasing of the initial dye concentration, while remaining in the sorption capacities of BR on GAC are higher than those of AB, and
same order (i.e. about 19%) for the various concentrations, except increase with increasing of initial concentration.
that of 20 mg/L which exceeds 25%. The adsorption capacities at
equilibrium time (qe), for the used concentrations (20, 40, 60 and
4
12

8
q e (mg/g)
qe (mg/g)

4
1

0
0
0 20 40 60 80 100 120 140 160 180 0 50 100 150 200 250 300
Time (min) Time (min)

Fig. 2. Effect of initial Acidic Blue concentration on adsorption capacity of granular Fig. 4. Effect of initial Reactive Yellow concentration on adsorption capacity of
activated carbon. VS = 1.7 L; mad = 3.4 g; 1p = (12 mm); stirring = 500 rpm; pH 6 granular activated carbon. VS = 1.7 L; mad = 3.4 g; 1p = (12 mm);
7; T = 294 K. stirring = 500 rpm; pH 67; T = 294 K.
500 K.D. Belaid et al. / Journal of Environmental Chemical Engineering 1 (2013) 496503

Table 3
Experimental data and operational conditions of dye adsorption kinetics, at ambient temperature and various initial dye concentrations.

C0 (mg/L) m/V (g/L) dpi (mm) pH Ce (mg/L) qe (mg/g)

Acidic Blue 20 2 12 7 15.0 2.5


40 32.1 4.0
60 48.3 5.7
80 64.8 7.6

Basic Red 20 2 12 7 6 6.7


40 14.8 12.5
60 22.2 18.9
80 29.7 25.1

Reactive Yellow 32 2 12 7 30.7 1.1


65 62.1 1.5
94 90.6 2.0
123 117.9 2.5

Adsorption of the reactive dye (RY)


300

Fig. 4 shows the results of the adsorption kinetics of RY on the 32 mg/L


GAC. The same observations were also made in this case (two 65 mg/L
94 mg/L
different straight-lines slopes). Nevertheless, the slowest stage
123 mg/L
begins about approximately 90 min. During the adsorption process 200
in aqueous solutions, using porous adsorbents, the consecutive

t/q t
stages of mass transfer take relatively a long contact time, due to
complex structure of adsorbent [35]. The sorption results of qt
show that the reactive dye has the lowest rate of elimination in the
rst hour of reaction. The percentages of elimination decrease with 100
increasing of dye concentration, however they remain in the same
order (4%) for the various concentrations, except for that of 32 mg/
L which exceeds 6%. The extracted dye amounts per unit of
adsorbent mass increase from 1.1 mg/g (lowest concentration) to
2.5 mg/g (highest concentration). 0
0 60 120 180 240 300
The experimental data for the adsorption of the three dyes are
summarized in Table 3. As the results indicate, the initial dye Time (min)
concentration is a signicant parameter controlling the amount of Fig. 5. Adjustment of Reactive Yellow adsorption to pseudo-second order model at
extracted dye from water. The sorption capacity increases with various initial dye concentrations.
increasing of initial dye concentration, whereas the percentage of
color removal decreases. Under the same operating conditions, the
equilibrium time of adsorption is rstly reached for RY and AB
neglected, this model expresses the proportionality between the
(anionic dyes). Although the basic dye (BR) required more contact
reaction rate and the aqueous dye concentration. It was found that
time to reach equilibrium, it was the best adsorbed dye, while the
this model was not suitable for the three considered systems (GAC/
reactive dye RY had the lowest rate of elimination. The reactive dye
AB), (GAC/BR) and (GAC/RY). This behavior is was expected if the
has a long structural chain (C52) and high molecular weight;
external diffusion is not the determining step in the adsorption
therefore it has the lowest rate of elimination during the rst
process because since its linear expression has a similar form as
minutes. The basic dye having the smallest formula and weight
that of the traditional model of external diffusion. Besides, the
(C15) was the most adsorbed dye; it is more uid and penetrates
pseudo-rst order was generally used in case of physical
more easily through the pores, taking a long time to reach the
adsorption onto homogeneous adsorbents [39].
internal surface of the adsorbent. It is known that the activated
carbon is composed by a complex porous internal structure [37],
allowing a slow penetration of adsorbate through the pores. The
Table 4
equilibrium of adsorption process is, therefore, a function of
Pseudo-second order parameters of dye adsorption onto granular activated carbon
contact time. In addition, it was observed that the lowest initial dye at various initial dye concentrations.
concentration for each dye favors the best elimination. It is known
Dye C0 (mg/L) qe(exp) qe(cal) k2 r2
that the adsorption process is inuenced by the low adsorbate
concentrations (effect of dilution) [38]. This can be explained by Acidic Blue 20 2.52 2.42 0.12399 0.983
40 3.95 3.98 0.07175 0.9997
the fact that the weak adsorbate molecules concentration favors
60 5.75 5.76 0.06173 0.9996
their high mobility. The absence of the molecules inside the pores 80 7.62 7.60 0.10742 0.9998
facilitated their penetration into the material.
Basic Red 20 6.73 7.79 0.00377 0.992
40 12.49 12.69 0.00611 0.993
Kinetics models 60 18.85 19.12 0.00558 0.997
80 25.1 25.24 0.00506 0.997

Pseudo-rst order Reactive Yellow 32 1.06 1.05 0.24359 0.992


The pseudo-rst order model due to Lagergren was used in 65 1.51 1.54 0.07800 0.996
order to check its probable applicability for the adsorption results 94 1.96 2.06 0.03278 0.998
123 2.53 2.55 0.14656 0.9996
onto the granular coal (Eq. (2)). If the reaction of desorption is
K.D. Belaid et al. / Journal of Environmental Chemical Engineering 1 (2013) 496503 501

Pseudo-second order Table 5


Elovich model parameters of dye adsorption onto granular activated carbon at
The pseudo-second order model (Eq. (3)) was applied to the
various initial dye concentrations.
three studied systems. Fig. 5 (adsorption of RY) shows a very good
agreement between the extrapolated kinetic values and the C0 (mg/L) b a r2
experimental dye removal results, at various initial dye concen- Acidic Blue 20 4.23155 0.28860 0.966
trations. The same observation was made in case of the two other 40 2.90808 0.74206 0.948
dyes (AB and BR). Therefore, this model is valid for all intervals of 60 3.80315 0.81288 0.980
80 9.47060 0.22166 0.987
contact time. The different obtained data (initial sorption, pseudo-
second order constant, adsorption capacity and linear regression Basic Red 20 0.72836 1.5  101 0.982
coefcients) are grouped in Table 4. The adsorption constant values 40 0.68835 5.4  102 0.966
60 0.45448 5.1  106 0.980
for each dye were similar; the basic dye had the lowest ones. 80 0.40262 3.4  1012 0.981
Generally, the constant values decrease when the dye concentra-
tion increases, except in case of the highest concentration of the Reactive Yellow 32 2.33628 0.33308 0.988
65 2.09437 0.38206 0.990
anionic dyes (AB and RY) yielding very high values. The cationic 94 1.84254 0.40334 0.996
dye (BR) had a different behavior, and gave a low value for the 123 1.16818 0.71507 0.987
2
lowest dye concentration. The initial adsorption rate (h k q2e )
presents some differences between the cationic (BR) and the
anionic dyes (AB and RY): it increases for the rst case when the
concentration increases, but decreases for the second one, while The two constants were determined from the intercepts and slope
remaining in the same order for each dye. On the other hand, the of plots. It was noted that both b values of the used dyes were
variation of the sorbed amounts of dyes at equilibrium (qe(exp)) similar, and increase with increasing concentration (acid dye),
were in proportional relationship with the dye concentration. The except for the lowest concentration. Conversely, they decrease
regression coefcients (r2  0.99) indicate that the experimental with increasing concentration (basic and reactive dye). Moreover
points are very adjusted to the theoretical model line. On the other the extension of the covered surface by anionic dye molecules was
hand, the calculated and experimental data are almost the same. more signicant than that of the cationic dye. The chemi-sorption
With the overall pseudo-second order reaction, two elementary rates, indicated by the coefcient a, vary with dye concentration;
rst-order reactions between adsorbate and free sites, then the best values were obtained in case of the basic dye. The initial
between adsobate and solution the two-partial order with respect dye concentration increases with increasing chemi-sorption rate,
to the free sites concentration and the zero-partial order of the except for the highest concentration of the acid dye. From r2 values,
solute in the solution could be assumed. Ho and McKay [40] it may be deduced that Elovich model can be accepted as one of
indicated that if the dye removal is controlled by a chemical characteristics of the adsorption reaction. Elovich equation,
kinetics, the pseudo-second order constants will not depend on the initially used to express the beginning of sorption process, long
particle diameter but in contrast, the stirring velocity will depend time before equilibrium, can be used correctly in case of chemi-
on the concentration of ions in solution. sorption with highly heterogeneous materials [41]. Several authors
showed that an initial fast adsorption followed by a slow
Elovich equation chemisorption is well expressed by Elovich equation, in particular
The adsorption of the three studied systems was modeled when the adsorption process follows the pseudo-second order
according to the Elovich equation (Eq. (4)). The three systems were [42]. According to each studied system, the phenomenon was
well modeled by this equation. Fig. 6 gave the example of GAC/AB differently explained, by the presence of different nature sites with
system, showing a very good adjustment of the experimental data different energies on the adsorbent surface, or by the modication
on the acid dye removal at various initial dye concentrations. of the nature of the bonding between adsorbate and adsorbent. In
Table 5 presents the results deduced from the linear plots of qt addition, during the adsorption process, the energy state of the still
versus ln t, where b is a constant related to the extension of vacant sites can be modied by a surface contamination.
covered surface, and a is in relationship with chemi-sorption rates.

12
20 mg/L
40 mg/L 30 20 mg/L
10 60 mg/L 40 mg/L
80 mg/L 60 mg/L
80 mg/L
8
20
q e (mg/g)
q t (mg/g)

4
10

0
0
2 3 4 5 6 0 3 6 9 12 15
1/2
ln(t) (t)

Fig. 6. Adjustment of Acidic Blue adsorption to standard Elovich model at various Fig. 7. Adjustment of Basic Red adsorption to intra-particle diffusion simple model
initial dye concentrations. at various initial dye concentrations.
502 K.D. Belaid et al. / Journal of Environmental Chemical Engineering 1 (2013) 496503

Table 6 On the other hand, the suitable model to express the reactive dye
Intra-particle diffusion parameters of dye adsorption onto granular activated
adsorption was represented by Eq. (6) since the found values of
carbon at various initial dye concentrations. V = 1700 mL; m = 3.4 g; stir-
ring = 500 rpm. constants tend toward zero. From the values of r2, the diffusion of
dyes through the pores of granular carbon seems to be a
C0 (mg/L) Time (min) Cst kid r2
determinant stage, controlling the adsorption kinetics of RY dye
Acidic Blue adsorption onto GAC. This phenomena was expected because of
20 0300 1.37  0.02 0.05266 0.989 the relatively high diameter of coal particles (1 mm < d < 2 mm),
40 040 2.23  0.10 0.22012 0.958
allowing the activated carbon to be a highly porous material. Allen
60 040 4.42  0.05 0.15462 0.991
80 040 7.06  0.02 0.06102 0.989 et al. [43] indicated that the activated carbon, compared with other
sorbents, can have both high surface area of 1100 m2 g1 and
Basic Red
20 5150 0.21  0.17 0.55701 0.981
porosity of 47%.
40 5180 6.72  0.16 0.37491 0.976
60 5180 12.16  0.11 0.44251 0.994
80 10180 17.22  0.18 051315 0.991 Conclusions
Reactive Yellow
32 050 0.02  0.08 0.16337 0.955 The effect of initial dye concentration of two anionic dyes (AB,
65 040 0.01  0.04 0.20161 0.992 RY) and cationic dye (BR) on adsorption kinetics has been
94 040 0.02  0.02 0.24068 0.999 investigated. The elimination rates of the three dyes slightly
123 020 0.01  0.09 0.53546 0.991
decrease with increasing of the initial dye concentration. However,
the sorption capacities of adsorbed dye per gram of adsorbent for
all sorbent/dye systems increase.
Diffusion models The reactive dye possesses the lowest rate of elimination during
the rst minutes, while the basic dye, being more uid, has been
External diffusion the most adsorbed dye.
In order to examine the reliability of the experimental results The adsorption process is governed by the pseudo-second-
with the transfer of dyes from the liquid phase onto the solid phase, order reaction, at various initial dye concentrations for the two
known as external diffusion stage, Eq. (5) was applied for the three dyes BA and BR. Moreover intra-particle diffusion represents a
considered systems (GAC/AB, GAC/BR and GAC/RY). It was found determinant stage, controlling the adsorption kinetics of dyes the
that this model is not suitable to express all the cases studied; RY dye onto porous granular activated carbon.
therefore the external diffusion is not a determining stage in the Elovich model describes very well the experimental results,
sorption process. This is probably attributed to the perfect stirring predicting a chemisorption process of dyes onto different nature
of mixtures during all the experiments. Although it is agreed that sites of heterogeneous activated carbon.
during the initial stage of adsorption (rst minutes), the
intraparticle resistance is negligible, and the transport of the Acknowledgements
aqueous species toward the solid phase is mainly ensured by the
external diffusion mechanism [38], this stage is not determining, K.D. Belaid and S. Kacha would like to thank the Ministry of
especially if the experimental system is well stirred up [20]. Higher Education and Scientic Research of Algeria for nancial
According to the external diffusion equation (Eq. (5)) and the support.
pseudo-rst order equation (Eq. (2)), it may be easier to notice
their similarity. We might say that because the process does not
References
follow the pseudo-rst order model, the external diffusion cannot
be the adsorption determining. [1] B.K. Nandi, A. Goswami, M.K. Purkait, Removal of cationic dyes from aqueous
solutions by kaolin: kinetic and equilibrium studies, Appl. Clay Sci. 42 (2009) 583
Intra-particle diffusion 590.
[2] M.F. Hamoda, I. Al-Ghusain, N.Z. Al-Mutairi, Sand ltration of wastewater for
The experimental data were compared with the intra-particle
tertiary treatment and water reuse, Desalination 164 (2004) 203211.
diffusion model to check their conformity with Eq. (6). The testing [3] B.Y. Shi, G.H. Li, D.S. Wang, C.H. Feng, H.X. Tang, Removal of direct dyes by
of the model for the three systems (GAC/AB, GAC/BR and GAC/RY) coagulation: the performance of preformed polymeric aluminum species, J.
shows a good agreement; the linearity extends as of the rst Hazard. Mater. 143 (2007) 567574.
[4] Y.M. Slokar, A.M. Lemarechal, Methods of decoloration of textile wastewaters,
minutes until the equilibrium, with high correlation coefcients Dyes Pigments 37 (1998) 335356.
(r2  0.96). For instance, Fig. 7 presents the application of this [5] Y.Z. Fu, T. Viraraghavan, Fungal decolorization of dye wastewaters: a review,
model to GAC/BR system for the used initial dye concentrations Bioresour. Technol. 79 (2001) 251262.
[6] G. Crini, Non-conventional low-cost adsorbents for dye removal: a review,
(20, 40, 60 and 80 mg/L). Table 6 expresses the obtained data Bioresour. Technol. 97 (2006) 10611085.
corresponding to the linear part of the curve. Kinetic constants for [7] L.J. Kennedy, J.J. Vijaya, G. Sekaran, K. Kayalvizhi, Equilibrium, kinetic and ther-
each dye are similar; the smallest ones were those of BR dye. The modynamic studies on the adsorption of m-cresol onto micro- and mesoporous
carbon, J. Hazard. Mater. 149 (2007) 134143.
intra-particle diffusion constants generally increase with increas- [8] S. Kacha, Z. Derriche, S. Elmaleh, Equilibrium and kinetics of color removal from
ing of the concentration for the two systems: GAC/BR and GAC/RY. dye solutions with bentonite and polyaluminum hydroxide, Water Environ. Res.
In case of the GAC/AB system, the opposite was observed: when the 75 (2003) 1520.
[9] S.K. Alpat, O. Ozbayrak, S. Alpat, H. Akcay, The adsorption kinetics and removal of
concentration increases the constant decreases, except for the
cationic dye, Toluidine Blue O, from aqueous solution with Turkish zeolite, J.
lowest concentration. The initial dye concentration inuences the Hazard. Mater. 151 (2008) 213220.
process kinetics, and the intra-particle diffusion constant kid varies [10] S.S. Ahluwalia, D. Goyal, Microbial and plant derived biomass for removal of heavy
metals from wastewater, Bioresour. Technol. 98 (2007) 22432257.
proportionally with the dye concentration, except in the case of AB.
[11] C. Namasivayam, S. Sumithra, Removal of direct red 12B and methylene blue from
Moreover, Eq. (7) appears to be the adequate model to represent water by adsorption onto Fe(III)/Cr(III) hydroxide, an industrial solid waste, J.
the two GAC/BR and GAC/AB systems, because the intercept of Environ. Manage. 74 (2005) 207215.
plots do not pass by zero, but by values which vary proportionally [12] M. Dai, Mechanism of adsorption for dyes on activated carbon, J. Colloids Inter-
faces Sci. 97 (1997) 610.
with the initial dye concentration. The pseudo-second order may [13] B.H. Hameed, L.H. Chin, S. Rengaraj, Adsorption of 4-chlorophenol onto activated
be regarded as the determining adsorption step for these two dyes. carbon prepared from rattan sawdust, Desalination 225 (2008) 185198.
K.D. Belaid et al. / Journal of Environmental Chemical Engineering 1 (2013) 496503 503

[14] I.A.W. Tan, A.L. Ahmad, B.H. Hameed, Adsorption of basic dye on high-surface- [29] O. Hamdaoui, Batch study of liquid-phase adsorption of methylene blue using
area activated carbon prepared from coconut husk: equilibrium, kinetic and cedar sawdust and crushed brick, J. Hazard. Mater. 135 (2006) 264273.
thermodynamic studies, J. Hazard. Mater. 154 (2008) 337346. [30] G. McKay, S.J. Allen, Surface mass transfer processes using peat as an adsorbent for
[15] S. Qianqian, Z. Jian, Z. Chenglu, L. Cong, Z. Bo, H. Weiwei, X. Jingtao, Z. Ran, dyestuffs, Can. J. Chem. Eng. 58 (1980) 521526.
Preparation of activated carbon from cattail and its application for dyes removal, J. [31] J.R. Weber, J.C. Morris, Kinetics of adsorption on carbon from solution, J. Sanitary
Environ. Sci. 22 (2010) 9197. Eng. Division: Am. Soc. Civil Eng. 89 (1963) 3160.
[16] A.A. Amina, W.E. Rashwan, S.A. Khedr, Capacity of activated carbon in the removal [32] G.E. Boyd, A.W. Adamson, L.S. Myres, Kinetics of ionic exchange adsorption
of acid dyes subsequent to its thermal treatment, Dyes Pigments 69 (2006) 128 processes, J. Am. Chem. Soc. 69 (1947) 28362848.
136. [33] E.N. El Qada, S.J. Allen, G.M. Walker, Kinetic modeling of the adsorption of basic
[17] J.J.M. Orfao, A.I.M. Silva, J.C.V. Pereira, S.A. Barata, I.M. Fonseca, P.C.C. Faria, M.F.R. dyes onto steam-activated bituminous coal, Ind. Eng. Chem. Res. 46 (2007) 4764
Pereira, Adsorption of a reactive dye on chemically modied activated carbons 4771.
inuence of pH, J. Colloids Interfaces Sci. 296 (2006) 480489. [34] B.H. Hameed, D.K. Mahmoud, A.L. Ahmad, Sorption equilibrium and kinetics of
[18] G.M. Walker, L.R. Weatherley, Kinetics of acid dye adsorption on GAC, Water Res. basic dye from aqueous solution using banana stalk waste, J. Hazard. Mater. 158
33 (1999) 18951899. (2008) 499506.
[19] V. Gupta, K. Suhas, Application of low-cost adsorbents for dye removal a review, [35] P.K. Malik, Dye removal from wastewater using activated carbon developed from
J. Environ. Manage. 90 (2009) 23132342. sawdust: adsorption equilibrium and kinetics, J. Hazard. Mater. B 113 (2004) 81
[20] Y.S. Ho, G. McKay, Kinetic models for the sorption of dye from aqueous solution by 88.
wood, Trans. IChem E 76 (1998) 183191. [36] S.H. Gharaibeh, S.V. Moore, A. Buck, Efuent treatment of industrial wastewater
[21] P.C.C. Faria, J.J.M. Orfao, M.F.R. Pereira, Adsorption on anionic and cationic dyes on using processed solid residue of olive mill products and commercial activated
activated carbons with different surface chemistries, Water Res. 38 (2004) 20432052. carbon, J. Chem. Technol. Biotechnol. 71 (1998) 291298.
[22] M.F.R. Pereira, S.F. Soares, J.J.M. Orfao, J.L. Figueiredo, Adsorption of dyes on [37] R.S. Juang, R.L. Tseng, F.C. Wu, Role of microporosity of activated carbons on their
activated carbons: inuence of surface chemical groups, Carbon 41 (2003) 811821. adsorption abilities for phenols and dyes, Adsorption 7 (2001) 6572.
[23] S. Lagergren, About the theory of the so-called adsorption of soluble substances, [38] T. Ozlem, H. Tanaci, Z. Aksu, Potential use of cotton plant wastes for the removal of
Kun. Sven. Vetenskapsakad. Handl. 24 (1898) 139. Remazol Black B reactive dye, J. Hazard. Mater. 163 (2009) 187198.
[24] V.C. Srivastava, M.M. Swamy, D. Malli, B. Prasad, I.M. Mishra, Adsorptive removal [39] J. Torres-Perez, M. Solache-Ros, A. Coln-Cruz, Sorption and desorption of dye
of phenol by bagasse y ash and activated carbon: equilibrium, kinetics and Remazol Yellow onto a Mexican surfactant-modied clinoptilolite-rich tuff and a
thermodynamics, Colloids Surf. A 272 (2006) 89104. carbonaceous material from pyrolysis of sewage sludge, Water Air Soil Pollut. 187
[25] Y.S. Ho, G. McKay, Pseudo-second order model for sorption processes, Process (2008) 303313.
Biochem. 34 (1999) 451465. [40] Y.S. Ho, G. McKay, The kinetics of sorption of divalent metal ions onto sphagnum
[26] K.V. Kumar, Pseudo-second order models for the adsorption of safranin onto moss peat, Water Res. 34 (2000) 735742.
activated carbon: comparison of linear and non-linear regression methods, J. [41] W. Plazinski, W. Rudzinski, A. Plazinska, Theoretical models of sorption kinetics
Hazard. Mater. 142 (2007) 564567. including a surface reaction mechanism: a review, Adv. Colloid Interface Sci. 152
[27] C.W. Cheung, J.F. Porter, G. McKay, Sorption kinetics for the removal of copper and (2009) 213.
zinc from efuents using bone char, Sep. Purif. Technol. 19 (2000) 5564. [42] C.E. Chitour, Physicochemistry of the Surfaces, Algerian Ofce of University
[28] M.R. Cortes, M.V. Martinez, R.M. Solache, Evaluation of natural and surfactant- Publications (OPU), Algeria, 1994.
modied zeolite in the removal of cadmium from aqueous solutions, Sep. Sci. [43] S.J. Allen, Q. Gan, R. Matthews, P.A. Johnson, Kinetic modeling of the adsorption of
Technol. 39 (2004) 27112730. basic dyes by kudzu, J. Colloid Interface Sci. 286 (2005) 101109.