Chemical Engineering Journal 270 (2015) 621–630

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Chemical Engineering Journal

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

Calcium alginate–bentonite–activated carbon composite beads as highly

effective adsorbent for methylene blue
Assia Benhouria a,b, Md. Azharul Islam a,c, H. Zaghouane-Boudiaf b, M. Boutahala b, B.H. Hameed a,⇑
a
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
b
Laboratoire de Génie des Procédés Chimiques (LGPC), Faculté de Technologie, Université Ferhat Abbas Sétif-1, 19000 Sétif, Algerie
c
Forestry and Wood Technology Discipline, Khulna University, Khulna 9208, Bangladesh

h i g h l i g h t s

 An activated carbon–bentonite–alginate (ABA) composite was synthesized facilely.

 ABA showed a prominent existence of exchangeable cations.
 ABA was proven to be an extraordinary adsorbent for the removal of model dye methylene blue.
 The regenerated ABA was successfully employed several times for the adsorption.

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

Article history: Three adsorbents, namely, bentonite–alginate beads, activated carbon–alginate beads, and activated car-
Received 20 November 2014 bon–bentonite–alginate beads (ABA) were prepared for the adsorption of methylene blue (MB). The
Received in revised form 5 February 2015 effects of solution pH (3–11), temperature (30, 40, and 50 °C), initial concentration (25–500 mg/L), and
Accepted 6 February 2015
contact time were investigated. Results showed that the maximum monolayer adsorption capacity of
Available online 14 February 2015
ABA beads for the adsorption of MB was 756.97 mg/g at 30 °C. Furthermore, the adsorption kinetics illus-
trated the suitability of employing the pseudo-second-order kinetic model. The equilibrium adsorption
Keywords:
data fitted the Freundlich isotherm well. In addition, the ABA composite exhibited more than 70% adsorp-
Adsorption
Alginate
tion uptake capacity after six regeneration cycles. The outcomes of this study suggest the potential of ABA
Bentonite composite for cationic dye removal.
Composite Ó 2015 Elsevier B.V. All rights reserved.
Methylene blue
Activated carbon

1. Introduction solutions. All these methods have advantages and disadvantages

Dyes are broadly utilized in various industries, such as textile,
paper, food, cosmetics, pharmaceuticals, and others. The effluents
from these industries usually contain dyes, which cannot be
removed by conventional processes. Some of the most commonly
used dyes and their metabolites are carcinogenic and possess a
potential health hazard to all forms of life. These compounds, with-
out correct treatment, can be stabilized and remain in the water for
a long time. For these reasons, colored effluents are a serious envi-
ronmental problem, and thus, proper treatment processes need to
be developed [1]. Several methods of wastewater treatment such
as coagulation [2], aerobic or anaerobic digestion [3], advanced
oxidation process [4], adsorption [5,6], and others have been effec-
tively applied for the removal of various dye stuff from aqueous
⇑ Corresponding author. Tel.: +60 45996422; fax: +60 45941013.
E-mail address: chbassim@usm.my (B.H. Hameed).
in terms of their effectiveness, cost, and environmental impact
[7]. Adsorption has been vastly reported as the most widely used
technique for the removal of toxic organic and inorganic micropol-
lutants from wastewater because of its performance and ease of
operation [8,9].
Activated carbon is an extensively used adsorbent applied for
the removal of pollutants because of its high specific surface area
and surface reactivity [10]. The main problem associated with acti-
vated carbon involves the costs of preparation and raw materials;
however, this drawback can be alleviated by utilizing low-cost
materials. Good operation techniques alone cannot ensure system
sustainability if raw material supply is not perpetual. For these rea-
sons, several revealing research works have highlighted the
removal of different pollutants by several activated carbons pro-
duced from low-cost precursors [11].
Clay minerals have also been recognized as very good adsor-
bents because of their amazing textural properties, abundance,

http://dx.doi.org/10.1016/j.cej.2015.02.030
1385-8947/Ó 2015 Elsevier B.V. All rights reserved.
622 A. Benhouria et al. / Chemical Engineering Journal 270 (2015) 621–630
and inexpensiveness [12,13]. Errais et al. [12] extensively
described the efficiency of raw clay minerals to uptake anionic
dyes from a liquid solution. The Algerian bentonite-type clay has
been widely used in catalysis [14], sorption of dyes [15], herbicides
[16], metals, and drilling of oil wells for its rheological properties. A
key issue in this context is that neat clay minerals are not very effi-
cient in removing micropollutants from water compared with acti-
vated carbon because of their low surface area. Furthermore, the
difficulty experienced in recovering clay particles from solutions
after adsorption process makes them even less attractive as adsor-
bents for industrial water treatment. This problem ultimately
makes regeneration of these colloidal particles quite difficult. In
addition, clay minerals have a poor affinity for organics because
the hydration of clay mineral surface tends to reduce the accessi-
bility of the interlayer spaces to aromatic molecules. Thus, these
clay minerals lose a substantial amount of their adsorption capa-
city when they are regenerated for reuse.
Alginates are natural polysaccharides that are produced by
brown algae. Based on the exact nature of the seaweed species,
they represent 10–45 wt.% of dry matter [17]. Their high bioavail-
ability and easy extraction process explain their low cost. Alginates
are widely used in many different applications because of their
versatile properties that can be monitored according to different
stimuli (concentration, temperature, pH, etc.). In aqueous solution,
alginates are usually employed as thickening agents to increase the
viscosity of the medium [18]. In the presence of cations (usually
divalent or trivalent), they can produce a hydrogel according to a
complexation mechanism. The transformation is known under
the designation ‘‘ionotropic gelation.’’ Given its biocompatibility,
Ca2+ is the most applied and studied gelling agent [19]. Calcium
alginate is widely used in immobilizing activated carbon [20], car-
bon nanotubes [21], titania nanoparticles [22], and magnetite
nanoparticles [23] to create different adsorbents to remove wastes
like dyes, pigments, and metals from aqueous solutions.
The individual features of activated carbon, bentonite, and algi-
nate toward adsorption are not always very promising and identi-
cal; thus, the idea of combining them to make an effective
composite material for dye removal was conceptualized.
Moreover, the inherited problems linked with the individual adsor-
bents might be minimized by combining them. In this study, com-
mercial powdered activated carbon named ‘hydrodarco C’ was
used as activated carbon, which was produced by steam activation
of lignite coal under carefully controlled conditions. Therefore, the
objectives of this study were as follows: first, to prepare a variety
of composite beads from the combination of bentonite–alginate
beads (BA), activated carbon–alginate beads (AA), and activated
carbon–bentonite–alginate beads (ABA) via a simple fabrication
method; second, to compare and verify the best composite among
the prepared samples; third, to evaluate the best composite as an
adsorbent for the removal of the model dye methylene blue (MB)
from aqueous solution; finally, to implement an easy regeneration
technique and application to recover composite beads from solu-
tions after adsorption.
2. Materials and methods
2.1. Chemicals
The bentonite clay was supplied by the Enterprise Nationale des
Substances Utiles et des Produits Non Ferreux, Hammam
Boughrara, Algeria, it was grinded to a particle size that ranges
from 20 lm to 45 lm. Sodium alginate and calcium chloride were
purchased from R&M Chemicals, R&M Marketing Essex, UK, and
hydrodarco C was obtained from Norit Nederland. Methanol and
methylene blue (chemical formula: C16H18N3SCl, molecular
weight: 319.85 g/mol, solubility in water: 40 g/L) were supplied
by Merck Chemical Company. All other chemicals were used with-
out any further purification. Deionized water was used for the
preparation of all the required solutions.
2.2. Preparation of the ABA adsorbent
A 2% (w/v) sodium alginate solution was prepared by mixing 2 g
of sodium alginate in 100 mL deionized water with stirring for 1 h,
and then 2 g of bentonite clay and 2 g of hydrodarco c were added.
The mixture was stirred overnight. When the mixture became
homogeneous, it was dropped through a burette into 4% (w/v) cal-
cium chloride to form beads with vigorous stirring. The excess
unbounded calcium chloride from the bead surface was removed
by washing many times with deionized water. The washed beads
were then dried for 48 h at room temperature and stored in a clean
bottle. The same method was employed for the preparation of BA
and AA composites.
2.3. Characterization of adsorbents
The scanning electron microscope (SEM) micrographs of the
adsorbents were obtained using Zeiss (Model Supra 35 VP,
Germany). Brunauer–Emmett–Teller (BET) surface area was deter-
mined by N2 adsorption–desorption method using an automated
Micromeritics ASAP 2020 surface area analyzer at 77 K. The sample
was degassed at 200 °C for 2 h before BET analysis.
Fourier transform infrared spectroscopy (FTIR) analysis of the
adsorbent before and after adsorption was carried out in KBr pel-
lets in the range of 4000–400 cm1 with 4 cm1 resolution using
Perkin–Elmer Spectrum GX infrared spectrometer.
The point of zero charge (pHpzc) was determined according to
the method described by Auta and Hameed [24]. In brief, the initial
pH (pHi) of aqueous solutions (200 mL) were adjusted to a pH
range of 2–12 using 0.1 M HCl or NaOH. Then, 0.2 g of adsorbent
was added to each sample. The dispersions were stirred for 48 h
at 30 °C, and the final pH of the solutions (pHf) was determined.
The point of zero charge was obtained from a plot of (pHf  pHi)
versus pHi.
2.4. Selection of the best composite as an adsorbent
The percentage removal of MB at 100 mg/L of the initial concen-
tration in 30 °C were 84.35%, 83.22%, and 95.71% for AA, BA, and
ABA composites, respectively, and all other adsorption parameters
were kept constant as described in Section 2.5. Based on the pre-
liminary assessment of the different composites in terms of the
percentage removal of MB, ABA was the best adsorbent among
the samples tested. Therefore, all further experiments were per-
formed using the ABA composite.
2.5. Batch adsorption studies
Batch experiments were performed with 200 mL of MB solu-
tions of predetermined initial concentration (25–500 mg/L) in an
array of 250 mL flasks. Exactly 0.2 g of adsorbent was added to
each flask, and the solution was agitated in a preselected tem-
perature-controlled (30, 40, and 50 °C) water bath shaker set at
130 rpm until equilibrium was attained. After that, the MB solu-
tions were collected from the flasks at the end of the experiment
and analyzed using SHIMADZU UV/Vis 1601 spectrophotometer
at kmax = 665 nm.
The adsorption capacity of MB by the adsorbent at equilibrium
qe (mg/g) was calculated according to the following equation:
ðC o  C e Þv
qe ¼ ð1Þ
W
 A. Benhouria et al. / Chemical Engineering Journal 270 (2015) 621–630
The percentage removal (R%) by the adsorbent was described by
the following:
ðC o  C e Þ
R% ¼  100
Co
where Co and Ce, (mg/L) are the liquid-phase concentration of MB at
initial and equilibrium, respectively; v is the volume of the solution
in L; and W is the weight of the adsorbent in g.
2.6. Kinetic study
Kinetic studies were followed according to the method of batch
equilibrium studies outlined in Section 2.5. The adsorption capa-
city qt (mg/g) at different contact time t (min) was determined
using the following equation:
ðC o  C t Þv
qt ¼
W
where Ct (mg/L) is the concentration of MB at time t (min) in the
solution.
2.7. Effect of pH
The effect of initial pH on ABA was executed from pH 3 to 11, at
a fixed ABA dosage of 0.2 g, constant initial concentration of
100 mg/L, and temperature of 30 °C. The pH was regulated using
0.1 M HCl or NaOH and detected with a pH meter (EUTECH
instrument).
2.8. Regeneration study
The regeneration study was carried out immediately after the
equilibrium condition was reached. For this, the MB initial concen-
tration used was 100 mg/L. The ABA samples saturated with MB
were collected from 100 mg/L concentration contained in the flask
and then washed mildly with distilled water to remove residual
dye particles. After that, the ABA particles were dried and poured
into 250 mL flask that contains 200 mL of methanol. The mixture
was then agitated on water bath shaker as described in
Section 2.5 to obtain dynamic equilibrium, and the equilibrium
concentration was calculated. These experiments were repeated
six times, and percentage removal was determined using Eq. (2).
Fig. 1. The BET analysis and pore size distribution of ABA.
623
3. Results and discussion
3.1. ABA characterization
ð2Þ
The nitrogen adsorption–desorption isotherms at 77 K for ABA
is shown in Fig. 1. The BET surface area and cumulative pore vol-
ume for ABA obtained were 185.28 m2/g and 0.158578 cm3/g,
respectively. A clear hysteresis loop, which is associated with type
IV isotherm according to IUPAC classification, is observed from the
isotherm. The isotherm also suggests the typical characteristics of
mesoporous materials [25].
Based on Fig. 1(inset), the average pore size is approximately
5.97 nm, and most of the pores fall within the range of mesoporous
structure according to the IUPAC pore size classification [26].
Usually, micropores are not capable of receiving large molecules
of MB, but mesopores can. Thus, the mesoporous ABA composite
ð3Þ (5.97 nm) can effectively adsorb MB molecules because the mole-
cular size of the MB is only 1.382 nm [27].
SEM images were taken at 100 (Fig. 2 (a1, b1, c1)) and 3000
(Fig. 2 (a2, b2, c2)) magnifications to observe the surface mor-
phologies of BA, AA, and ABA, as shown in Fig. 2. A heterogeneous
and rough surface caused by numerous bulges on the beads of all
composites was observed. More bulges with folds were observed
in ABA (Fig. 2 (c1, c2)) than in BA (Fig. 2 (b1, b2)) and AA (Fig. 2
(a1, a2)). Similar images were also observed in previous studies
on alginate-activated carbon composite [10].
The FTIR spectra of MB before and after adsorption are depicted
in Fig. 3. The wide band at approximately 3468 cm1 corresponds
to the stretching of O–H (hydroxyl) groups and that at
3420 cm1 is responsible for the O–H vibrations, which suggest
the existence of a phenolic group. The strong asymmetric and weak
symmetric stretching vibration bands of C–O–O observed at 1627
and 1388 cm1 are caused by the alginate molecule. The peaks at
1130 and 1045 cm1 are ascribed to C–O stretching and O–C–O
ring (shoulder) [28]. The adsorption band near 775 cm1 can be
attributed to the stretching of the Al–O bond in ABA, and the
adsorption band around 470 cm1 is due to the Si–O stretching
that originated from bentonite clay [29].
After the adsorption of MB onto ABA, many functional groups
shifted to different bands or disappeared. The bands at 3421,
2384, 1627, and 1130 cm1 transferred to higher frequencies at
3433, 2395, 1631, and 1165 cm1, respectively, whereas the peak
624 A. Benhouria et al. / Chemical Engineering Journal 270 (2015) 621–630

Fig. 2. SEM image of the (a) AA, (b) BA, and (c) ABA samples.

Fig. 3. The FTIR spectrum of ABA (a) before, and (b) after adsorption of MB.

1
at 3468 cm slightly shifted to a lower frequency band at
3464 cm1. On the contrary, the peak at 1045 and 775 cm1 disap-
peared after adsorption. The shift and disappearance of different
active functional groups on the ABA after adsorption indicated
the possible interaction of surface sites with MB ions.
concentrations. This observation may be attributed to the highly
available active sites with lesser amount MB dye molecules at
low concentration. The superior adsorption capacity at high initial
concentration is perhaps due to the generation of significant driv-
ing forces caused by pressure gradient [30].

3.2. Effect of concentration on ABA 3.3. Effect of pH

The effect of different MB initial concentrations from 25 to
500 mg/L on ABA adsorption is presented in Fig. 4. The adsorption
uptake of MB dye gradually increases when the concentration
increases. In addition, at initial concentrations of 25 and 50 mg/L,
the point of equilibrium is reached more quickly than at high
The adsorptions reactions between the adsorbate and surface
depend on pH because pH regulates the ionization in the solution.
Fig. 5 illustrates the role of pH on the adsorption of MB dye at
30 °C. For this, the initial concentration was 100 mg/L, the pH
range was 3–11, and all other factors remained constant at their
 A. Benhouria et al. / Chemical Engineering Journal 270 (2015) 621–630 625

Fig. 4. Effect of initial concentration and kinetic modeling on MB adsorption (V = 200 mL, W = 0.2 g, shaking speed of 130 rpm and temperature = 30 °C).

Fig. 5. Effect of solution pH on MB adsorption on ABA (V = 200 mL, initial MB dye concentration = 100 mg/L, W = 0.2 g, shaking speed of 130 rpm and temperature = 30 °C).

respective levels. The results showed that the lowest percentage 3.4. Kinetic of MB adsorption on ABA
removal of MB was found at pH 3 (68.2%), and it gradually
increased up to a certain pH and removed 92.8% of MB. The The kinetic data in this study were applied on pseudo first-order
pHpzc for this study was 8.97. The surface charge of ABA below and pseudo second-order models. The nonlinear form of Lagergren
pH 8.97 (pH < pHpzc) is positive and in more acidic medium pseudo first-order model can be expressed as [32]:
(pH < pKa) the majority of the dye species prevailing in ionic form,  
dissociated MB+ (mainly from the positive charge of amino and sul- qt ¼ qe 1  expk1 t ð4Þ
fur group of the dyes). Moreover, the FTIR analysis showed that for
where qe and qt are the adsorption capacities at equilibrium and at
the –OH group on the surface of ABA, generally in acidic medium,
time t (min), respectively, and k1 (l/min) is the rate constant of first-
the protonation of –OH (i.e., Cx–OH + H+ Cx = Carbon) produced
order adsorption.
more H+ ions that produce electrostatic repulsion force ultimately
The nonlinear form of pseudo second-order kinetic model can
reduces the uptake percentage. In more basic medium (pH > pKa),
be expressed as [33]:
the non-ionic form is predominant in MB but the surface charge
of ABA above pH > pHpzc is found to be more negative that can q2e k2 t
easily interact with the positive ions of MB and finally result to qt ¼ ð5Þ
1 þ qe k2 t
high MB adsorption. Similar results were also reported by several
authors [10,31] in order to the removal of MB prepared from the where k2 (g/mg.min) is the rate constant for the second-order
activated carbon–alginate and clay–alginate composites. kinetic model.
626 A. Benhouria et al. / Chemical Engineering Journal 270 (2015) 621–630

Table 1
Kinetic non linear models parameters for MB adsorption by ABA at 30 °C.

MB conc. (mg/L) qexp (mg/g) Pseudo first order Pseudo second order
3 2
Kl (1/min)  10 qcal R RMSE K2 (g/mg.min)  105 qcal R2 RMSE
25 19.5 1.56 19.5 0.923 1.184 4.7 26.62 0.999 1.003
50 43.1 2.07 44.53 0.994 1.276 3.31 57.00 0.996 0.224
100 94.7 2.55 95.48 0.964 4.336 2.17 116.92 0.960 0.566
200 210.3 3.26 210.24 0.998 4.04 1.53 244.73 0.991 0.623
300 316.7 2.88 317.29 0.988 9.60 0.808 379.05 0.975 1.448
400 408.3 2.84 408.06 0.998 8.61 0.635 484.88 0.994 1.022
500 479.6 3.05 477.81 0.994 12.46 0.609 561.63 0.996 0.669

The pseudo first-order and pseudo second-order kinetic para-
meters determined at 30 °C along with the determination of coef-
ficient (R2) and residual root-mean squared error (RMSE) function
values are presented in Table 1. The R2 and RMSE can be deter-
mined by the following equations [34,35]:
Pn  2
qt:exp:n  qt:cal:n
R2 ¼ 1  Pnn¼1 2
n¼1 qt:exp:n  qt:exp:n
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1 X n low R2 values for the intraparticle diffusion model presented in
RMSE ¼ ðq  qt:cal:n Þ2
n  1 n¼1 t:exp:n
where qt.exp and qt.cal are the experimental adsorption capacity at
time t and the calculated adsorption capacity at time t from the
models, respectively; n is the number of observations.
According to Table 1 and the nonlinear fitted plots presented in
Fig. 4, the adsorption kinetics of MB onto ABA is better described
by the pseudo second-order kinetic model because of the high R2
and low RMSE values than the pseudo first-order model at all ini-
tial concentrations. Previous results related to the adsorption
kinetics of MB by different alginate composites also support the
pseudo second-order model [36,37].
3.5. Adsorption mechanism
To investigate the changes in the concentration of the adsorbate
onto the sorbent with stirring time, the kinetic data of MB sorption
onto ABA composite were fitted into Morris–Weber intraparticle
diffusion [38]:
qt ¼ kid t0:5 þ C ð8Þ
where C is the intercept related to the boundary layer effect and kid
is the intraparticle diffusion rate constant (mg/g min0.5), which can
ð6Þ be evaluated from the slope of the linear plots of qt versus t0.5
(Fig. 6). The linearity of the data in qt versus t0.5 plot ensured the
intraparticle diffusion process mechanism. Based on Fig. 6 and the
ð7Þ Table 2, the plots are nonlinear for the whole range of concentra-
tions studied, indicating that intraparticle diffusion is not the only
rate-limiting step, but other process may also be involved in the
adsorption process. Two different sharp stages were clearly
observed in Fig. 6. The first sharp part describes the instant adsorp-
tion stage where MB adsorption rate is high because of large surface
area and low competition between the dye molecules. The second
part describes the slow adsorption stage caused by the low concen-
tration gradients and that finally produced the equilibrium condi-
tion [36].
Therefore, verifying whether the adsorption process is intra-
particle diffusion controlled or film diffusion controlled is impor-
tant. The process can be identified by the Boyd kinetic equation
according to the following equation [39]:
 
q
 ln 1  t ¼ kfd t ð9Þ
qe

Fig. 6. Weber and Morris intra-particle diffusion plot for the removal of MB by ABA composite beads at 30 °C.
 A. Benhouria et al. / Chemical Engineering Journal 270 (2015) 621–630 627

Table 2
Intraparticule diffusion and film diffusion parameters at 30 °C.

MB conc. (mg/L) Intraparticle diffusion model Film diffusion model

Parameters Step 1 Step 2 Kfd R2
2 2
kid R kid R
25 0.772 0.906 0.392 0.921 0.00174 0.966
50 1.942 0.972 0.744 0.923 0.00229 0.990
100 4.233 0.995 1.402 0.952 0.00296 0.997
200 9.066 0.997 2.286 0.943 0.00315 0.997
300 14.290 0.997 3.907 0.966 0.00304 0.998
400 16.372 0.993 5.697 0.955 0.00285 0.998
500 19.487 0.996 6.005 0.968 0.00283 0.997

where kfd is the liquid film diffusion constant. The adsorption

Table 3
process follows the film diffusion mechanism when the plots Langmuir and Freundlich isotherm parameters for the adsorption of MB onto ABA.
of –ln (1  qt/qe) versus t at different initial concentrations are linear
Parameters ABA
or nonlinear but does not pass through the origin. The Boyd plots
are linear (figure not shown) but do not pass through the origin, 30 °C 40 °C 50 °C
thereby explaining the influence of film diffusion mechanism on Langmuir isotherm qm (mg/g) 756.97 982.47 994.06
the adsorption rate. Likewise, by comparing the data presented in Ka (L/mg) 0.0215 0.0149 0.113
Table 2, the R2 values for the film diffusion model were higher than R2 0.960 0.993 0.829
RMSE 20.885 21.008 42.312
those of intraparticle or pore diffusion model, thereby suggesting
that film diffusion controls the adsorption rate of MB onto ABA Freundlich isotherm Kf ((mg/g)(L/mg)1/n) 38.143 25.007 22.862
n 1.7088 1.399 1.43
under the studied conditions. R2 0.985 0.975 0.9598
RMSE 12.789 16.82 20.569
3.6. Equilibrium adsorption isotherm studies

Adsorption isotherm is very important in describing the rela-

tionship between the adsorbate and adsorption. Moreover, by iso-
therm analysis, the adsorption capacity of the adsorbent, which is
an important parameter in the industrial design for adsorption
process, was predicted. The Langmuir and Freundlich isotherm
models were used to determine the MB adsorption isotherm para-
meters on the ABA composite. The Langmuir model [40] explains
the monolayer adsorption process that occurs on the homogeneous
adsorbent surface, whereas the Freundlich isotherm [41] presumes
that the multilayer of the adsorption process occurs on a heteroge-
neous surface. The nonlinear form of Freundlich (Eq. (10)) and
Langmuir (Eq. (11)) isotherm models can be described by the fol-
lowing equations, respectively:
qe ¼ K f C 1=n
e
qm K a C e
qe ¼
1 þ K aCe
where Kf is the Freundlich adsorption coefficient and n is the expo-
nential coefficient that is related to the adsorption intensity; qm
(mg/g) is the Langmuir maximum adsorption capacity of the ABA
and Ka is the Langmuir’s constant related to the adsorption energy.
The applicability of these two models was evaluated by the R2
and RMSE function values. The highest R2 and the lowest RMSE val-
ues at all studied temperatures determine the best isotherm model
followed by this study. The R2 and RMSE were determined using
Eqs. (12) and (13):
Pn  2
2 n¼1 qe:exp:n  qe:cal:n
R ¼ 1  Pn  2
n¼1 qe:exp:n  qe:exp:n
The Langmuir and Freundlich parameters such as Ka, qm, Kf, and
n in conjunction with the R2 and RMSE values are shown in Table 3.
Given the high R2 and low RMSE values, the adsorption data of MB
dye on ABA at different temperatures is better described by the
Freundlich model than the Langmuir model.
The better fitting of the isotherm data to the Freundlich model
indicates that the removal of MB on heterogeneous surface of ABA
may involve multi-layer adsorption, which also supports the pro-
posed physisorption mechanism [42].
The shape of the isotherm provides information about the
adsorption mechanisms. According to Giles classification of
adsorption isotherm [43], the MB adsorption onto ABA forms an
ð10Þ L-shape curve (Fig. 7), which indicates that MB molecules are prob-
ably adsorbed in a flat position because of low competition from
solvent molecules. Moreover, in this study, the Freundlich expo-
ð11Þ nential factor n that was found to be greater than 1 for all studied
temperature indicates a favorable adsorption process. The
Langmuir monolayer adsorption capacities were 756.97, 982.47,
and 994.06 mg/g at 30, 40, and 50 °C, respectively, which are very
promising compared with other alginate composites for MB
adsorption described in Table 4.
3.7. Thermodynamics of adsorption
The experimental data for MB adsorption on ABA at various
temperatures were applied to determine the thermodynamics
parameters such as Gibbs free energy (DG°), enthalpy variation
(DH°), and entropy variation (DS°) using Gibbs and Van’t Hoff
ð12Þ
equations [44]:

sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi DG ¼ RT ln K o ð14Þ

1 X n
 2
RMSE ¼ q  qe:cal:n ð13Þ He
n  1 n¼1 e:exp:n Ko ¼ ð15Þ
Ce
where qe.exp and qe.cal are the experimental adsorption capacity at
equilibrium and the calculated adsorption capacity at equilibrium DG DS DH
ln K o ¼ ¼  ð16Þ
from the models, respectively. RT R RT
628 A. Benhouria et al. / Chemical Engineering Journal 270 (2015) 621–630

Fig. 7. Langmuir and Freundlich isotherms for MB adsorption on ABA at 30 °C.

Table 4 ranging from 303 to 323 K. All DG° values were negative and
Comparison of monolayer adsorption of MB onto various adsorbents. decreases with increasing temperature, indicating that the MB
Adsorbents Maximum monolayer References adsorption process on ABA was spontaneous. The negative DH°
adsorption value (8.897 kJ/mol) of MB adsorption on ABA confirmed the
capacities(mg/g) involvement of an exothermic process. The value of enthalpy
Calcium alginate–bentonite–activated 994.06 This work changes DH° was lower than 84 kJ/mol, which indicates the
carbon composite beads physisorption adsorption process [45]. The entropy (DS°) value
Calcium alginate Activated carbon beads 892 [27] was also negative (9.802 J/mol.K), which explains the decreased
NaAlg-g-p(AA-co-St)/organo-I/S 1843.46 [37]
NaAlg-g-p(AA-co-St)/I/S 1797.34 [37]
randomness at the solid/solution interface during the adsorption
GO/CA 181.81 [36] process. Li et al. [36] also found similar results for the adsorption
Polydopamine microspheres 90.7 [47] of MB on graphene oxide/calcium alginate.
Calcium alginate beads 800 [27]
Activated carbon produced from 274.62 [48]
3.8. Regeneration studies
buriti shells
Flamboyant pods 874.68 [49]
Cotton stalk 147.06 [50] The regeneration of adsorbent is a significant economic factor
for the treatment process. This process explains the mechanism
of dye-loaded adsorbents for regeneration, recycling, and reusing
where He and Ce are the equilibrium concentrations of dye on ABA of spent adsorbents to save money and the environment from sec-
and solution; Ko is the equilibrium constant; R is the universal gas ondary pollution [46]. Treatment with methanol successfully elut-
constant (8.314 J/mol K); and T is the solution temperature (K). ed 93.05% of the MB loaded onto ABA after six cycles of sorption–
The values of DS° and DH° were determined from the intercept desorption test (Fig. 8). No significant difference was found in the
and slope of plot ln Ko against 1/T. The values of Gibbs free energy percentages of desorbed MB in the six sorption–desorption cycles
(DG°) were 5.920, 5.844, and 5.723 kJ/mol at temperatures for ABA (94.42%, 90.33%, 86.07%, 80.14%, 79.15%, and 75.47%).

Fig. 8. The results of regeneration test for the adsorption of MB onto ABA composite.
 A. Benhouria et al. / Chemical Engineering Journal 270 (2015) 621–630
This result demonstrated the high reusability of the developed ABA
composite without observable loss in their MB removal capacities,
thereby making the rehabilitation of dye-contaminated waste-
water more sustainable and economical [47].
4. Conclusion
The study revealed that the synthesized ABA composite has
high adsorption capacity for the adsorption of MB dye. The results
showed that the MB adsorption was highly dependent on initial
concentration, contact time, initial solution pH, and temperature.
The MB adsorption kinetic and equilibrium data at various process
parameters were analyzed using the nonlinear method. The
obtained results indicated that the pseudo second-order model fits
the experimental data suitably well. In addition, both Freundlich
and Langmuir model fit the experimental data well, but
Freundlich isotherm was better according to error functions. The
ABA showed high resilience on adsorption efficiency after six
regeneration cycles. Conclusively, ABA is an efficient, high-poten-
tial adsorption for the removal of MB and other cationic dyes and
can be used a number of times before disposal.
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