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ISOTHERMAL AND KINETIC ADSORPTION OF ANIONIC DYE ONTO

IMPREGNATED SILICA GELS WITH ALUMINUM

Article  in  Environmental Engineering and Management Journal · August 2020

DOI: 10.30638/eemj.2020.123

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Environmental Engineering and Management Journal August 2020, Vol. 19, No. 8, 1299-1308
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“Gheorghe Asachi” Technical University of Iasi, Romania

ISOTHERMAL AND KINETIC ADSORPTION OF ANIONIC DYE

ONTO IMPREGNATED SILICA GELS WITH ALUMINUM

Yudi Aris Sulistiyo1, Faizatur Rofi’ah1, Suwardiyanto1, Ari Satia Nugraha2, Zulfikar3,
Gagus Ketut Sunnardianto4
1
Inorganic Material for Energy and Environment Research Group, Department of Chemistry,
Faculty of Mathematics and Natural Science, University of Jember, Jember, Indonesia 68121
2Drug Utilisation and Discovery Reseach Group, Faculty of Pharmacy,

University of Jember, Jember, Indonesia 68121

3Sensor and Chemical Instrumentation Research Group, Department of Chemistry,

Faculty of Mathematics and Natural Science, University of Jember, Jember, Indonesia 68121
4Research Center for Chemistry, Indonesian Institute of Sciences (LIPI),

Kawasan Puspitek Serpong, Tangerang Selatan, 15314, Indonesia

Abstract

Impregnation of aluminium ion onto silica gel (SG) surface (Al/SG) is to increase the adsorption capacity of an anionic dye such as
Indigo carmine (IC). The impregnation was carried out using wetness impregnation. The change of the functional group was
evaluated by FTIR, crystallinity was determined using XRD, surface morphology were studied by SEM-EDX, while surface area
and pore size using N2 gas adsorption-desorption analyzer. Meanwhile, the best of IC adsorption condition onto SG and Al/SG
occurred consecutively at pH 2 and 3. The optimum adsorption of both adsorbent was 25.707 and 88.143 mg.g−1 with the adsorption
efficiency 21.82% and 80.47%, respectively. Whereas, isothermal adsorption model of SG and Al/SG consecutively followed
Langmuir and Freundlich model. The equilibrium adsorption was achieved in 60 min of contact time following pseudo-second order
kinetic model. This study provides information about the replacing negative charge in the surface of the adsorbent with cation would
increase the adsorption capacity of the anionic adsorbate.

Key words: adsorption isotherm, adsorption kinetic, aluminum impregnation, anionic dye indigo carmine, modified silica gels

Received: August, 2019; Revised final: March, 2020; Accepted: April, 2020; Published in final edited form: August, 2020

1. Introduction 2019; Tang et al., 2019). Indigo Carmine is also a

group of anionic indigoid dyes with high toxicity
Industrial coloring activities such as textiles, levels and skin and eye irritant (Carvalho et al., 2011).
printing, paper, and plastic used approximately 50% Biological, chemical and physical methods are
of the anionic dyes (Alver and Metin, 2012; Zhou et used to solve anionic dye problems. The biological
al., 2019). In the coloring process, they would methods such as bioremediation and biodegradation
discharge about 10-15% unused dye into the aquatic by microorganisms are the most eco-friendly (Mishra
environment as wastes (Mahmoodi et al., 2011a). and Malik, 2014; Wangpradit and Chitprasert, 2014),
Even at low concentrations, the anionic dye is colorful but the degradation rates of the dye were generally
and challenging to be degraded naturally (Chen and slow (Amir et al., 2017). The advantage using
Chen, 2018; Ma et al., 2011). The anionic dye is one chemical methods i.e. coagulation, flocculation,
of the acidic dyes that highly reactive, harmful to the oxidation, ozonation, electrochemical, and photo-
environment, and carcinogenic to humans (Jiang et al., degradation are usually efeective, but they have the

Author to whom all correspondence should be addressed: e-mail: [email protected]; Phone: +62331334293; Fax: +62331330225
 Sulistiyo et al./Environmental Engineering and Management Journal 19 (2020), 8, 1299-1308

problems such as produce sludge, need large amounts evaluated by toward pH, initial concentration of
of chemical reagent, need high energy and technically indigo carmine, and contact time of adsorption in
difficult to apply (Zhou et al., 2019). Meanwhile, the batch systems. The performance of the adsorbents was
physical treatment such as filtration with the studied by the isothermals and kinetic models of
membrane and adsorption was good removal of wide adsorption.
variety of dye and relatively easy to implement (Salleh
et al., 2011). Adsorption is the most promising method 2. Experiments
to solve the anionic dye problems because its
technology is easy, inexpensive, effective, and does 2.1. Material
not generate new environmental problems (Silva et al.,
2013). On its process, adsorption needs materials that The chemicals are Al(NO3)3.9H2O (Merck,
have high sorption capacity for anionic dye. 98,5%), NaOH (Merck, 99%), fuming HCl (Merck,
The most economical adsorbent is natural 37%), H2SO4 (Merck, 95-97%), anionic dye is Indigo
materials such as zeolite, fly ash, clay, active carbon, Carmine manufactured by Merck with molecular
and biomass. The optimum removal of ramazol red weight 466.36 g.mol−1, λmax 610 nm, and the
dye was 11.83 mg.g−1 that determined by the SiO2 structure shown in Fig. 1, fly ash from PT. IPMOMI
content of the adsorbent (Costa and Paranhos, 2019). Paiton Probolinggo, East Java, Indonesia.
On the other hand, Fly ash that has SiO2 content
around 64.97% was a potential adsorbent to remove
dye pollutants (Adak et al., 2014). Fly ash was
produced from coal combustion of power plant around
750 million tons in 2015 (Yao et al., 2015), and only
12% was recycled into useful products (Gollakota et
al., 2019). So, the utilization of fly ash as adsorbent is
not only able to solve the dye pollutants problem, but
also the coal combustion waste problem. However, the Fig. 1. Chemical structure of indigo carmine
metal oxides contained in the fly ash can decrease the
sorption capacity of dye. It was shown in the 2.2. Material preparation
adsorption capacity of methylene blue by fly ash, and
amorphous silica from fly ash was 0.12 mg.g−1 Silica was extracted from 10 g of Fly Ash with
(Karaca et al., 2018) and 323.63 mg.g−1 (Yuan et al., NaOH 3 mol.L−1 and produced sodium silicate.
2019), respectively. Hence conversion fly ash to be Sodium silicate titrated with HCl 1 M until pH 7 to
silica gels is a potential method to produce a material form solid silica through the sol-gel process. The soft
having excellent performance as the adsorbent gel of silica was aged for 18 h, subsequently washed
(Manchanda et al., 2017). Moreover, silica has high with distilled water and dried at 100 °C for 12 h.
thermal and chemical stability, possible reuse, Powder of silica gel (SG) produced was calcined at
relatively rapid to obtain the equilibrium, and high 550 °C for 4 h. SG 5 g was immersed in 50 mL of 10%
surface area (Mahmoodi et al., 2011b). aluminium solution and stirred for 2 h. Without
The primary challenge to apply the adsorbent decantation, the mixture was dried to evaporate the
to the anionic dyes is the negative charge from the water content and calcined at 550 °C for 4 h to produce
surface of the material. The negative charge of the modified aluminium onto silica gel (Al/SG).
surface of silica was from Si-O and Si-OH group,
which suitable for the positive charge of adsorbate and 2.3. Material characterization
prevented negative charge (Anbia et al., 2010). The
negative charge of the material causes a repulsive The different structure of SG and Al/SG was
force with the anionic dye. It is certainly not beneficial confirmed by diffractogram of XRD (PANanalytical
and requires a transformation of the surface charge of X’Pert) using Cu-Kα radiation in λ 1,5404 Å with 2θ
the material from negative to positive. The = 5-50°. FTIR spectra were collected on Shimadzu
modification of the surface charge can be carried out Prestige 21 at a wavelength of 400–4000 cm−1.
using metal impregnation. Surface morphology was studied using SEM FEI
Aluminum with amphoteric nature can be Inspect-S50 with 40.000 times magnification and
chosen as an excellent modifier because it has a wide elemental analysis was performed by EDAX
range of pH tolerance. The previous study showed that AMETEK. Surface area and pore size were
the addition of Aluminum 10% onto SBA-15 be able determined using Quantachrome Instrument NOVA
to adsorb anionic phosphate about 862 mol.g−1, while 1200e.
without impregnation SBA-15 cannot adsorb the
phosphate due to the negative charge of SBA-15 (Shin 2.4. Indigo carmine adsorption
et al., 2004). In this paper, a study of the indigo
carmine uptake as the representation of anionic dye A mixture of 25 mL indigo carmine with
was carried out using impregnated aluminum ion onto various concentration (25-500 mg.L−1) and 50 mg
silica gel. The silica gel was prepared from fly ash adsorbent (SG or Al/SG) was placed in a conical flask.
from a power plant combustion. The adsorption is The pH of the mixture (2–11) was adjusted by the

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 Isothermal and kinetic adsorption of anionic dye onto impregnated silica gels with aluminum

addition of 0.1 mol.L−1 NaOH or HCl solution. The adsorbate (mg.L−1), qe is the amount of adsorbate that
mixture was shaken for 60 minutes to reach the adsorbed per unit mass (mg.g−1), KF is Freundlich
adsorption equilibrium. The initial and residual constant related to the adsorption capacity of the
concentration of indigo carmine was measured by UV- adsorbent, n is the Freundlich constants related to
Visible Spectrophotometer Shimadzu Spectronic 20 at surface heterogeneity.
wavelength λmax = 611 nm. The adsorption capacity qe
(mg.g−1) and efficiency E (%) toward Indigo carmine Temkin Isothermal Adsorption Model
was calculated as Eqs. (1-2), respectively. The higher The models assume that interactions between
adsorption capacity of both adsorbents (SG and adsorbate species and adsorbent cause the decreasing
Al/SG) was the better as an adsorbent for indigo linearly of the heat adsorption in the layer of all
carmine removal. molecules, and adsorption is characterized by a
uniform distribution of binding energies. The model is
qe  (C0  C f )V / m (1) described as shown in (Eq. 6) by ploting qe vs ln(Ce).

E  ((C 0  C f )C 0 )  100 % (2) qe   ln Kr   ln(Ce )  

where: β = RT/bt, where bt is the Temkin constant

where: C0 and Cf are respectively the initial and
related to the heat of adsorption (J.mol−1), KT is
remaining concentration of indigo carmine in mg.L−1,
equilibrium binding constant (L.g−1), R is the universal
V is the volume of the indigo carmine in L and m is the
gas constant (8.314 J.mol−1.K−1), and T is the
mass of the adsorbent in g.
temperature of adsorption (K).
2.5. Adsorption isotherm model
2.6. Adsorption kinetics model
The Isothermal adsorption were evaluated from
The studies of kinetics adsorption was
equilibrium of adsorption data using liniearity models
calculated by pseudo-first-order, pseudo-second-
as follows:
order, Intra-particle, and Elovich Diffusion Equations
Langmuir Isotherm Adsorption Model
models, as follows:
The model depicts that adsorption occures as a
Pseudo-first-order Model was determined by
single layer of adsorbed material on homogeneous
the plot between log (qe-qt) versus t, (Eq. 7):
solid surface. The Linear plot of the Langmuir model
can be expressed according to (Eq. 3) by ploting 1/qe
vs 1/Ce. Log (qe  qt )  Log (qe )  (k1 / 2.203)  t (7)

1 / qe  (1 / Ce K L q max )  (1 / q max )   Pseudo-second-order Model was determined by plot
t/qt versus t, (Eq. 8):
where: Ce is the equilibrium concentration (mg.L−1), 2
qe is the amount of adsorbed Indigo Carmine on the t / qt  1  (k 2  qe )  (1 / qe )  t (8)
equilibrium (mg.g−1), qmax is the complete monolayer
sorption capacity (mg.g−1), KL is Langmuir Intra-particle Diffusion Model was determied by plot
equilibrium constant related to the free energy of qt vs t1/2, (Eq. 9):
adsorption (L.mg−1).
Langmuir isotherm of constant separation qt  k t  t 1 / 2  C (9)
factor (RL) was used for defining the favorability of
the adsorption process. RL is defined as (Eq. 4); The Elovich Equation Model was determined by plot qt vs
irreversible isotherm indicated the values of RL = 0, ln(t). (Eq. 10):
favorable (0 < RL < 1), linear (RL = 1) or unfavorable
(RL > 1).
qt  1 /  ln( )  1 /  ln(t ) (10)
RL  1 /(1  bC0 0) (4)
where: qt and qe are the amounts of adsorbate adsorbed
in time t and equilibrium (mg.g−1), k1 is a constant
Freundlich Isotherm Adsorption Model pseudo-first-order (min−1) and t is the interaction time
The model is appropriate for interaction (min), k2 is the Pseudo-second-order costant
between adsorbed molecules in multilayer with (g.mg−1.min−1), kt is the rate constant of intra-particle
heterogeneous active sites of the adsorbent. The diffusion (mg.g−1.min−1/2) and C showes the
Freundlich model following linear plot in (Eq. 5) by relationship boundary layer thickness. The larger of
ploting Log(qe) vs Log(Ce). the value of C was the greater of the effect of the
barrier layer. α is the adsorption rate constant at first
Log (qe )  log K F  1 / nLog (Ce ) (5) (mg.g−1.min−1) and parameter β is the relations of the
surface that covered and chemisorption activation
where: Ce is the equilibrium concentration of energy (g.mg−1).

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 Sulistiyo et al./Environmental Engineering and Management Journal 19 (2020), 8, 1299-1308

frameworks during the impregnation process. Shin et

3. Results and discussion al. (2004) reported that aluminum ion interacted with
Si-OH of silica structure (SBA-15), and also attacked
3.1. Characterization of SG and Al/SG Si-O bonding in the mesoporous framework.
Consequently, Al3+ were incorporated by reaction
Metal oxides within fly ash such as Al2O3, with the silanol functional group of silica framework.
Fe2O3, CaO, and MgO can reduce adsorption capacity, Further characterization was carried out by
so purification should be applied. The metal oxides XRD analysis, scanning electron microscope (SEM),
were separated through acid leaching, isolation of and N2 gas adsorption analyzer. Diffraction patterns in
SiO2 with NaOH to produce Na2SiO3 and acidification Fig. 3 show an inordered structure in both SG and
of Na2SiO3 result in silica gel. Aluminum Al/SG. It can lead to the conclusion that the materials
impregnation onto silica gel was intended to change are amorphous. The amorphous structure of silica gels
the surface charge of silica gel into negative. FTIR can also be found in silica from rice straw (Lu and
spectra show the structural changes caused by Hsieh, 2012).
modification SG with Aluminium ion. Both SG (Fig. It also indicated the high dispersion of
2.a) and Al/SG (Fig. 2.b) have similar frameworks, impregnated Al3+ in the surface of Silica. The
i.e., siloxane (Si-O-Si) and silanol (Si-OH). The peaks significantly lower intensity of Al/SG than SG on 2θ
with a wavenumber of 455, 804, and 1080 cm−1 (Peak above 15° (Peak 1) and the peak shifts in 2θ around
3 - 5) indicate the bending, symmetric stretching and 25° to 23.5° (Peak 3 to Peak 2) for SG and Al/SG
asymmetric stretching of the intratetrahedral oxygen proved the existence of Al3+. Hashemian et al. (2014)
atom in Si-O-Si structure. reported the broad peak at a 2θ angle of around 22o
Meanwhile, the band at 1639 and 3284 cm−1 depicted the amorphous structure of silica with a high
(Peak 1 and 2) are asymmetric stretching and bending dispersion of metal ion on its surface. That
of Si-OH. Impregnated Al3+ decreased both the peak argumentation was in line with another investigation
intensity of 1639 and 1080 cm−1 (Peak 2 and 3). The using the morphology image by SEM in Fig. 4 that
decreased peak in 1639 cm−1 of Al/SG was attributed shows both SG and Al/SG have irregular sphericle
to the interaction between the Si-OH group of the shapes. Since the particle size of Al/SG was bigger
silica surface with impregnated Al, while in 1080 cm−1 than SG, it was indicating that Aluminium was
depicted the Al3+ also interacted with Si-O impregnated onto the surface of silica.

Fig. 2. FTIR spectra of SG and Al/SG

Fig. 3. Diffractogram X-ray of SG and Al/SG

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 Isothermal and kinetic adsorption of anionic dye onto impregnated silica gels with aluminum

Fig. 4. SEM image of a) SG and b) Al/SG

That was also supported by elemental analyses 3.2. Adsorption studies

using EDX (Table 1) in increasing of Al3+ content in
Al/SG compared with SG. Isothermal N2 gas 3.2.1. Effect of pH
adsorption analyzer profile in Fig. 5. depicted the One of the important parameters in this
decreasing of adsorbed N2 gas volume and loop adsorption process is the pH of the solution. It affects
hysteresis in Al/SG than SG. It was affected by the charge distribution and binding site of both adsorbent
decrease of the surface area and pore volume of Al/SG and adsorbate (Kamboh et al., 2011). The adsorption
than in SG (Table 2). Thes most probable phenomena was studied in pH of 2-11 with the initial
are Al3+ block the SG pore and minimize N2 traping in concentration of Indigo carmine of 200 mg.L−1 and
the pore structure of Al/SG. contact time of 60 minutes. The result is presented in
Fig. 6. The highest adsorption capacity of SG and
Table 1. Elemental analysis in the adsorbent by EDX Al/SG toward indigo carmine are achieved at pH 2 and
pH 3, respectively. In the acid condition, anionic dye
Adsorbent Element Wt (%) generates a negative charge from the presence of SO3−
SG O 50.276
group (Rashwan et al., 2019).
Si 43.213
Al 2.653
Whereas adsorbent Al/SG has a positive charge
Na 3.270 that determined from Al3+, [Al(OH)2]+, and
Al/SG O 49.100 [Al(OH)]2+, while SG without modification was from
Si 44.506 Si-OH2+. The acid condition may influence anionic
Al 6.390 exchange between the positive charge on the surface’s
materials with a negative charge in SO3− of a group of
Table 2. Surface area and pore size analysis of the dye (Errais et al., 2011). Chen and Chen (2018) also
adsorbent assumed that lower pH enhanced the electrostatic
interaction between negative charge of sulfonated
Adsorbent Surface Pore Size Pore Volume groups of indigo carmine and positive charge of
Area (nm) (m2.g−1) adsorbent by the ion exchange. So, the possible
(m2.g−1)
interaction between both adsorbent and indigo
SG 143.55 1.909 0.279
Al/SG 125.45 1.907 0.198
carmine was represented consecutively in Eqs. (11-
12). Moreover, OH− excess in the solution system
caused aluminum in species [Al(OH)4] − and the
surface of Al/SG has the negative charge, while the
negative charge in SG was resulted by protonated
silanol group to be Si-O−. The present of OH− in the
solution system reduced the anion exchange that
resulted by electrostatic repulsion force between
anionic indigo carmine molecule and negative charge
surface of adsorbent (Almoisheer et al., 2019).
Anion Exchange in Al/SG (Eq. 11)

Si  O  Al 3 X   IC   Si  O  Al 3 IC   X  (11)

Anion Exchange in SG (Eq. 12)

Fig. 5. Isothermal ads-Des of N2 curve of the adsorbents Si  O  H 2 X   IC   Si  O  H 2 IC   X  (12)

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 Sulistiyo et al./Environmental Engineering and Management Journal 19 (2020), 8, 1299-1308

efficiency decreased from 98.8 % to 80.47% with the

increasing initial concentration of indigo carmine.
3.2.3. Adsorption isotherms
The models of adsorption of indigo carmine by
SG and Al/SG can be studied using the adsorption
isotherm parameters. The adsorption isotherms were
fitted by three isothermal equation models, i.e.,
Langmuir, Freundlich, and Temkin that depicted in
Fig. 7. Adsorption isotherms were used for evaluating
qualitative information on the adsorption capacity of
adsorbents when the adsorption process reaches
equilibrium (Tang et al., 2019). Isothermal models are
also used to describe the design process of adsorption
Fig. 6. Effect pH system of adsorption indigo carmine occurring between indigo carmine and SG or Al/SG.
Meanwhile, the adsorption constants of Indigo
3.2.2. Effect of initial indigo carmine concentration carmine by SG and Al/SG are calculated and tabulated
The removal of indigo carmine was examined in Table 3.
by different initial concentrations ranging between 25 Table 3. Isothermal model parameters for removal
mg.L−1 and 500 mg.L−1 in optimum pH systems indigo carmine by the adsorbent (adsorbent dosage 50
depicted in Fig. 7.a. The adsorption capacity of SG mg, initial indigo carmine concentration 25-500 mg.L−1)
increased with increasing indigo carmine
concentration. The maximum adsorption capacity of Adsorbents
Adsorption Models
SG toward indigo carmine is reached at an initial Al/SG SG
qe exp (mg.g−1) 88.143 25.707
concentration of 200 mg.L−1. These phenomena
Langmuir
indicated that the indigo carmine blocked the active qmax(mg.g−1) 89.286 23.679
site of the adsorbents. Then, the surface of adsorbent KL (L.mg−1) 0.013 0.005
is saturated, and as a result, no more adsorbed indigo RL 0.281 0.479
carmine at higher concentrations. The maximum R2 0.835 0.972
amount of adsorbed indigo carmine on SG was 25.707 Freundlich
mg.g−1 with removal efficiency was 21.82%. Whereas KF (L.g−1) 2.944 0.424
Al/SG has a different profile, the amount of adsorbed nF 1.636 1.099
indigo carmine increased with increasing initial R2 0.970 0.962
concentration. However, no plateau profile illustrated Temkin
the no saturated condition was achieved. In the initial bt x 102 0.504 3.775
concentration of 200 mg.L−1, the amount of adsorbed KT 3.137 22.910
indigo carmine is 88.143 mg.g−1. However, removal R2 0.892 0.861

Fig. 7. (a) Effect of initial concentration of IC on the adsorption, plot of isotherm adsorption models,
(b) Langmuir, (c) Freundlich, (d) Temkin

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 Isothermal and kinetic adsorption of anionic dye onto impregnated silica gels with aluminum

The adsorption model of SG was best fitted impregnation Al3+ onto SG significantly increase the
with the Langmuir adsorption isotherm model with the adsorption capacity of indigo carmine.
highest coefficient correlation values (R2 = 0.972) as The adsorption capacity of Al/SG and SG,
compared with Freundlich (R2 = 0.962) and Temkin calculated by the three models of adsorption isotherm,
(R2 = 0.861). The adsorption process was assumed that were to understand the level of adsorption efficiency.
indigo carmine adsorbed in the homogeneous surface, Table 4 listed the adsorption efficiency of the indigo
and the interactions were the monolayer. The RL carmine using both adsorbents in comparison with
values (0.479) also confirm these phenomena for the other potential adsorbents from the previous
SG. This range value (0 < RL < 1) indicates the publications. In conclusion, Al/SG had high
favorable adsorption isotherm, which followed the adsorption efficiency and could be classified as a
Langmuir adsorption isotherm model. The linearity potential adsorbent to remove indigo carmine.
plot of the experimental data was between 1/qe and
1/Ce on the variation of the initial concentration that 3.2.4. Kinetics of adsorption
indicated the maximum sorption capacity and The adsorption kinetics experiments were
Langmuir constant (qmax and KL) of the slope and performed to understand the adsorption diffusion form
intercepts, respectively. The maximum adsorption and the reaction mechanism of indigo carmine on
capacity, qmax, of SG was 23.679 mg.g−1. Al/SG and SG. Fig. 9a showed the relationship
At the same time, the adsorption process of between contact time and adsorption capacities.
Al/SG could be better matched with Freundlich According to the figure, the rapid adsorption process
corresponding with the coefficient correlation (R2 = was at the beginning, then increased slightly, and
0.970) than Langmuir (R2 = 0.835) and Temkin (R2 = finally reached the equilibrium in 60 min for both
0.892). It indicated the surface site of Al/SG had adsorbent. It was also observed that the adsorption rate
different binding energy, and the adsorption on the of Al/SG was much faster than SG. The adsorption
surface of Al/SG was multilayer adsorption from kinetics were analyzed by using pseudo-first-order
heterogeneous distribution of indigo carmine (Eq. 7), pseudo-second-order (Eq. 8), intraparticle
interaction. The value of the heterogeneity factor (n) diffusion (Eq. 9) and Elovich (Eq. 10) models. Table
was 1.636 (more than 1) that showed the physical and 5 shows the relevant parameter of the kinetics models
chemical reaction in the adsorption process (Chen and that calculated from each of the slopes and the
Chen 2018). Multilayer adsorption might be generated intercepts of linear regression. The adsorptions indigo
from the interaction between the positive charge of carmine on both adsorbent were best expressed using
adsorbent surface and negative charge from SO3− the pseudo-second-order model with the highest
group of indigo carmine, in the acid condition. correlation coefficients (R2 = 0.99). It indicated that
Moreover, protonated of -NH groups of IC formed - the active site of the adsorbent and molecule of indigo
NH2+ group and facilitated the interaction with another carmine influence in the adsorption process by
SO3− group. The hypotetic interaction between Al/SG electron transfer (Sulistiyo et al. 2017; Rashwan et al.,
and IC depicted in Fig. 8. That showed that 2019).

Table 4. The comparison of adsorption capacity of indigo carmine on various adsorbent

Initial IC Adsorption Removal

Adsorption
Adsorbent pH Concentration Capacity Efficiency Reference
Time (min)
(mg.L−1) (mg.g−1) (%)
Calcium Hydroxide Arenas et al.
- 300 75 0.4 58
(2017)
Zeolite from fly ash - 240 11 1.23 90 Carvalho et
Fly ash - 45 14.7 1.48 84 al. (2011)
Silica Gel from fly ash 2 25.71 21.82
60 200 This Study
Aluminium/Silica Gel 3 88.14 80.47
Fe-zeolitic tuff 32.83 -
Gutierrez-
Carbonaceous material
6.5 2400 200 Segura et al.
from pyrolyzed sewage 92.83 -
(2009)
sludge
Pistia Stratiotes dry Ferreira et al.,
- 120 200 41.2 20.6
biomass activated H2SO4 (2019)
Mesoporous Mg/Fe LDH Ahmed et al.,
9.5 30 55.92 55.8 -
Nanoparticle (2017)
Surface modified Yazdi et al.,
5 120 20 154.5 77.3
composite nanofiber (2018)
CuAl-LDH 89.46 8.9
SWCNTs nanocomposite 179.5 18 Almoisheer et
2 360 500
CuAl-LDH/SWCNTs 294.1 29.4 al. (2019)
nanocomposite

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 Sulistiyo et al./Environmental Engineering and Management Journal 19 (2020), 8, 1299-1308

Fig. 8. Hypotetical interaction models of IC on Al/SG

Fig. 9. (a) Adsorption kinetics of indigo carmine by adsorbents, plots of (b) Pseudo-first-order, (c) Pseudo-second-order,
(d) Intra particle diffusion, (e) Elovich. (200 mg.L−1 adsorbate, 50 mg of adsorbents

Table 5. Kinetic parameter models of the adsorption of 4. Conclusions

indigo carmine
Kinetic Model Parameter Al/SG SG In conclusion, adsorbent Al/SG was prepared
Pseudo-first- qe (mg.g−1) 1.00 1.00 from SG and Al3+ using wetness impregnation method
order k1 (min−1) 1.95 1.91 for removal indigo carmine as anionic dye
R2 0.62 0.96 representation. Physicochemical properties of
Pseudo-second- qe (mg.g−1) 84.03 20.32 adsorbent described that impregnated Al3+ covered
order k2.103 168.94 2.10 active site of SG. In consequence, particle size of
(mg.g−1.min−1) 0.99 0.99 Al/SG was bigger than SG while the surface area and
R2 pore volume decrease.
Intra-particle kp 2.04 0.30
The adsorption character of Al/SG and SG on
diffusion (mg.g−1.min−1/2) 59.27 16.01
C (mg.g−1) 0.79 0.97 indigo carmine was influenced by initial solution pH,
R2 initial dye concetration, and contact time. Adsorption
Elovich α.104 0.68 1304.63 isotherms showed that SG and Al/SG consecutively
(mg.g−1.min−1) 0.14 1.11 fitted better with Langmuir and Freundlich, which
β (g.mg−1) 0.92 0.85 adsorption model following monolayer and multilayer
R2 mechanism, respectively.

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 Isothermal and kinetic adsorption of anionic dye onto impregnated silica gels with aluminum

Adsorption condition was better carried out in and carbonaceous material from pyrolyzed sewage
pH 2 for SG and pH 3 for Al/SG. The optimum sludge, Journal of Hazardous Materials, 170, 1227-
adsorption capacity (qmax) of both adsorbents was 1235.
25.707 mg.g−1 and 88.143 mg.g−1 in optimal condition Gollakota A.R.K., Volli V., Shu C.M., (2019), Progressive
utilisation prospects of coal fly ash: A review, Science
50 mg adsorbent dosage, 200 mg/L−1 indigo carmine, of the Total Environment, 672, 951-989.
2 h adsorption time. The adsorption kinetic models of Hashemian S., Sadeghi B., Mangeli M., (2014),
SG and Al/SG followed pseudo-second-order model. Hydrothermal synthesis of nano cavities of Al-MCF for
The result describes that Al/SG can be a potential adsorption of indigo carmine from aqueous solution,
adsorbent for removal indigo carmine dye from waste Journal of Industrial and Engineering Chemistry, 21,
water. 423-427.
Jiang C., Wang X., Qin D., Da W., Hou B., Hao C., Wu J.,
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