Journal of Cleaner Production xxx (2016) 1e13

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Journal of Cleaner Production

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Evaluation of physicochemical methods in enhancing the adsorption

performance of natural zeolite as low-cost adsorbent of methylene
blue dye from wastewater
Kar Yan Hor a, 1, Jasmine Mun Cheng Chee a, 1, Meng Nan Chong a, b, *, Bo Jin c,
Christopher Saint d, Phaik Eong Poh a, b, Rupak Aryal d
a
School of Engineering, Chemical Engineering Discipline, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway, Selangor DE 47500, Malaysia
b
Sustainable Water Alliance, Advanced Engineering Platform, Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway,
Selangor DE 47500, Malaysia
c
School of Chemical Engineering, The University of Adelaide, North Terrace Campus, Adelaide, 5005 South Australia, Australia
d
Centre for Water Management and Reuse, University of South Australia, Mawson Lakes Campus, Mawson Lakes, 5095 South Australia, Australia

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

Article history: The main aim of this study was to evaluate different facile and cost-effective physicochemical methods in
Received 10 September 2015 enhancing the adsorption capacity of natural zeolite and subsequently demonstrate the removal of
Received in revised form methylene blue (MB). Four different physicochemical methods, namely: acid treatment (AT), base
14 January 2016
treatment (BT), combined acid-thermal (ATT) and base-thermal treatments (BTT) were investigated. This
Accepted 24 January 2016
was followed by understanding the impact of the physicochemical methods on the surface characteristics
Available online xxx
and properties of modified zeolite through advanced characterisations using field emission-scanning
electron microscopy, Fourier-transformed infrared spectroscopy and BrunauereEmmetteTeller specific
Keywords:
Adsorption
surface area and porosity measurements. Batch adsorption studies were carried out using the modified
Modified zeolite zeolite adsorbents, in order to evaluate the highest removal efficiency of MB under varying adsorption
Acidebase treatment conditions of: pH, initial MB concentration and modified zeolite loading. Results showed that both the
Thermal treatment physicochemical methods of AT (using 0.4 M HCl) and BT (using 4.0 M NaOH) are able to enhance the
Adsorption isotherm adsorption capacity of natural zeolite from 41% to 98.8% and 52.2%, respectively. Surprisingly, the
Kinetic model combined physicochemical methods of ATT and BTT showed a reduction in adsorption performance
when benchmarked to AT and BT alone. The adsorption data were analysed and modelled using Lang-
muir, Freundlich, Redlich-Peterson and Koble-Corrigan isotherm models, also the adsorption kinetics
were evaluated using pseudo-first and pseudo-second order models. It was found that the adsorption
data and kinetics were best represented using the Koble-Corrigan and pseudo-second order models. The
improvements yielded through both the AT and BT modified zeolites were found to be promising and
have the potential to be used as low-cost adsorbents for wastewater treatment.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction microbes (Chong et al., 2010, 2011a) unless it is properly treated

(Malik et al., 2015). If wastewater remains untreated and is
Wastewater is a by-product that consists of a mixture of solid discharged directly into the environment, water pollutants can
and liquid after the usage of water from households, industries and enter the natural water systems and cause negative impacts
commercial establishments. Typically wastewater is no longer towards the environment and public health (Chong et al., 2011b).
serving a useful purpose compared to high-quality mains water Various industries such as textiles, cosmetics, plastics and paper
usage, and may contain significant amount of pollutants and industries are known to heavily use synthetic dyes in their
production to impart colour to their finished products. A significant
amount of dyes are commonly present in the effluents of these
* Corresponding author. School of Engineering, Chemical Engineering Discipline, industries and need to be treated before being discharged into the
Monash University Malaysia, Jalan Lagoon Selatan, Bandar Sunway, Selangor DE environment (Reddy et al., 2012). In the absence of proper treat-
47500, Malaysia. Tel.: þ60 3 5514 5680; fax: þ60 3 5514 6207. ment methods, synthetic dyes which have aromatic structures may
E-mail address: Chong.Meng.Nan@monash.edu (M.N. Chong).
1
Joint first author.
pose a threat to aquatic life due to their non-biodegradable nature,

http://dx.doi.org/10.1016/j.jclepro.2016.01.056
0959-6526/© 2016 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
2 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13

and some are even carcinogenic (Gupta and Suha, 2009). There can adsorption capacity of natural zeolite and subsequently demon-
also be significant secondary effects of dyes, such as hindering strating these utilising removals of methylene blue (MB). Four
sunlight from penetrating into the water bodies and thus, depriving different physicochemical methods, namely: acid treatment (AT),
aquatic life of vital light-sensitive chemical reactions (Robinson base treatment (BT), combined acid-thermal (ATT) and base-
et al., 2001; Zhou et al., 2014). Thus, the proper treatment and thermal treatments (BTT) were investigated. This was followed by
removal of synthetic dyes from wastewater is essential before the investigating the impact of the physicochemical methods on the
remaining effluent is discharged into the environmental water surface characteristics and properties of modified zeolite through
streams. advanced characterisations using field emission-scanning electron
At present, there are various wastewater treatment methods microscopy (FE-SEM), Fourier-transformed infrared spectroscopy
available for the proper treatment and removal of synthetic dyes (FTIR) and BrunauereEmmetteTeller (BET) specific surface area
from wastewater sources, such as anaerobic digestion, membrane and porosity measurements. A batch adsorption study was carried
separation, adsorption (Vimonses et al., 2010; Toor et al., 2015), out using the modified zeolite adsorbents, in order to evaluate for
sedimentation, filtration and photocatalysis (Hameed et al., 2007; the highest removal efficiency of MB under varying adsorption
Chong et al., 2015). Anaerobic digestion (AD) occurs in the conditions of: pH, initial MB concentration and modified zeolite
absence of oxygen, whereby large amounts of organic matter are loading. The adsorption data were analysed and modelled using
broken down into fundamentally carbon dioxide. AD demands low Langmuir, Freundlich, Redlich-Peterson and Koble-Corrigan
energy input while having a minimal sludge formation and nutri- isotherm models, in addition adsorption kinetics were evaluated
ents demand for its microbial processes. Although AD is an using pseudo-first and pseudo-second order models. Through this
attractive method due to the low energy requirement, the presence study, it is anticipated that a facile and cost-effective physico-
of inhibitory substances (i.e., phenolic compounds) are toxic and chemical method can be determined to enhance the adsorption
hinder the activities of vital constituents of the AD process, such as performance of natural zeolite in promoting it as a low-cost and
methanogenic bacteria (Jime
nez et al., 2003). On the other hand, alternative adsorbent for wastewater treatment.
the membrane bioreactor (MBR) is another widely used waste-
water treatment method for the removal of synthetic dyes from 2. Materials and methods
wastewater sources. This is due to the high reliability of MBR
operation, which is independent of solid and hydraulic loads, low 2.1. Materials
space requirements, as well as producing high-quality treated ef-
fluents (Laera et al., 2011). However, it is known that MBR is subject Natural zeolite (particle size < 45 mm, catalogue no.: 1318-02-1,
to high operational cost due to the cross-flow along the membrane SigmaeAldrich) was subjected to four different physicochemical
and required pressure gradient for optimum removal efficiency modification methods, as proposed in this study. MB (catalogue no.:
(Busch et al., 2007). Thus far, adsorption using activated carbon (AC) 440167-09087, HmbG Chemicals) was prepared to the experi-
is the most common and effective wastewater treatment method mental concentrations by dissolving the solid dye powder in
(Akgül and Karabakan, 2011). This is due to the large specific sur- aliquot volume of deionised water. Hydrochloric acid (HCl) 37%
face area to volume ratio of AC. However, the effective adsorption (catalogue no.: H8040-1-2500, Friendemann Schmidt) and sodium
using AC comes at the expense of material, treatment and regen- hydroxide (NaOH) pellets (catalogue no: S5158-1-1000, Friend-
eration costs (Gupta and Suha, 2009). emann Schmidt) were prepared accordingly in deionised water, as
Previously, various alternative adsorbents such as rice husk ash the pH corrective chemicals.
(Liu et al., 2012), sawdust (Shukla et al., 2002), industrial waste (Ali MB is a cationic dye and is also classified as a heterocyclic aro-
et al., 2012; Crini, 2006), and natural clays (Yan et al., 2009; matic chemical compound (Jamil et al., 2011). Supplementary Fig. 1
Cantuaria et al., 2016) have been investigated for their potential shows the molecular structure of MB, with the molecular formula
applications in the removal of synthetic dyes from wastewater of C16H18N3SCl. Despite the variety of applications of MB in the
sources. Among all, natural clays have proven to have a high biology and chemistry fields, it has been reported that the presence
potential to be used as adsorbents in wastewater treatment due to of MB could cause harm to human health and the environment
the fact that they are naturally abundant and environmental (Valde
s et al., 2012; Wang et al., 2005). Thus, the removal of MB
friendly. Zeolite is a type of naturally abundant clay adsorbent that from wastewater sources before environmental discharge is of
has a high potential to be used as a low-cost and alternative to AC paramount importance to ensure a healthy ecosystem. In this study,
adsorbent in wastewater treatment. Typically, zeolite has a rela- MB was chosen as the surrogate indicator for treatment efficiency
tively lower specific surface area (SSA) but pore structure of mo- due to its positively charged surface, which could readily be drawn
lecular dimensions, high thermal stability that permits towards the anionic layers of zeolite. This made MB suitable for the
regenerative uses and the ability to host strong Bronsted and Lewis evaluation of adsorption performance in modified zeolites (Gürses
acid sites compared to AC adsorbent (Tarach et al., 2014). However, et al., 2006).
the adsorption performance of natural zeolite in the removal of
synthetic dyes from wastewater sources is limited by its micropore 2.2. Physicochemical methods for modification of natural zeolite
structure as the dye molecules are usually bulky and measure over
1 nm in size (Yan et al., 2009). Previously, Christensen et al. (2007) Different aqueous HCl solutions with concentrations of 0.05 M,
reported that the adsorption of dyes on natural zeolite is highly 0.1 M, 0.3 M, 0.4 M and 0.5 M were prepared. In order to carry out
restricted by its diffusional limitations. In order to enhance the the AT method, natural zeolite was mixed with the acid solution in
adsorption performance of natural zeolite, previous studies have the ratio of 1:10 (g zeolite:mL acid). A magnetic stirrer was used to
attempted various modification approaches such as using acid mix the sample mixture solution for 20 min at 300 rpm. The AT was
pre-treatment, surfactant modification and thermal activation on terminated by adding a large amount of deionised water. The
natural zeolite (Li et al., 2011; Le Van Mao et al., 1997). All these sample mixture solution was then filtered using a vacuum filtration
studies have shown considerably positive results in terms of pump set. The filtrate samples were washed repeatedly with
enhancing the adsorption performance of natural zeolite. deionised water until neutral pH was obtained. Finally, the filter
The main aim of this study was to evaluate different facile and cake was left to dry at 60  C for 12 h before being stored in a
cost-effective physicochemical methods in enhancing the desiccator.

Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13 3

Different aqueous NaOH solutions with concentrations of 0.1 M, 2.5. Analytical method and error analysis
2 M, 3 M, 4 M and 5 M were prepared. In order to perform the BT
method, natural zeolite was mixed with the base solution in the Since the MB concentration was determined colorimetrically, a
ratio of 1:10 (g zeolite:mL base). A magnetic stirrer was used to mix calibration curve between the measured absorbance values at
the sample mixture solution for 20 min at 300 rpm. The BT was lmax ¼ 668 nm and concentrations of stock MB solution was
terminated by adding a large amount of deionised water. The established. This was to enable a quick estimation of the attenuated
sample mixture solution was then filtered using a vacuum filtration MB concentrations over time. The percentage (%) removal of MB
pump set. The filtrate samples were washed repeatedly using and the amount of MB uptake per unit of modified zeolite adsor-
deionised water until neutral pH was obtained. Finally, the filter bent (q) were estimated using the Eqs. (1) and (2):
cake was left to dry at 60  C for 12 h before being stored in a
desiccator. %MB removal ¼ ðCi  Ce Þ  100=Ci (1)
The combined treatment was performed by heating 2 g each of
AT and BT modified zeolites to the desired thermal treatment q ¼ ðCi  Ce Þ  V=m (2)
temperature of 200  C and 400  C, respectively. The temperature
rate during the thermal treatment was set at 10  C/min and where Ci is the initial MB concentration (mg/L), Ce is the MB
maintained at the desired temperature for 10 min. The thermally concentration at adsorption equilibrium (mg/L), V is the volume of
treated samples were left to cool and stored in a desiccator. MB solution (mL) and m is the mass of modified zeolite adsorbent
used (g).
Furthermore, the Chi-squared (c2) test was used to analyse the
errors in experimental data. Typically, the Chi-squared test was
2.3. Characterisation of modified zeolites conducted to identify the inherent bias due to the linearisation of
the isotherm model. Chi-squared is calculated according to Eq. (3):
FE-SEM images were obtained using the Hitachi SU8010 elec- X .
tron microscope at an accelerating voltage of 5 kV, in order to c2 ¼ ðqee  qec Þ2 qec (3)
measure and observe the particle size and morphology of the
modified zeolites. BET specific surface area and porosity measure- where qee is the equilibrium capacity of modified zeolite adsorbent
ments of modified zeolites were carried out using adsorption iso- obtained from experiments (mg/g) and qec is the calculated equi-
therms obtained from the Micromeritics BET ASAP 2020 surface librium capacity according to the dynamic model (mg/g). A low
area and porosity analyser at 77 ± 0.5 K in liquid nitrogen and by value of Chi-squared indicates the experimental data fitted better
using the BET equation. The sample vessels containing modified to the isotherm model. In order to confirm and validate the best-fit
zeolites were degassed at high temperatures overnight before isotherm and kinetic model for modified zeolite adsorption, it is
being analysed for SSA, pore size and volume. FTIR spectroscopy necessary to analyse the experimental data set using the combined
was used to understand the impact of physicochemical methods on Chi-squared test with the correlation coefficient (R2).
the surface chemistry of modified zeolites. The FTIR spectra were
collected and recorded in the region of 500e4000 cm1. Prior to the 2.6. Adsorption isotherms
analysis, the modified zeolite samples were placed in an oven for
2 h at 60  C and kept in a desiccator while cooling down in order to Adsorption isotherm represents the equilibrium relationship
prevent contact with humidity in the surrounding air. between the amount of adsorbate in adsorbed and solution phases,
respectively. In addition, it is also useful in determining the affinity
of an adsorbate for a particular adsorbent as well as estimating its
adsorption capacity. In this study, four different isotherm models
2.4. Batch adsorption experiments were investigated for representing the adsorption data including
Langmuir, Freundlich, Redlich-Peterson and Koble-Corrigan models
100 ppm stock solution of MB was prepared by dissolving 0.1 g (Han et al., 2009).
of MB powder in 1 L of deionised water. The stock solution was Langmuir isotherm is the most straightforward and useful
diluted subsequently to obtain the desired concentrations of MB isotherm for physical and chemical adsorption types. This isotherm
solution for batch adsorption experiments. Unless specified other- model assumes a homogeneous surface with no interaction
wise, the batch adsorption experiment was generally carried out at between adsorbate molecules, presence of dynamic equilibrium
modified zeolite loading of 0.6 g, neutral pH, room temperature of between adsorption and desorption, and the maximum adsorption
25  C and 18 ppm MB solution. During the batch adsorption analogous to a complete monolayer (Vafajoo et al., 2014). The
experiments, the MB solution was added and agitated with modi- saturated monolayer isotherm model can be expressed in Eq. (4):
fied zeolite adsorbent at a constant speed of 200 rpm. Each set of
data was collected over a period of 120 min, whereby aliquots of qm KL Ce
qe ¼ (4)
samples were taken at 1, 5, 9, 13, 17, 21, 40, 60, 80, 100 and 120 min. 1 þ KL Ce
At each sampling interval, the extracted samples were centrifuged
using a micro centrifuge at 13,500 rpm for 4 min. The supernatant where qe is the amount of MB adsorbed onto per unit mass of
was then extracted using a micropipette to be tested for its absor- modified zeolite (mg/g), qm is maximum adsorption capacity at
bance using the UVeVis spectrophotometer at the MB character- monolayer (mg/g), KL is the Langmuir adsorption constant (L/mg)
istic monochromatic wavelength (lmax) of 668 nm. For the studies related to the binding sites affinity and energy of adsorption and Ce
on the effects of pH, initial MB concentration and modified zeolite is the equilibrium concentration (mg/L).
loading, one adsorption parameter was varied while the remaining From previous studies, it was known that the separation factor
parameters remain unchanged. All the batch adsorption experi- (RL) is crucial in determining the suitability of Langmuir isotherm
ments were carried out in triplicate and the average values were model to model the adsorption process (Yan et al., 2009; Fil et al.,
reported in order to minimise the random experimental and 2012). A value of 0 <RL < 1 indicates that it is a favourable
systematic errors. adsorption process, while RL > 1 shows that it is an unfavourable

Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
4 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13

adsorption, RL ¼ 1 means linear adsorption, and RL ¼ 0 signifies t 1 t

¼ þ (11)
irreversible adsorption. Mathematically, RL can be estimated by qt k2 q2e qe
using Eq. (5):
where k2 is the pseudo-second order rate constant (g mg1 min1).
1
RL ¼ (5)
1 þ KL Ci
3. Results and discussion
where RL is the separation factor (dimensionless), KL is the Lang-
muir adsorption constant (L/mg) and Ci is the initial concentration 3.1. Optimisation of physicochemical methods
of MB (mg/L).
Meanwhile, Freundlich isotherm is an empirical equation that is 3.1.1. Acid and base treatment
derived by assuming a heterogeneous surface with a non-uniform In this study, natural zeolite was treated with HCl and NaOH to
distribution of the heat of adsorption over the surface of adsor- produce AT and BT modified zeolites and subsequently used for
bent. It is commonly expressed as per Eq. (6): batch adsorption studies on the removal of MB dye. The rationale of
acid and base treatment was to enhance the dealumination and
qe ¼ KF Ce
1=n
(6) desilication processes whereby; Al3þ and Si4þ ions were removed
respectively from zeolite leaving behind a structure of high SSA and
where both KF (mg/g) (L/mg) (1/n) and n are the Freundlich con- porosity. In order to determine the optimum concentration of HCl
stants related to the adsorption capacity and intensity of the and NaOH required, the adsorption removal efficiency of MB was
modified zeolite adsorbent used, respectively. measured. This is to ensure the cost-effectiveness of the treatment
The Redlich-Peterson isotherm model is a three-parameter (i.e. minimal amount of HCl and NaOH required in the aqueous
empirical model, which consists of both Langmuir and Freundlich solution). Fig. 1 shows the adsorption removal efficiency of modi-
isotherm models. Due to the versatility of this isotherm model, it fied zeolites that are treated with different HCl and NaOH
can be used for either homogeneous or heterogeneous systems. It concentrations. It was found that the general trend of acid and base
can be represented by Eq. (7): treatment enhanced the adsorption removal efficiency with
increasing concentration until it reached a plateau. From Fig. 1, it
AR Ce can be observed that the maximum adsorption removal efficiencies
qe ¼ (7)
1 þ BR Ceg were achieved when 0.4 M HCl and 4 M NaOH were used during the
acid and base treatment, respectively. The higher adsorption
where AR, BR and g are the Redlich-Peterson isotherm parameters removal efficiency is due to the physical enhancement in specific
and g has a value of 0 < g < 1. surface area as characterised in Section 3.2.2 (Toor et al., 2015).
Another three-parameter isotherm model, the Koble-Corrigan Whilst the decrease in adsorption removal efficiency after the
isotherm model is also used to represent the equilibrium adsorp- plateau is likely attributed to the decrease in specific surface area
tion data in this study. This isotherm model is given in Eq. (8): due to diffusion of HCl and NaOH into the voids, causing extreme
leaching of Al3þ and Si4þ ions respectively. This eventually leads to
AK Ccn the collapse of the layered structure in zeolite and hence results in
qe ¼ (8)
1 þ BK Cen close packing of the particles and a significant reduction of surface
area and adsorption sites (Korichi et al., 2012). Subsequently, the
where AK, BK and n are the Koble-Corrigan isotherm parameters. maximum adsorption removal efficiencies of both AT and BT
This adsorption isotherm model is only valid when the value of n is modified zeolites were compared against the natural zeolite that
greater than 1. was used as a control sample. From Fig. 2, it can be observed that
adsorption removal efficiencies of AT and BT modified zeolites were
significantly enhanced as compared to the natural zeolite sample.
2.7. Kinetic models In this instance, the AT modified zeolite showed a better adsorption
performance than the BT modified zeolite. This could be due to the
Generally adsorption kinetics is the base in determining the duration of acid and base treatment used, whereby the BT modified
performance of a fixed-bed or a flow-through adsorption system. In zeolite might require a longer duration in order for NaOH to
order to determine the rate of MB adsorption on modified zeolites, effectively and adequately leach the Si4þ ions from the zeolite
adsorption kinetic models such as pseudo-first-order and pseudo- structure. Owing to the better adsorption performance and signif-
second-order models can be used (Qiu et al., 2009). The pseudo- icantly reduced requirements in terms of acid concentration and
first order kinetic model is given in Eq. (9): treatment duration, the AT modified zeolite is preferred and proven
to be a cost-effective solution.
dq=dt ¼ k1 ðqe  qt Þ2 (9)
An integrated form of Eq. (9), after applying boundary condi- 3.1.2. Combined acid/base-thermal treatment
tions t ¼ 0 to t ¼ t and qt ¼ 0 to qt ¼ qt is as follows: Previously, it was discovered that thermal pre-treatment only
would contribute to a higher adsorption removal efficiency of
log ðqe  qt Þ ¼ log qe  k1 t=2:303 (10) organic compounds owing to the removal of physisorbed and
chemisorbed water molecules and other bound volatile compounds
where qt is the amount of adsorbate adsorbed at time t (mg/g), qe is (Vimonses et al., 2009a, 2009b). This will contribute directly to a
the adsorption capacity at equilibrium (mg/g), k1 is the zeolite structure with higher SSA and porosity. However, there have
pseudo-first-order adsorption rate constant (min1), and t is the been limited studies that investigated this combined treatment. In
adsorption contact time (min). In this instance, the values of the this study, the combined treatment involving sequential acid and
pseudo-first order adsorption rate constants, k1, were determined base treatment followed by thermal treatment was performed to
from the plot of log (qe e qt) against t. Meanwhile, the pseudo- modify the physicochemical properties of natural zeolite. The
second order kinetic model is given in Eq. (11) as below: resultant ATT and BTT modified zeolites were evaluated for their

Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13 5

Fig. 1. Removal efficiency of zeolites treated by (a) HCl and (b) NaOH. Conditions: zeolite loading 0.6 g; MB concentration 18 ppm; operating temperature 25  C; neutral pH; average
relative error ±5%.

adsorption removal efficiency of MB in the batch adsorption study From Fig. 4, it can be observed that the surface morphology of
and the results are shown in Fig. 3. From Fig. 3, it can be observed that natural untreated zeolite is different when compared to the
the adsorption removal efficiency of AT modified zeolite was higher modified zeolites. The surface morphology of the natural untreated
at 200  C while the highest was observed at 400  C for BT modified zeolite (Fig. 4(a)) appeared to be smooth with regular edges. In
zeolite. However, it was found that the adsorption performance contrast, the surface morphologies of the AT modified zeolites with
obtained after thermal treatment yielded lower removal efficiency different HCl concentrations (Fig. 4(bed)) show a rougher appear-
as compared to the zeolite samples without thermal treatment. ance with worn-out edges. Such an edge modification will poten-
Thus, it can be concluded that the combined treatment within the tially increase the overall specific surface area as well as the pore
range of 200e400  C was unable to enhance the adsorption size and volume of the natural zeolite adsorbent. The impact of acid
performance of ATT and BTT modified zeolite adsorbents. This might treatment on the BET specific surface area, pore size and volume
be due to the insufficient duration and temperature used during was verified in Section 3.2.2. Generally, it was found that the
thermal treatment to alter the zeolite structure. surface roughness increases with HCl concentration whereby this
was also linearly correlated to the increasing removal efficiencies of
3.2. Characterisation of modified zeolites MB during the batch adsorption experiments. On the other hand,
the BT modified zeolites with different NaOH concentrations
3.2.1. Field Emission-Scanning Electron Microscopy (FE-SEM) (Fig. 4(eeg)) were observed to have intermediate surface rough-
Fig. 4 shows the FE-SEM images of the AT, BTT and combined ness between that of natural untreated zeolite and AT modified
ATT and BTT modified zeolite adsorbents investigated in this study. zeolites. In this instance, the surface morphologies of the BT

Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
6 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13

Fig. 2. Comparison of the adsorption performance of natural, AT and BT zeolites based on their MB removal efficiency. Average relative error ±5%.

Fig. 3. Effect of thermal treatment on the MB removal efficiency by modified zeolites. Conditions: zeolite loading 0.6 g; MB concentration 18 ppm; operating temperature 25  C;
neutral pH; average relative error ±5%.

zeolites showed relatively smooth surfaces with a non-distinctive surface area leads to a better adsorption performance for the
change when observed on the FE-SEM images. However, the modified zeolites adsorbents. The impact of higher specific surface
impact of base treatment on the BET specific surface area, pore size area on the adsorption removal efficiency of MB was subsequently
and volume was subsequently quantified in Section 3.2.2 while the investigated and validated in Section 3.3. On the other hand, it was
adsorption removal efficiency of MB is detailed in Section 3.3. observed that the acid treatment actually induced the formation of
Surprisingly, the surface morphologies of combined ATT and BTT mesopores within the natural zeolite. This was evident from the
modified zeolites (Fig. 4(hei)) did not show obvious change when shift in pore size from 1.81 nm (natural zeolite) to 3.09 (AT modified
compared to the FE-SEM images obtained prior to heat treatment. zeolite). Typically, the threshold value for micropores is a diameter
This was well reflected in the adsorption removal efficiencies of MB below 2 nm while the mesopore has a diameter between the range
in Section 3.3. of 2 nm and 50 nm. Similarly, the base treatment also induced the
formation of mesopores in natural zeolite but to a less profound
effect, where the pore size was only shifted from 1.81 nm to
3.2.2. BrunauereEmmetteTeller (BET) 2.06 nm. The formation of mesopores within natural zeolite upon
Table 1 presents BET analysis of the four physicochemical acid and base treatment are linked to the dealumination and
modified types of zeolites, namely AT, BT, ATT and BTT as well as the desilication processes, respectively (Akgül and Karabakan, 2011).
natural zeolite as sample control. From the results presented in The increase in pore size also facilitates the adsorption process, as
Table 1, it can be observed that the specific surface areas of both AT the large MB molecules are able to bind onto the adsorption sites
(21.40 m2/g) and BT (6.50 m2/g) modified zeolites are higher than more easily, and thus improves the adsorption capacity and overall
that of natural zeolite (2.90 m2/g). Generally, the increase in specific adsorption removal efficiency.

Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13 7

Fig. 4. FE-SEM images of natural and modified zeolites: (a) natural zeolite; (b) AT modified zeolite (0.05 M HCl); (c) AT modified zeolite (0.1 M HCl); (d) AT (0.4 M HCl); (e) BT
modified zeolite (0.1 M NaOH); (f) BT modified zeolite (2 M NaOH); (g) BT modified zeolite (4 M NaOH); (h) ATT modified zeolite (0.4 M HCl at 200  C); (i) BTT modified zeolite (4 M
NaOH at 400  C).

Table 1 stretching. It was also observed that there was a strong peak around
BET analysis data for natural and modified zeolites. the wavenumber of 1000 cm1for the natural, acid-treated and
Sample SBET (m2/g)a Vtotal (cm3/g)b DBET (nm)c base-treated zeolites samples. Previously, Korichi et al. (2012) dis-
Natural zeolite 2.90 0.00131 1.81
cussed that this peak is due to the SieO stretch. From Fig. 5, it can be
0.4 M HCl zeolite 21.40 0.00949 3.09 observed that the intensity of SieO stretching was the weakest for
4 M NaOH zeolite 6.50 0.00291 2.06 base-treated zeolite and this indicates that the amount of Si in the
200  C HCl zeolite 22.40 0.01747 3.12 zeolite structure has been reduced due to the desilication process.
400  C NaOH zeolite 7.60 0.00446 2.06
The small peaks around wavenumber 1650 cm1 are linked to the
a
BET surface area. adsorbed water in the zeolite samples. Meanwhile, the impact of
b
Total pore volume. the dealumination process as induced by the acid treatment was
c
Pore size.
evident between wavenumbers of 3000 and 3700 cm1. This is an
OeH stretch with hydrogen-bonded molecules. The broad stretch
in this wavenumber range is attributed to the loosely-bound water
3.2.3. Fourier-Transformed Infrared (FTIR) spectroscopy molecules hydrogen bonded SieOH groups in nest defects due to
FTIR analysis was used to determine the minerals and functional vacancies of Al in the zeolite structure (Garcia-Basabe et al., 2010).
groups that present in the natural and modified zeolite adsorbents.
Fig. 5 shows the FTIR spectra of the natural and modified zeolites in
the range of 500e4000 cm1. The characteristic of zeolite, which 3.3. Adsorption studies
consists of a tetrahedral ring, was reflected by the peaks at the
wavenumber of 550e580 cm1 (Deepesh et al., 2013). A weak peak The adsorption studies were carried out only based on both the
was observed at the wavenumber 670 cm1, indicating AleOeSi AT (0.4 M HCl) and BT (4 M NaOH) modified zeolites adsorbents,

Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
8 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13

Fig. 5. FTIR spectra of natural, AT and BT modified zeolites.

since they possess higher adsorption capacity and removal effi- eventually leads to an overall enhancement in adsorption
ciency than the ATT and BTT modified zeolites as per Section 3.1. performance.

3.3.1. Effect of pH 3.3.2. Effect of zeolite loading

Generally, pH is an important parameter in the batch adsorption In this study, the effect of zeolite loading on the adsorption
study as it is capable of influencing the adsorption process through capacity was evaluated by varying the dosages of both AT and BT
changes in the surface charge distribution of adsorbents used modified zeolites used between 0.2 g and 1.5 g. From Fig. 7(a), it can
(Li et al., 2013). In this study, the effect of pH on the adsorption of be observed that the adsorption removal efficiency increased from
MB using both AT and BT modified zeolites was investigated in the 95.3% to 99.25% when the AT modified zeolite dosage was increased
range of pH 3 to pH 11. Fig. 6 shows the effect of pH on the from 0.2 g to 1.5 g. In this instance, the increase in adsorption
adsorption removal efficiency of MB using both AT and BT modified removal efficiency is likely attributed to the presence of more
zeolite adsorbents. From Fig. 6(a), it can be seen that there is an adsorption sites (Alver and Metin, 2012; Liu et al., 2014). Whilst
increasing trend in the adsorption removal efficiency of MB when Fig. 7(a) also shows that the adsorption capacity of AT modified
pH increases from pH 3 to pH 11. Initially, there was a distinct zeolite adsorbent decreased with increasing zeolite loading. This is
increase in the adsorption removal efficiency of MB from 82.5% (at possibly the consequence of agglomeration of AT modified zeolite
pH 3) to 97.4% (at pH 5). Thereafter, there was only a small increase particles when high dosage was utilised (Li et al., 2011).
in the adsorption removal efficiency of MB from pH 5 up to the Similarly, the BT modified zeolite adsorbent also experienced an
maximum of 99.6% (at pH 11). Similarly, the BT modified zeolites increase in the adsorption removal efficiency when the dosage was
also exhibit an increasing trend in the adsorption removal increased from 0.2 g to 1.5 g. In this instance, however, the increase
efficiency of MB when the pH increases from pH 3 to pH 11 in the adsorption removal efficiency by BT modified zeolite adsor-
(Fig. 6(b)). In this instance, the adsorption removal efficiency of MB bent was more significant from 16.9% to 85.5%. This indicated that
was seen to increase from 47.4% (at pH 3) to the maximum of 54.3% the BT modified zeolite adsorbent is more dependent on the zeolite
(at pH 11). loading as compared to the AT modified zeolite adsorbent. As
Previously, Sohrabnezhad and Pourahmad (2010) also reported shown in Fig. 7(b), the adsorption capacity of BT modified zeolite
such an increasing trend in the adsorption removal efficiency of MB adsorbent increased from 0.720 mg/g to 0.788 mg/g when the
whereby both the AT and BT modified zeolite adsorbents have zeolite loading was increased from 0.2 g to 0.4 g, before dropping
shown better adsorption performance at higher pH conditions. This abruptly to 0.487 mg/g when 1.5 g of zeolite was used. The initial
is mainly attributed to the cationic nature of the MB dye. In acidic increase in adsorption capacity is likely due to the considerable
medium (pH < 7), there will be excess Hþ ions present in the differences in the amount of dye removed when the zeolite loading
solution to compete for the available adsorption sites with the was increased from 0.2 g to 0.4 g. Thus, the optimum loading for BT
cationic MB dye molecules and thus, decreasing the dye uptake on modified zeolite adsorbent was found at 0.4 g loading as it led to
the modified zeolite adsorbents (Sohrabnezhad and Pourahmad, more than the doubling of adsorption removal efficiency without
2010). In addition, the presence of Hþ ions will also protonate the compromising the adsorption capacity.
surface of modified zeolites and this would lead to electrostatic
repulsion between the positively-charged surface of modified 3.3.3. Effect of initial MB concentration
zeolites and the cationic MB dye molecules (Fil et al., 2012). On the In this study, the effect of initial MB concentration on the
contrary, the surface of modified zeolites will be deprotonated in an adsorption capacity of AT and BT modified zeolites was examined
alkaline medium (pH > 7). This is due to the decrease in positive by varying the initial MB concentration between 5 ppm and
charge density on the adsorption edges caused by the increase in 20 ppm. Fig. 8(a) and (b) show the general trend is such that the
the number of hydroxyl groups (Fil et al., 2012). This results in a adsorption capacity increases with the increase in the initial MB
strong electrostatic attraction between the negatively charged concentration. Such an observation is likely attributed to the
modified zeolites with positively charged MB molecules, which accelerated diffusion of MB molecules onto the modified zeolites

Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13 9

Fig. 6. Effect of pH on adsorption removal efficiency of MB using: (a) AT modified zeolite and (b) BT modified zeolite. Conditions: zeolite loading 0.6 g; MB concentration 18 ppm;
operating temperature 25  C; average relative error ±5%.

due to the increase in concentration gradient between MB mole- used to evaluate the adsorption systems utilising various
cules and zeolite adsorbents (Vimonses et al., 2009b; Liu et al., physicochemical-modified zeolite adsorbents.
2010). It can be proposed that an increase in the initial MB Generally, an adsorption isotherm model is distinguished by the
concentration would lead to an eventual increase in adsorption respective parameters in the model that indicate the affinity and
capacity due to the driving force of increasing concentration surface properties of a particular adsorbent used (Han et al., 2009).
gradient, causing an increase in mass transfer of MB molecules onto Table 2 shows the parameters for each adsorption isotherm model
the surface of both AT and BT modified zeolite adsorbents (Han evaluated, together with the computed c2 values. The Langmuir
et al., 2009). isotherm model is based on the assumption that all adsorption sites
are alike and equally energetic, making the surface homogeneous
3.4. Adsorption isotherms and kinetic modelling (Vimonses et al., 2009b). Whilst the Langmuir constant (qm)
represents monolayer saturation at equilibrium when the adsor-
3.4.1. Adsorption isotherms bent surface is covered by dye molecules and helps to explain the
In order to evaluate the different physicochemical methods in adsorption performance. From the fitting of experimental data
enhancing the adsorption performance of natural zeolite, it using the Langmuir isotherm, it was found that there were differ-
necessitates a similar equilibrium condition to provide a better ences between the model-fitted and experimentally measured
comparison and understanding of the adsorption process. For this adsorption capacities. These differences could be due to the steric
study, four different adsorption isotherm models of Langmuir, hindrance originating from the bulky size of MB molecules (Alver
Freundlich, Redlich-Peterson and Koble-Corrigan models were and Metin, 2012). The other Langmuir constant (KL) is used to

Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
10 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13

Fig. 7. Effect of zeolite loading on the removal efficiency and the adsorption capacity (mg/g) of: (a) AT modified zeolite and (b) BT modified zeolite. Conditions: initial MB con-
centration 18 ppm; neutral pH; operating temperature 25  C; average relative error ±10%.

indicate the affinity of dye molecules for the adsorbents used, approaching that of the Langmuir isotherm model. Meanwhile, the
whereby a lower KL value dictates lower affinity and vice versa. It Koble-Corrigan isotherm model is exponentially dependent to the
was found that the affinity of MB molecules for AT modified zeolite equilibrium concentration. According to the c2 values in Table 2, it
was significantly higher than that of BT modified zeolite. The sep- was shown that the Koble-Corrigan isotherm model was best
aration factor (RL) for both AT and BT modified zeolites were correlated to the experimental data. In this instance, the c2 value
computed to be within the favourable range of 0 < RL < 1. This obtained for this model was the lowest among the evaluated
validated a favourable adsorption process of MB removal using adsorption isotherm models, indicating the least deviation
physicochemical-modified zeolite adsorbents. between the model-fitted and experimental-measured adsorption
On the other hand, the Freundlich isotherm model is usually capacities. Thus, this confirmed that the Koble-Corrigan isotherm
used to describe a heterogeneous adsorption system. From this model provided the best fit for MB adsorption on AT and BT
study, it was found that the Freundlich constant (KF) for both AT and modified zeolite adsorbents.
BT modified zeolites was in the range of 0.3e1.6. In addition, it was
also found that one of the Freundlich parameters (1/n) had values 3.4.2. Adsorption kinetics
within the range of 0.39e0.45 that the isotherm deemed favourable According to Vimonses et al. (2009b), the Lagergren's kinetics
for the experimental data. As for the Redlich-Peterson isotherm equation (i.e., more commonly known as pseudo-first order equa-
model, it can be seen that the g-values for both AT and BT modified tion) is used for the adsorption process in an aqueous solution. It
zeolites were close to unity, indicating that the isotherm was assumes that the solute uptake rate is directly proportional to the

Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13 11

Fig. 8. Effect of initial MB concentration on the adsorption capacity (mg/g) of: (a) AT modified zeolite and (b) BT modified zeolite. Conditions: zeolite loading 0.6 g; neutral pH;
operating temperature 25  C; average relative error ±5%.

Table 2
Adsorption isotherm model parameters and error analysis for the adsorption of MB molecules onto modified zeolites.

Isotherm model Parameters AT modified zeolite BT modified zeolite

Langmuir qm (mg/g) 2.113 1.089

KL (L/mg) 3.032 0.3575
RL 0.0171 0.1275
c2 0.1338 0.07535
(1/n)
Freundlich KF (mg/g)$(L/mg) 1.624 0.3524
1/n 0.449 0.3928
c2 0.1917 0.09589
Redlich-Peterson AR 6.413 0.3898
BR 3.036 0.3589
g 0.999 0.999
c2 0.1339 0.07539
Koble-Corrigan AK 357.51 0.01506
BK 235.8 0.01915
n 3.345 5.968
c2 0.00098 0.00171

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zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
12 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13

Table 3
(a) Pseudo-first order analysis for AT modified zeolite and BT modified zeolite in the adsorption of MB dye. (b) Pseudo-second order analysis for AT modified zeolite and (b) BT
modified zeolite in the adsorption of MB dye. Conditions: zeolite loading 0.6 g; neutral pH; operating temperature 25  C.

MB concentration (ppm) AT modified zeolite BT modified zeolite Experimental data

AT modified zeolite BT modified zeolite

1 1
qec (mg/g) k1 (min ) c2
qec (mg/g) k1 (min ) c2
qex (mg/g) qex (mg/g)

(a) Pseudo-first order kinetic Parameters (R2 ¼ 0.0652e0.12147)

5 0.0783 0.0053 6.0338 0.2121 0.0023 4.8689 0.4127 0.2890
10 0.1768 0.0032 0.1066 0.0053 0.8450 0.6362
15 0.3567 0.0018 0.1952 0.0044 1.2021 0.7592
20 1.2034 0.0018 1.8493 0.0009 1.5033 0.8122
(b) Pseudo-second Order Kinetic Parameters (R2 ¼ 0.99994e1)
5 0.4106 116.5356 0.00012 0.2845 322.6825 0.00048 0.4127 0.2890
10 0.8382 21.9299 0.6316 41.2936 0.8450 0.6362
15 1.1962 110.9359 0.7555 48.0050 1.2021 0.7592
20 1.4972 446.0904 0.7953 21.9591 1.5033 0.8122

difference between saturation concentration and the amount of performance. Following the physicochemical methods, batch
solid uptake with time. Table 3(a) shows the pseudo-first order adsorption studies were carried out to evaluate the highest removal
analysis for AT and BT modified zeolites in the adsorption of MB efficiency of MB under varying adsorption conditions of: pH, initial
dye. From the table, it is apparent that the pseudo-first order model MB concentration and modified zeolite loading. Results showed
provides a poor fitting for the experimental data obtained by that the AT modified zeolite (using 0.4 M HCl) and BT modified
varying the initial MB concentration between 5 ppm and 20 ppm. It zeolite (using 4 M NaOH) are capable of enhancing the adsorption
can also be observed that the computed equilibrium adsorption capacity of natural zeolite from 41% to 98.8% and 52.2%, respec-
capacities based on the kinetic model were not acceptable, as they tively. The fitting of adsorption data to isotherm and kinetic models
were essentially lower than that of the experimental data. These showed that the data were best represented using the Koble-
disparities are further substantiated by lower R2 values of Corrigan and pseudo-second order models. Owing to the better
0.06e0.12, and higher c2 values ranging from 4 to 6 for both AT and adsorption performance and significantly lesser requirements in
BT modified zeolites. Therefore, it is validated that the adsorption of terms of acid concentration and treatment duration, the AT modi-
MB on both AT and BT modified zeolites does not follow the fied zeolite is preferred and proven to be a cost-effective solution to
pseudo-first-order model in all the studied cases. be used as low-cost adsorbent for wastewater treatment.
This kinetic model is applicable through the assumption that the
overall adsorption rate is limited by the rate of adsorbate diffusion
in the adsorbent pores (Plazinski et al., 2013). Table 3(b) shows the Acknowledgement
pseudo-second order analysis for AT and MT modified zeolites.
From the table, it can be observed that the experimental data fit to The authors are grateful to the financial support from the
the pseudo-second order kinetic model for both AT and BT modified Chemical Engineering Discipline, School of Engineering, Monash
zeolites. It was found that the experimental data were perfectly University Malaysia. Similar gratitude also goes to the Advanced
fitted to this model, as supported by exceptionally high R2-values of Engineering Platform (AEP), Monash University Malaysia. In addi-
greater than 0.9999, as well as insignificant c2 values that are lower tion, the authors are also highly indebted to the endless assistance
than 0.0005. The fitting of experimental data to the pseudo-second given by the Subject Editor, Dr. Krzysztof Urbaniec, on improving
order kinetics model implies that the adsorption mechanism re- the quality of the manuscript.
volves around the adsorbate and adsorbent (Vimonses et al.,
2009a).
Appendix A. Supplementary data

Supplementary data related to this article can be found at http://

4. Conclusion
dx.doi.org/10.1016/j.jclepro.2016.01.056.
Through this study, it was found that simple physicochemical
methods of treating natural zeolite with acid, base and combined References
thermal treatment are capable of enhancing its adsorption capacity
and therefore its removal efficiency. From the optimisation studies Akgül, M., Karabakan, A., 2011. Promoted dye adsorption performance over desili-
involving different physicochemically modified zeolite adsorbents cated natural zeolite. Micro. Meso. Mater 145, 157e164.
Ali, I., Asim, M., Khan, T.A., 2012. Low cost adsorbents for the removal of organic
of AT, BT, ATT and BTT types, it was found that both the AT and BT pollutants from wastewater. J. Environ. Manage 113, 170e183.
modified zeolites are far superior to those involving combined Alver, E., Metin, A.Ü., 2012. Anionic dye removal from aqueous solutions using
acid/base and thermal treatment (i.e. ATT and BTT modified zeo- modified zeolite: adsorption kinetics and isotherm studies. Chem. Eng. J.
200e202, 59e67.
lites). Further understanding on the impact of acid and base Busch, J., Cruse, A., Marquardt, W., 2007. Modeling submerged hollow-fiber
treatments on the surface characteristics and properties of AT and membrane filtration for wastewater treatment. J. Membr. Sci. 288, 94e111.
BT modified zeolites were achieved through advanced characteri- Cantuaria, M.L., de Almeida Neto, A.F., Nascimento, E.S., Vieira, M.G.A., 2016.
Adsorption of silver from aqueous solution onto pre-treated bentonite clay:
sation using FE-SEM, FTIR and BET measurements. It was found that
complete batch system evaluation. J. Clean. Prod. 112, 1112e1121.
acid treatment was more effective than base treatment in Chong, M.N., Jin, B., Zhu, H., Saint, C., 2010. Bacterial inactivation kinetics, regrowth
increasing the overall BET specific surface area of up to 21.40 m2/g, and synergistic competition in a photocatalytic disinfection system using
as well as the formation of mesopores with diameter range of anatase titanate nanofiber catalyst. J. Photochem. Photobiol. A 214, 1e9.
Chong, M.N., Jin, B., Saint, C.P., 2011a. Bacterial inactivation kinetics of a photo-
2 nme50 nm for AT modified zeolite. These physical changes are disinfection system using novel titania-impregnated kaolinite photocatalyst.
found to be strongly correlated to the enhancement in adsorption Chem. Eng. J. 171, 16e23.

Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056
 K.Y. Hor et al. / Journal of Cleaner Production xxx (2016) 1e13 13

Chong, M.N., Jin, B., Laera, G., Saint, C.P., 2011b. Evaluating the photodegradation of Liu, Y., Zheng, Y., Wang, A., 2010. Enhanced adsorption of Methylene Blue from
Carbamazepine in a sequential batch photoreactor system: impacts of effluent aqueous solution by chitosan-g-poly (acrylic acid)/vermiculite hydrogel
organic matter and inorganic ions. Chem. Eng. J. 174, 595e602. composites. J. Environ. Sci. 22, 486e493.
Chong, M.N., Tneu, Z.Y., Poh, P.E., Jin, B., Aryal, R., 2015. Synthesis, characterisation Liu, Y., Guo, Y., Gao, W., Wang, Z., Ma, Y., Wang, Z., 2012. Simultaneous preparation
and application of TiO2-zeolite nanocomposites for the advanced treatment of of silica and activated carbon from rice husk ash. J. Clean. Prod. 32, 204e209.
industrial dye wastewater. J. Taiwan. Inst. Chem. Eng. 50, 288e296. Malik, O.A., Hsu, A., Johnson, L.A., De Sherbinin, A., 2015. A global indicator of
Christensen, C.H., Johannsen, K., Tornqvist, E., Schmidt, I., Topsoe, H., wastewater treatment to inform the Sustainable Development Goals (SDGs).
Christensen, C.H., 2007. Mesoporous zeolite single crystal catalysts: diffusion Environ. Sci. Policy 48, 172e185.
and catalysis in hierarchical zeolites. Catal. Today 128, 117e122. Plazinski, W., Dziuba, J., Rudzinski, W., 2013. Modeling of sorption kinetics: the
Crini, G., 2006. Non-conventional low-cost adsorbents for dye removal: a review. pseudo-second order equation and the sorbate intraparticle diffusivity.
Biores. Technol. 97, 1061e1085. Adsorption 19, 1055e1064.
Deepesh, B., Radha, T., Purnima, K.S., Yogesh, G., Pankaj, S., 2013. Hydrothermal Qiu, H., Lu, L., Pan, B.-C., Zhang, Q.-J., Zhang, W.-M., Zhang, Q.-X., 2009. Critical
synthesis and characterization of zeolite: effect of crystallization temperature. review in adsorption kinetic models. J. Zhejiang Uni. Sci. A 10, 716e724.
Res. J. Chem. Sci. 3, 1e4. Reddy, B.S., Veni, V.K., Ravindhranath, K., 2012. Removal of methylene blue dye
€
Fil, B.A., Ozmetin, C., Korkmaz, M., 2012. Cationic dye (Methylene blue) removal from waste waters using new bio-sorbents derived from Annona squamosa and
from aqueous solution by Montmorillonite. Bull. Korean. Chem. Soc. 33, Azadiracta indica plants. J. Chem. Pharma. Res. 4, 4682e4694.
3184e3190. Robinson, T., Mcmullan, G., Marchant, R., Nigam, P., 2001. Remediation of dyes in
Garcia-Basabe, Y., Rodriguez-Iznaga, I., De Menorval, L.-C., Llewellyn, P., Maurin, G., textile effluent: a critical review on current treatment technologies with a
Lewis, D.W., Binions, R., Autie, M., Ruiz-Salvador, A.R., 2010. Step-wise deal- proposed alternative. Biores. Technol. 77, 247e255.
umination of natural clinoptilolite: structural and physicochemical character- Shukla, A., Zhang, Y.-H., Dubey, P., Margrave, J.L., Shukla, S.S., 2002. The role of
ization. Micro. Meso. Mater 135, 187e196. sawdust in the removal of unwanted materials from water. J. Hazard. Mater 95,
Gupta, V.K., Suha, S., 2009. Application of low-cost adsorbents for dye removal e a 137e152.
review. J. Environ. Manage 90, 2313e2342. Sohrabnezhad, S., Pourahmad, A., 2010. Comparison absorption of new methylene
Gürses, A., Dogar, Ç., Yalcin, M., Acikyildiz, M., Bayrak, R., Karaca, S., 2006. The blue dye in zeolite and nanocrystal zeolite. Desal 256, 84e89.
adsorption kinetics of the cationic dye, methylene blue, onto clay. J. Hazard. Tarach, K., Gora-Marek, K., Tekla, J., Brylewska, K., Datka, J., Mlekodaj, K.,
Mater 131, 217e228. Makowski, W., Igualada Lopez, M.C., Martinez Triguero, J., Rey, F., 2014. Catalytic
Hameed, B.H., Ahmad, A.A., Aziz, N., 2007. Isotherms, kinetics and thermodynamics cracking performance of alkaline-treated zeolite Beta in the terms of acid sites
of acid dye adsorption on activated palm ash. Chem. Eng. J. 133, 195e203. properties and their accessibility. J. Catal. 312, 46e57.
Han, R., Zhang, J., Han, P., Wang, Y., Zhao, Z., Tang, M., 2009. Study of equilibrium, Toor, M., Jin, B., Dai, S., Vimonses, V., 2015. Activating natural bentonite as a cost-
kinetic and thermodynamic parameters about methylene blue adsorption onto effective adsorbent for removal of Congo-red in wastewater. J. Ind. Eng.
natural zeolite. Chem. Eng. J. 145, 496e504. Chem. 21, 653e661.
Jamil, T.S., Abdel Ghafar, H.H., Ibrahim, H.S., Abd El-Maksoud, I.H., 2011. Removal of Vafajoo, L., Ghanaat, F., Ghalebi, A., 2014. An investigation of a petrochemical
methylene blue by two zeolites prepared from naturally occurring Egyptian wastewater treatment utilizing GAC: a study of adsorption kinetics. APCBEE
kaolin as cost effective technique. Solid. State. Sci. 13, 1844e1851. Procedia 10, 131e135.
Jime
nez, A.M., Borja, R., Martin, A., 2003. Aerobiceanaerobic biodegradation of beet Valde
s, H., Tardon, R.F., Zaror, C.A., 2012. Role of surface hydroxyl groups of acid-
molasses alcoholic fermentation wastewater. Process. Biochem. 38, 1275e1284. treated natural zeolite on the heterogeneous catalytic ozonation of methylene
Korichi, S., Elias, A., Mefti, A., Bensmaili, A., 2012. The effect of microwave irradia- blue contaminated waters. Chem. Eng. J. 211e212, 388e395.
tion and conventional acid activation on the textural properties of smectite: Vimonses, V., Lei, S., Jin, B., Chow, C.W.K., Saint, C., 2009a. Adsorption of congo red
comparative study. Appl. Clay. Sci. 59e60, 76e83. by three Australian kaolins. Appl. Clay. Sci. 43, 465e472.
Laera, G., Chong, M.N., Jin, B., Lopez, A., 2011. An integrated MBR-TiO2 photo- Vimonses, V., Lei, S., Jin, B., Chow, C.W.K., Saint, C., 2009b. Kinetic study and equi-
catalysis process for the removal of Carbamazepine from simulated pharma- librium isotherm analysis of Congo Red adsorption by clay materials. Chem.
ceutical industrial effluent. Biores. Technol. 102, 7012e7015. Eng. J. 148, 354e364.
Le Van Mao, R., Le, S.T., Ohayon, D., Caillibot, F., Gelebart, L., Denes, G., 1997. Vimonses, V., Chong, M.N., Jin, B., 2010. Evaluation of the physical properties and
Modification of the micropore characteristics of the desilicated ZSM-5 zeolite photodegradation ability of titania nanocrystalline impregnated onto modified
by thermal treatment. Zeolites 19, 270e278. kaolin. Micro. Meso. Mater 132, 201e209.
Li, C., Dong, Y., Wu, D., Peng, L., Kong, H., 2011. Surfactant modified zeolite as Wang, S., Zhu, Z.H., Coomes, A., Haghseresht, F., Lu, G.Q., 2005. The physical and
adsorbent for removal of humic acid from water. Appl. Clay Sci. 52, 353e357. surface chemical characteristics of activated carbons and the adsorption of
Li, Y., Du, Q., Liu, T., Sun, J., Wang, Y., Wu, S., Wang, Z., Xia, Y., Xia, L., 2013. Methylene methylene blue from wastewater. J. Colloid. Interface. Sci. 284, 440e446.
blue adsorption on graphene oxide/calcium alginate composites. Carbohyd. Yan, C., Wang, C., Yao, J., Zhang, L., Liu, X., 2009. Adsorption of methylene blue on
Polym. 95, 501e507. mesoporous carbons prepared using acid- and alkaline-treated zeolite X as the
Liu, S., Ding, Y., Li, P., Diao, K., Tan, X., Lei, F., Zhan, Y., Li, Q., Huang, B., Huang, Z., template. Colloid. Surf. A 333, 115e119.
2014. Adsorption of the anionic dye Congo red from aqueous solution onto Zhou, K., Zhang, Q., Wang, B., Liu, J., Wen, P., Gui, Z., Hu, Y., 2014. The integrated
natural zeolites modified with N,N-dimethyl dehydroabietylamine oxide. Chem. utilization of typical clays in removal of organic dyes and polymer nano-
Eng. J. 248, 135e144. composites. J. Clean. Prod. 81, 281e289.

Please cite this article in press as: Hor, K.Y., et al., Evaluation of physicochemical methods in enhancing the adsorption performance of natural
zeolite as low-cost adsorbent of methylene blue dye from wastewater, Journal of Cleaner Production (2016), http://dx.doi.org/10.1016/
j.jclepro.2016.01.056