Materials and Design 101 (2016) 210–217

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Materials and Design

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

Nitrophenols removal from aqueous medium using Fe-nano

mesoporous zeolite
Pham-Thi Huong, Byeong-Kyu Lee ⁎, Jitae Kim, Chi-Hyeon Lee
Department of Civil and Environmental Engineering, University of Ulsan, Nam-gu, Ulsan 680-749, Republic of Korea

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

Article history: In this study, Fe-nano zeolite was applied to the removal of ortho, meta and para-nitrophenols to evaluate its po-
Received 14 November 2015 tential applications as an effective adsorbent. Scanning electron microscopy, Fourier-transformed infrared spec-
Received in revised form 28 March 2016 troscopy, and gas adsorption analysis were used to compare the advanced properties of Fe-nano zeolite with
Accepted 7 April 2016
those of commercial activated carbon (AC). The Fe-nano zeolite with a greatly improved surface area was partic-
Available online 9 April 2016
ularly effective in the removal of the nitrophenols. The maximum adsorption capacity of m-, o- and p-nitrophenol
Keywords:
were 168.7, 193.9 and 223.1 mg/g, respectively. These adsorbents were applied to the remediation of wastewater
Fe-nano zeolite containing high p-nitrophenol concentration of 380 mg/L. The results revealed 92.8% removal efficiency of p-
Economic effect nitrophenol from wastewater by Fe-nano zeolite, which is much higher than those AC (56.5%). The regeneration
Nitrophenols characteristics of the p-nitrophenol-loaded adsorbent were analyzed. Even after 15 adsorption-desorption cycles,
Wastewater the removal efficiencies of p-nitrophenol by Fe-nano zeolite and AC were 78.6 and 57.9%, respectively. The re-
Adsorption quired adsorption cost for the treatment of 1000 kg wastewater containing 380 mg/L of p-nitrophenol using
Regeneration Fe-nano zeolite was 67.6% lower than that using AC. Based on these results, Fe-nano zeolite can be used as eco-
nomic and effective adsorbent for removal of nitrophenols from wastewater.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction there has been increasing interest in the synthesis of nano-crystalline

Nitrophenols are important chemical intermediates that serve as a
precursor for many pharmaceuticals and pesticides [1]. A range of in-
dustries, such as the plastics and paper industries use nitrophenols ex-
tensively in their products. A significant amount of nitrophenols are
commonly present in the effluents of these industries and need to be
treated before being discharged into the environment [2–3].
Many methods are used to remove nitrophenols from wastewater
stream, including advanced oxidation processes for the removal of or-
ganic compounds, chemical oxidation, and adsorption. Among these
techniques, adsorption is used widely because it has easy operation
and simple design requirements [4–6]. Adsorption processes using bio-
logical materials, mineral oxides, and activated carbon (AC), or polymer
resins have been attractive for the effective removal of organic com-
pounds from water systems [7–8]. AC is one of the most commonly
used adsorbents for the adsorption removal of organic pollutants. On
the other hand, the high regeneration and purchase expenses of AC
has prompted many attempts to develop low-cost adsorbents to re-
move toxic organic compounds. Zeolites have been utilized as good ad-
sorbents, molecular sieves, membranes, ion exchangers and catalysts
for municipal and industrial pollution control. Many studies have exam-
ined the use of zeolites to remove organic pollutants [9–15]. Recently,
⁎ Corresponding author.
E-mail address: bklee@ulsan.ac.kr (B.-K. Lee).
zeolites to utilize their favorable properties for environmental treat-
ment [16–19].
The main aim of this study was to evaluate the feasibility of using
synthesized Fe-nano zeolite for removing o-, m- and p-nitrophenol
from water. A range of adsorption parameters were investigated, in-
cluding solution pH, reaction time, adsorbent dose, and initial concen-
tration of pollutants. The adsorption-desorption of nitrophenols in
wastewater containing a high concentration of 380 mg/L using Fe-
nano zeolite and commercial AC were studied.
This study also focused on reducing the adsorption cost for nitrophe-
nol removal in wastewater.
2. Materials and methods
2.1. Material
The commercial activated carbon “Activated Charcoal Norit®;
PCode: 101530190” used in this study was purchased from Daejung
Chemical and Metals Co. LTD., South Korea. Fe-nano zeolite was pre-
pared by mixing of 0.36 g NaOH and 0.152 g sodium aluminate salt in
H2O and aging it for 3 h at 20 °C with magnetic stirring. After adding
6.8 g of silica sol drop-wise, the resulting mixture was stirred at room
temperature for 10 h to produce a homogenous mixture that was then
heated for 12 h at 160 °C under autogenous pressure. The solid product
was centrifuged and washed with deionized water until its pH reached

http://dx.doi.org/10.1016/j.matdes.2016.04.020
0264-1275/© 2016 Elsevier Ltd. All rights reserved.
 P.-T. Huong et al. / Materials and Design 101 (2016) 210–217
4.0. After drying the synthesized nano zeolite, an appropriate amount
was immersed in a 0.3 M Fe(NO3)3 solution to obtain the Fe ion-
doped nano zeolite solid. The resulting solid was recovered by filtration,
washed with distilled water, dried at 50 °C for 12 h. The physical and
chemical properties were characterized and the product was used for
the adsorption experiments [20–21].
2.2. Characterization of adsorbent
Scanning electron microscopy (SEM) was performed using a Hitachi
S-4700 scanning electron microscope. The specific surface area was de-
termined using the Brunauer-Emmett-Teller (BET) method. The Fourier
transform infrared (FTIR) transmittance spectra in the region 4000–
500 cm−1 were recorded on a Perkin–Elmer Nicolet Nexus 470 FTIR
spectrometer at room temperature. The phase structure of the Fe-
nano zeolite was examined by powder X-ray diffraction (XRD, Bruker
AXN) using CuKα radiation, 30 kV/15 mA current and a Kβ-filter over
the 2θ range of 5–80°.
2.3. Adsorption experiments
The adsorption experiments were carried out by agitating 0.5 g of
adsorbent in 100 mL of an o-nitrophenol, m-nitrophenol, and p-
nitrophenol solution at concentrations ranging from 10 to 500 mg/L
and solution pHs (2.0 ≤ pH ≤ 10) with a mechanical shaker rotating at
150 rpm. The solution pH of the reaction mixture was measured using
a pH meter (Orion 5 Star). The adsorption effect of the solution pH
was analyzed by adjusting the pH of the o-nitrophenol, m-nitrophenol,
and p-nitrophenol solutions using 0.1 M HCl and 0.1 M NaOH solutions.
After the adsorption experiments, the samples were removed and fil-
tered using Whatman 45 filter paper. The o-, m- and p-nitrophenol con-
centrations in the supernatant liquid were analyzed by monitoring the
absorbance at 350, 330 and 315 nm, respectively, using a UV–Vis spec-
trophotometer (Model UV 2100).
The Langmuir and Freundlich adsorption isotherms were used to an-
alyze the equilibrium adsorption. The amount of nitrophenols adsorbed
per unit mass of adsorbent at equilibrium was obtained using the fol-
lowing Eq.(1):
Q e ¼ ðCo −Ce Þ  V=W
where V is the volume of the solution (L), Co the initial concentration
(mg/L), Ce is the equilibrium concentration (mg/L), and W is the mass
of the adsorbent (g).
After adding either the Fe-nano zeolite or AC to the wastewater, the
nitrophenol-loaded adsorbents were washed with distilled water be-
fore being treated with 100 mL of 30% C2H5OH for a contact time of
180 min at room temperature 20 ± 1°°C. The percentage desorption
Fig. 1. Scanning electron microscopy of: (A): AC; (B): Fe-nano zeolite.
211
was calculated using the following Eq. (2):
% Desorption ¼ ½ðCe −Cd Þ=Ce Þ  100 ð2Þ
where Cd (mg/L) represents the final nitrophenol concentration identi-
fied in the desorption medium. After desorption, the Fe-nano zeolite
and AC were washed with distilled water and reused for another ad-
sorption cycle.
3. Results and discussion
3.1. Morphology analysis of Fe-nano zeolite and AC
SEM is an extremely useful tool for examining the surface morphol-
ogy and physical state of an adsorbent surface. Fig. 1A and B showed the
differences in surface morphology of AC and Fe-nano zeolite, respective-
ly. The surface morphology of AC consisted mainly of multilayers with a
number of pores (Fig. 1A). On the other hand, a SEM image of the syn-
thesized Fe-nano zeolite with particles was composed of very small
nanocrystals (Fig. 1B).
3.2. The surface area (BET)
Table 1 presents the results of BET analysis of the Fe-nano zeolite and
AC. The specific surface areas of the Fe-nano zeolite and AC were 987.8
and 640.6 m2/g, respectively. Generally, an increase in specific surface
area would lead to a better adsorption performance for the adsorbent.
On the other hand, the pore size of Fe-nano zeolite and AC were 2.9
and 1.2 nm, respectively. An increase in surface area and pore size of Fe-
nano zeolite also facilitates the adsorption process, as the large nitro-
phenol molecules can bind to the adsorption site more easily, resulting
in an improved adsorption capacity of the nitrophenols compared to AC.
3.3. FTIR analysis
Fourier transform infrared (FTIR) spectroscopy is used to investigate
the functional groups present in the Fe-nano zeolite and AC (Fig. 2A
andB). The characteristics of Fe-nano zeolite (Fig. 2A), which consists
of Fe ions was reflected by the peaks at 480–560 cm−1 [22]. A strong
ð1Þ peak around 1000 cm−1 represented the Si\\O stretch. The small
peaks around 1650 cm−1 are linked to the adsorbed water in the nano
zeolite. The broad band range from 3320 to 3600 cm−1 was assigned
to the O\\H stretching vibrations of the hydrogen-bonded molecules.
The broad stretch in this wavenumber range was attributed to the
loosely-bound water molecules hydrogen-bonded to Si\\OH groups in
the nest defects due to Al vacancies in the zeolite structure [23]. Fig.
2B presents the FTIR spectra of AC. A wide band in the range, 3200–
3450 cm− 1, was assigned to the stretching peak of hydroxyl groups
212 P.-T. Huong et al. / Materials and Design 101 (2016) 210–217

Table. 1
Surface area and pore volume comparison between Fe-nano zeolite and AC.

Materials S BET (m2/g) V pores (cm3/g) Pore size (nm)

Fe-nano zeolite 987.8 0.04 2.9

AC 640.6 0.02 1.2

associated with hydrogen bonding. The band at 1630 cm−1 is indicative

of a stretching vibration of C_O bonds associated with carboxylic acids
or esters present in the AC. A band at approximately 2900 cm−1 corre-
sponds to a C\\H vibration, while a band at 1158 cm−1 was assigned
tentatively to a C\\O vibration [24].

3.4. XRD analysis

The X-ray diffraction (XRD) was used to analyze the crystallinity of

Fe-nano zeolite (see in Fig. 3). The peaks at 2θ values of 17, 24.3, 30.2
and 52.1° were assigned to the aluminate peak of the Fe-nano zeolite. Fig. 3. XRD analysis.
The peaks at 2θ = 7–9° correspond to the specific peaks of Al3 + and
Si4+ in the adsorbent. The high intensity of the peak at 2θ = 33° repre- The Langmuir model is represented by Eq. (4):
sents the Fe loaded nano zeolite. The peaks in the Fe-nano zeolite struc-
ture were similar to the structure of nano zeolite, ZMS-5 [23–24]. qe ¼ ðbqm Ce Þ=ð1 þ bCe Þ ð4Þ

3.5. Adsorption isotherms
The adsorption isotherm models of Langmuir and Freundlich were
used to investigate the adsorption of nitrophenols by using Fe-nano ze-
olite adsorbent. Generally, an adsorption isotherm model is distin-
guished by the respective parameters in the model that indicate the
affinity and surface properties of a particular adsorbent used.
The Freundlich isotherm is an empirical equation that is derived by
assuming a heterogeneous surface with a non-uniform distribution of
the heat of adsorption over the surface of the adsorbent; it is commonly
expressed as Eq. (3) below:
qe ¼ K f Ce 1=n
where Kf ((mg/g)(L/mg)1/n) is adsorption equilibrium constant, 1/n is
the Freundlich constant related to the intensity, Ce is the equilibrium
concentration (mg/L), and qe is the amount adsorbed at equilibrium
(mg/g).
where b is the equilibrium adsorption coefficient (L/mg) and qm the
maximum adsorption capacity (mg/g). Table 2 lists the adsorption iso-
therm results and the data fitting of the two adsorption models. The
Langmuir isotherm model is based on the assumption that all adsorp-
tion sites are alike and equally energetic, making the surface homoge-
neous [38–40]. The Langmuir constant (qm), however, represents the
monolayer saturation at equilibrium when the adsorbent surface is cov-
ered with nitrophenol molecules, which helps explain the adsorption
performance. The Langmuir adsorption model provides the best fit for
the experimentally determined data with respect to the adsorption of
nitrophenols (R2 = 0.97–0.99) (Fig. 4A). This shows the favorable ad-
sorption process of nitrophenol removal using Fe-nano zeolite. A fit of
the experimental data using the Langmuir isotherm revealed the maxi-
ð3Þ mum adsorption capacity of m-, o-, and p-nitrophenol to be 168.7, 193.9,
and 223.1 mg/g, respectively. These results suggest that Fe-nano zeolite
had high adsorption capacity for nitrophenol removal compared to the
other adsorbents, such as Coir pith carbon (12.8 mg/g), Activated car-
bons from sewage sludge (45.9 mg/g) and Activated carbon fibers
(125.9 mg/g) [25–27]. The adsorption capacities were observed in the
following order, m-nitrophenol b o-nitrophenol b p-nitrophenol, due
to the structure molecule, dipole moment and molecule size of the
three isomers. p-Nitrophenol had smallest size (0.67 nm) compared to
o-nitrophenol (0.81 nm) and m-nitrophenol (0.84 nm). The dipole mo-
ment of p-nitrophenol (5.7) was also larger than those of o-nitrophenol
(5.1) and m-nitrophenol (3.74) [28]. Based on these results, p-
nitrophenol would show higher adsorption capacity on Fe-nano zeolite.
On the other hand, the Freundlich isotherm model is generally used
to describe a heterogeneous adsorption system (Fig. 4B). Based on the
R2 values for the Freundlich isotherm (R2 = 0.79–0.87), it was conclud-
ed that the correlation coefficients for the Langmuir isotherm were bet-
ter for describing the sorption behavior of nitrophenols from aqueous
solutions than the Freundlich isotherm [29–30].

Table 2
Langmuir and Freundlich adsorption isotherms.

Langmuir isotherm Freundlich isotherm

Adsorbed
Qmax (mg/g) b R2
1/n Kf R2

m-nitrophenol 168.71 7.24 0.97 0.218 51.23 0.87

o-nitrophenol 193.89 8.42 0.98 0.192 53.89 0.85

p-nitrophenol 223.18 9.61 0.99 0.176 58.01 0.79

Fig. 2. Fourier transform infrared of (A): Fe-nano zeolite and (B): AC.
 P.-T. Huong et al. / Materials and Design 101 (2016) 210–217 213

Fig. 5. Effect of solution pH for removal of nitrophenols.

In the acidic condition (pH 2.0–4.0), there are high concentration of

H+ ions and it would be increased electrostatic repulsion on the surface
of Fe-nano zeolite, which resulted in slightly decreasing the adsorption
amount.
When the pH increased up to 5.0, the proton concentration would be
decreased, leading to increase the electrostatic attraction between the
positively charged surface of the adsorbent and the negative charge of
the nitrophenols molecule, thereby increasing the removal efficiency.
On the other hand, when the solution pH increased to higher, espe-
cially up to alkaline, nitrophenols molecules gradually ionized because
of the pKa values of m-, o-, and p-nitrophenols were 8.40, 7.17, and
7.15, respectively [28]. These adsorbed had a high negative charge and
the net charge on the surface of the Fe-nano zeolite also was negative.
Therefore, the removal efficiency of nitrophenols decreased significant-
ly based on the increasing negative charged of the adsorbed and the sur-
face of Fe-nano zeolite.

Fig. 4. A. The Langmuir isotherm. B. The Freundlich isotherm.

3.6. Influence of solution pH for nitrophenols removal

The solution pH strongly influences the adsorption process between

Fe-nano zeolite and nitrophenols.
As the solution pH was increased from 2.0 to 5.0, the removal effi-
ciencies increased from 20.9 to 92.27% for m-nitrophenol, 23.7 to
95.6% for o-nitrophenol and 26.1 to 98.6% for p-nitrophenol. The sorp-
tion percentage peaked at pH 5.0 and then decreased to 49.4, 52 and
60.1% at pH 10 for m-nitrophenol, o-nitrophenol and p-nitrophenol, re-
spectively (Fig. 5). On the other hand, one of the most useful chemical
parameters that can be characteristic of an adsorbent is the point of
zero charge. The point of zero charge (pzc) can be defined as the sus-
pension pH at which a surface has a net charge of zero. When the
pH b pHpzc, the surface of adsorbent has a net positive charge and if
the pH N pHpzc, the surface of adsorbent has a net negative charge. The
surface of the Fe-nano zeolite has the point of zero charge (pHpzc) at ap-
proximately pH 5.11 ± 0.1, and starts to build a partial negative charge
at pH N pHpzc. Fig. 6. Effect of reaction time for removal of nitrophenols.
214 P.-T. Huong et al. / Materials and Design 101 (2016) 210–217
3.7. Influence of reaction time for nitrophenols removal
Fig. 6 shows the effects of the different reaction times from 10 to
300 min on the adsorption of nitrophenols by Fe-nano zeolite. The ad-
sorption was rapid and almost complete in 180 min, which is almost
adsorption equilibrium. The adsorption capacity of m-, o-, and p-
nitrophenol were 142.3, 161.1, and 193.3 mg/g, respectively. The
nitrophenol adsorption rate was high in the initial stages of the adsorp-
tion experiment because more adsorption sites were available for nitro-
phenol adsorption. After 180 min, it was difficult for the remaining
vacant surface sites to be available for further nitrophenol adsorption
or removal due to the repulsion of the nitrophenol molecules on the sur-
face of the Fe-nano zeolite with increasing adsorption [31]. Further ad-
sorption was negligible and thus 180 min was chosen as the optimum
reaction time for the other experiments.
3.8. Adsorption kinetics
The adsorption kinetics is one of the most important parameters for
elucidating the removal/adsorption mechanism of nitrophenols and
assessing the performance of the adsorbents. Two kinetic models,
Fig. 7. A. First-order kinetic model. B. Second-order kinetic.
namely the pseudo-first-order and pseudo-second-order models, were
applied to the experimental data to predict the adsorption kinetics.
The reaction rate constant of nitrophenol adsorption was deter-
mined using first and second-order kinetic models. The first-order reac-
tion expression is given in Eq. (5):
logðqe −qÞ ¼ logqe −k1 t=2:303 ð5Þ
where qe and q are the amounts of nitrophenols adsorbed (mg/g) at
equilibrium and at time t (min), respectively, and k1 is the rate constant
of adsorption (min−1).
The second-order kinetic model is as Eq. (6):
t=q ¼ 1=k2 qe 2 þ t=qe ð6Þ
where k2 is the rate constant of second-order adsorption (g/(mg min)).
The pseudo-first order equation assumes that the solute uptake rate
is directly proportional to the difference between the saturation con-
centration and the amount of solid uptake with time. Fig. 7A show a
plot of log (qe − qt) vs. time (t) for the adsorption kinetics of
nitrophenols using Fe-nano zeolite. The pseudo-first order model pro-
vided a poor fit for the experimental data obtained and the computed
equilibrium adsorption capacities based on the kinetic model were not
acceptable because they were essentially lower than that of the experi-
mental data (see in Table 3). Therefore, the adsorption of nitrophenols
onto Fe-nano zeolite does not follow the pseudo-first-order kinetic
model.
Fig. 7B shows a fit of the experimental data to the linearized pseudo-
second order model of t/qt against time (t) for Fe-nano zeolite. The
added straight lines suggest the ideal fits to the pseudo-second order ki-
netic model for m-, o- and p-nitrophenols using Fe-nano zeolite. The ex-
perimental data was fitted perfectly to this model, as supported by the
exceptionally high R 2-values of 0.97, 0.98 and 0.99 for m-nitrophenol,
p-nitrophenol and o-nitrophenol, respectively. The fittingness of the ex-
perimental data to the pseudo-second order kinetics model suggests
that the adsorption mechanism revolves around the adsorbate and ad-
sorbents [32–34].
3.9. Effect of the adsorbent dose
The adsorbent dosage is an important parameter because it deter-
mines the capacity of an adsorbent for a given initial concentration of
adsorbate. Fig. 8 shows the relationship between adsorbent dose and
the nitrophenol removal efficiency by the Fe-nano zeolite at different
adsorbent doses ranging from 0.05 to 1 g. The removal efficiency of
the nitrophenols per unit weight of adsorbent increased rapidly with in-
creasing Fe-nano zeolite dose up to 0.5 g and the removal efficiencies for
m-nitrophenol, o-nitrophenol, and p-nitrophenol were 91.1, 95.8 and
98.3%, respectively. This can be attributed due to the increase in surface
area resulting from the increase in adsorbent mass or larger number of
adsorption sites for a fixed concentration of m-, o- and p-nitrophenol
onto the adsorbent. Above a dosage of 0.5 g, the percentage removal
of nitrophenols showed no further appreciable increase, possibly due
Table 3
Comparison of the first- and second-order adsorption rate constants and calculated and
experimental qe values for nitrophenols.
Adsorbate First-order kinetic model Second-order kinetic
model
qe (exp, mg/g) qe (cal, mg/g) R2 qe (cal, mg/g) R2
m-nitrophenol 91.25 54.96 0.75 89.91 0.97
o-nitrophenol 95.68 61.72 0.81 93.89 0.99
p-nitrophenol 97.48 64.17 0.78 77.24 0.98
Note, exp and cal stand for experimental and calculated, respectively.
 P.-T. Huong et al. / Materials and Design 101 (2016) 210–217
Fig. 8. Effect of adsorbent dose.
to the overlap of active sites at such a high dosage. Therefore, 0.5 g of Fe-
nano zeolite was chosen for further experiments [35–36].
3.10. Effect of the initial nitrophenol concentration
Fig. 9 shows the adsorption capacities of m-, o- and p-nitrophenol by
Fe-nano zeolite under the optimal pH conditions as a function of the ini-
tial nitrophenol concentration. The adsorption capacity increased with
increasing initial nitrophenol concentration range of 10–400 mg/L and
then reached saturation at approximately 400 mg/L. At low initial con-
centrations, the surface areas and the adsorption sites were available
for nitrophenol removal. At high initial nitrophenol concentrations
(above 400 mg/L), the adsorption capacity of the nitrophenols was im-
proved slightly and tended towards a constant value. The results sug-
gest that almost all of the active sites for further adsorption were
occupied by nitrophenols. This can be attributed to an increase in the
degree of saturation for the sorbent sites above a certain nitrophenol
concentration [37–41]. Further increases in the ratio of nitrophenols/ad-
sorbent saturated the active binding sites in the adsorbent surface, and
did not contribute to further nitrophenol adsorption.
Fig. 9. Effect of initial nitrophenols concentration.
215
Table 4
Wastewater properties.
Wastewater source Color pH Concentration of TOC
p-nitrophenol (mg/L) (mg/L)
Hyundai company, white 6.11 380 9610
Ulsan, South Korea
3.11. Evaluation of the potential of Fe-nano zeolite by applying to remove
the nitrophenols from wastewater
The test industrial wastewater was collected from the petrochemical
processes of Hyundai Company in Ulsan, South Korea. The p-
nitrophenol concentration in the test industrial wastewater at pH 6.11
was very high at 380 mg/L (Table 4), which may induce serious environ-
mental problems unless treated properly.
The treatment process, to evaluate the performance of Fe-nano zeo-
lite and AC for the removal of p-nitrophenol from wastewater, were car-
ried out under optimized conditions of pH 5.0, temperature of 20 °C ± 1,
adsorbent dosage of 0.5 g, and contact time of 180 min. Fig.10 shows the
p-nitrophenol removal efficiency of the investigated adsorbents for the
industrial wastewater with a high phenol concentration (380 mg/L).
The removal efficiencies of p-nitrophenol by Fe-nano zeolite and AC
were 92.8 and 56.5%, respectively. Fe-nano zeolite exhibited the
greatest adsorption percentage removal for p-nitrophenol from waste-
water compared to AC. FTIR spectroscopy indicated that Fe-nano zeolite
had a substantially larger number of hydroxyl functional groups than
AC, which is a favorable for removing p-nitrophenol. On the other
hand, Fe-nano zeolite had a higher surface area and pore size than AC,
leading to more adsorption of p-nitrophenol.
This high efficiency confirms the promising potential of Fe-nano ze-
olite as an adsorbent to remove toxic p-nitrophenol from industrial
wastewater.
3.12. Regeneration of the loaded adsorbents
To minimize the costs of the entire recovery process, the adsorbed p-
nitrophenol needs to be desorbed and the adsorbents regenerated for
further adsorption-desorption cycles. Fig. 11 shows the desorption effi-
ciencies of p-nitrophenol from the nitrophenol-loaded Fe-nano zeolite
and AC. Even after 15 consecutive regeneration (adsorption-
Fig. 10. Removal of p-nitrophenol from wastewater.
216 P.-T. Huong et al. / Materials and Design 101 (2016) 210–217

using Fe-nano zeolite and AC were determined. The additional costs re-
quired for one time adsorption-desorption were based on the adsorp-
tion costs of p-nitrophenol (on the Fe-nano zeolite and AC) and a
purchase price of C2H5OH 20% (0.2 US$/500 mL); it was estimated to
be 0.02 US$/g p-nitrophenol.
The adsorption cost required for p-nitrophenol removal on Fe-nano
zeolite and AC were calculated to be 262.2 and 805.6 US$/1000 kg
wastewaters, respectively. If Fe-nano zeolite is applied as an adsorbent
for the removal of p-nitrophenol from wastewater, an adsorption cost
of 543.4 US$/1000 kg wastewater can be saved (i.e., 67.6% lower than
AC).
On the other hand, the Fe-nano zeolite was reused 15 times. There-
fore, the recycling ability of Fe-nano zeolite would greatly reduce the
adsorption cost of p-nitrophenol from the wastewaters.
The high adsorption capacity and low preparation cost of Fe-nano
zeolite support its potential as an effective and low-cost adsorbent for
the removal of wastewater containing nitrophenols.

4. Conclusions

This study examined the feasibility of using synthesized Fe-nano ze-

Fig. 11. Adsorption-desorption cycles.
desorption) cycles, the desorption efficiencies of p-nitrophenol from p-
nitrophenol-loaded Fe-nano zeolite and AC were 78.6 and 57.9%, re-
spectively. The adsorbent (Fe-nano zeolite) retained its stable phase
and the adsorption capacity only decreased by 21.8% from the initial ad-
sorption capacity of p-nitrophenol. This high reusability, high adsorp-
tion capacity, combined with facile regeneration characteristics
highlight the potential of the Fe-nano zeolite as an effective adsorbent
for the removal of p-nitrophenol from wastewater.
3.13. Economic analysis
Table 5 compares the adsorption costs for the removal of p-
nitrophenol from wastewater using Fe-nano zeolite and commercial ac-
tivated carbon (AC), which has been widely used for the removal of or-
ganic pollutants from wastewaters. The adsorption costs of p-
nitrophenol were calculated simply based on the average adsorption ca-
pacity of p-nitrophenol and the purchase and preparation costs of the
adsorbents.
Adsorption cost ðUS$=g pnitrophenolÞ
    
US$ Kw
Chemicals purchase cost þ Energy cost ðUS$Þ
g g
¼    
mg g by the Korea Small and Medium Business Administration in 2014.
Adsorption capacity  10  3
g mg
The preparation cost of the Fe-nano zeolite was calculated based on
the purchase price of the chemicals and the energy cost. The costs of
chemicals were calculated using the Korean purchase price of NaOH,
NaAlO2, Fe(NO3)3, AC, H2O, and Si (OC2H5)4. The energy cost for synthe-
sizing the Fe-nano zeolite was determined by the Korean electricity cost
spent for heating and drying. Table 5 lists the simply estimated adsorp-
tion costs required for the removal of a unit weight of p-nitrophenol by
the Fe-nano zeolite and AC.
In this study, the adsorption costs required for the treatment of
1000 kg wastewater containing 380 mg/L nitrophenol in a batch reactor
olite as an adsorbent for o-, p- and m-nitrophenol removal. The optimal
removal efficiencies were obtained at a reaction time of approximately
180 min, pH 5.0, and adsorbent dose of 0.5 g. The adsorption data of
the nitrophenols indicated the Langmuir adsorption model to have a
better fit than the Freundlich isotherm model. The maximum adsorp-
tion capacities for m-nitrophenol, o-nitrophenol, and p-nitrophenol
were 168.7, 193.9, and 223.1 mg/g, respectively. In the application to re-
move p-nitrophenol from wastewater, Fe-nano zeolite showed higher
adsorption performance (92.8%) than AC (56.5%).
The regeneration process involved 15 adsorption-desorption cycles of
p-nitrophenol in wastewater using Fe-nano zeolite and AC. The desorp-
tion efficiencies of p-nitrophenol using Fe-nano zeolite and AC were
78.6 and 57.9%, respectively. The required adsorption cost for the treat-
ment of 1000 kg wastewater containing 380 mg/L of p-nitrophenol on
Fe-nano zeolite was 67.6% lower than those on AC. These results showed
that Fe-nano zeolite with high adsorption capacity and low preparation
cost can be used as an effective and economic adsorbent for the removal
of nitrophenols from wastewaters.
Acknowledgment
This work (C0193571) was supported by the Business for Coopera-
tive R&D between Industry, Academy, and Research Institute funded
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Table 5
Comparison of adsorption cost for removal of p-nitrophenol in wastewater by using Fe-nano zeolite and activated carbon (AC).

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