Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554564

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Journal of the Taiwan Institute of Chemical Engineers

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An investigation into the adsorption removal of ammonium by salt activated

Chinese (Hulaodu) natural zeolite: Kinetics, isotherms, and thermodynamics
Aref Alshameri a, Chunjie Yan a,*, Yasir Al-Ani b, Ammar Salman Dawood b, Abdullateef Ibrahim c,
Chunyu Zhou a, Hongquan Wang a
a
Engineering Research Center of Nano-geomaterial of Education Ministry, China University of Geosciences, Wuhan 430074, China
b
School of Environmental Studies, China University of Geosciences, Wuhan 430074, China
c
State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074, China

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

Article history: The development of the process of sodium activation of zeolite has been an effective technique for
Received 2 February 2013 enhancing the efciency of ammonium removal. In this research, the optimum conditions for the
Received in revised form 2 May 2013 activation of Chinese (Hulaodu) zeolite of the most effective parameters such as sodium concentration,
Accepted 6 May 2013
stirring time, and temperature were determined. The most efcient conditions were selected according
Available online 12 June 2013
to the highest ammonium removal capacity. The characteristics of activated zeolite (ActZ) and its
mechanism of ammonium removal were investigated and compared with that of natural zeolite (NZ).
Keywords:
Additionally, both zeolites were analyzed by scanning electron microscopy (SEM), Zeta potential, X-ray
Zeolite (clinoptilolite)
Adsorption
diffraction (XRD), thermogravimetry (TG) and BET surface analysis. The activated zeolite revealed the
Activated zeolite highest ammonium removal efciency reaching up to 98% based on stirring time, zeolite loading, initial
Ammonium removal ammonium concentration, temperature and pH. The adsorption kinetic was explored and tted best
Kinetics and isotherm with the pseudo-second-order model, whereas adsorption isotherm results illustrated that Langmuir
model (LM) provided the best t for the equilibrium data. Moreover, thermodynamic parameters such as
change in free energy (DG8), enthalpy (DH8) and entropy (DS8) were also calculated. The parameters
revealed that the exchange of ammonium ion by activated zeolite occurred spontaneously at ambient
conditions (25 8C). It was concluded that when Chinese (Hulaodu) zeolite is activated under the
condition of 1 M NaCl, 70 8C and stirring time of 30 min, an excellent removal of NH4+ was obtained.
2013 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction which contributes to the accelerated incidence of eutrophication

Clinoptilolite (Na,K,Ca)6(Si,Al)36O7220H2O is one of the natu-
rally existing zeolites. It is rich in silica and has a lower ion-
exchange capacity than other zeolites as well as less than that of
many of the available synthetic ion-exchange resins. It generally
exhibits a high selectivity for ammonium and metallic ions [1,2].
Clinoptilolite from different deposits has been widely reported as
adsorbent for ammonium removal from wastewaters [3,4]. Natural
zeolite, on the other hand, needs to be puried and modied in
order to improve its ion-exchange [5] and adsorption properties
before it can be used to remove ammonium effectively. Nitrogen
compounds in aqueous environments are usually found in the form
of ammonium ions (NH4+). Important sources of NH4+ include
efuent from municipal sewage treatment plants, the application
of fertilizer in agricultural practices and industrial processes all of
* Corresponding author. Tel.: +86 18971579917; fax: +86 027 67885098.
E-mail address: chjyan2005@126.com (C. Yan).
resulting in algal bloom in lakes and rivers [610]. Complete
removal of NH4+ is required due to its toxicity to the majority of
aquatic life. For example, the ammonium nitrogen concentration
for most sh species must not exceed 1.5 mg NH4+ ion [11,12].
NH4+ concentration, in certain surface waters serving as a source of
potable water, is much higher than the permissible level, due to
large quantities of industrial and municipal wastewater being
discharged into existing water resources [5,13]. This threatens the
availability of safe drinking water and, thus, human health. For this
reason, the prevention of nitrogen pollution with NH4+ removal
from wastewater is of great importance [7,9,14,15].
Various methods including air stripping, biological methods
and activated carbon have been used for NH4+ removal [1619].
However, since biological methods do not respond well to shock
loads of ammonium, unacceptable peaks of NH4+ over the
discharging levels may frequently appear in the efuent. Also,
high costs, poor regeneration and uncertainty of outcome are some
of the frequently encountered limitations in the application of the
biological method. Moreover, there is a high risk to safety during

1876-1070/$ see front matter 2013 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jtice.2013.05.008
 A. Alshameri et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554564
Nomenclature
C0 the starting equilibrium concentrations (mg/L)
Ce the nal equilibrium concentrations (mg/L)
V the volume of the working solution (L)
M the mass of added zeolite (g)
k1 and k2 (1/min) and (g/mg min) are constants of
adsorption
h the rate of adsorption (mg/g min)
K Langmuir constant (L/mg)
KF Freundlich adsorbent capacity (mg/g (L/mg)1/n)
n the reciprocal of reaction order
qt adsorption capacity at time t (mg/g)
qe adsorption capacity at equilibrium conditions
(mg/g)
qmax maximum adsorption capacity (mg/g)
Kid constant of intraparticle diffusion (mg/g min1/2)
a and k0 constants of Bangham equation
V the volume of solution (ml) of Bangham equation
m the weight of adsorbent (g/L) of Bangham equation
the subsequent processing such as the aeration process which
causes stripping effects for volatile compounds resulting in
accidental releases, often causing odor and aerosol with health
implications [20,21].
Contingency on temperature and climate conditions constitutes
another disadvantage in this process [22]. Compared with the
above mentioned methods, high safety, low cost [13,2326] and
relative simplicity of application and operation are some of the
attributes that are attracting an increasing focus on the use of
zeolite for environment applications [2,8,11].
The factors that inuence ammonium removal performances
are mainly pH, temperature, reaction time, initial concentration
of NH4+, and adsorbent dosage. Although many previous studies
have focused on these factors collectively [3,27,28], however,
comparison of the results from the available literature indicates
signicant variability in the reported behavior.
It seems that natural clinoptilolites from different places have
different characteristics [9,10,29,30]. These differences in the
characteristics of clinoptilolites are probably attributed to the
differences in the geological formation of zeolite sources
[21,31,32]. Therefore, each special zeolite material has its own
special characteristics and still requires to be researched individ-
ually [11,27,31].
The main aim of this study is to determine the optimal
conditions for the activation of Chinese (Hulaodu) zeolite to get the
best results for the adsorption of NH4+ by salt treatment. The main
focus of the study is the transformation of low grade Hulaodus
zeolite to a high cation exchanger under appropriate activation
conditions. An investigation and comparison of characteristics and
the equilibrium removal of NH4+ ion onto both zeolites was also
carried out.
The specic objectives of this research is to study the sodium
activation of zeolite samples and the effect of various parameters
on zeolite activation such as sodium concentration, stirring time,
and temperature. And to identify the key processes controlling the
rate of ammonium adsorption by zeolite. In addition, the effects of
pH, stirring times, initial concentration, adsorbent dosages and
temperature on NH4+ removal for both natural and activated
samples were investigated and compared. Adsorption isotherms,
thermodynamics and reusability of zeolite for the removal of NH4+
ions were examined.
555
2. Materials and methods
2.1. Raw materials
A natural zeolite (NZ) was collected from Huludao city in China.
Analytical grade inorganic chemicals, such as ammonium chloride
(NH4Cl), sodium chloride (NaCl), sodium hydroxide (NaOH) and
hydrochloric acid (HCl), were used.
2.2. Preparation and activation of zeolite
A natural zeolite (NZ) was ground and passed through 200
230 mesh sieves. The material was washed with distilled water to
remove any non-adhesive impurities, and then dried in an oven at
100 8C for 24 h and nely crushed. The activation process was
carried out by mixing NZ powder material with an aqueous
solution of sodium chloride under the different conditions detailed
below:
Effect of sodium concentration: To study the effect of sodium
concentration and batch activation, the sodium chloride
concentration was varied from 0.5 to 2 mol/L with zeolite/
solution ratio maintained as 1 g/10 ml. The suspension was
stirred in conical asks (500 ml) using a magnetic stirrer
water bath at a rate of 120 rpm and 90 8C for 2 h. Subsequently,
the suspension was ltered and washed with distilled water.
The wet activated material was dried at 70 8C in an oven for 24 h
and used in batch adsorption experiments at an initial
ammonium concentration of 100 mg/L with a pH 7 at 25 8C
and stirring time of 24 h. The best sodium ion concentration for
the activation of zeolite was selected as that corresponding to
the highest NH4+ removal capacity (mg/g).
Effect of time: For determining the optimum time required for
activation zeolite from aqueous solution, a weighed quantity of
zeolite (1 g) was added into the solution of 1 mol/L sodium
chloride concentration and stirring time ranging from 0.5 to 3 h.
The conditions applied above on the effect of sodium
concentration experiment were repeated. The optimum stirring
time for the activation of zeolite was selected as that
corresponding to the highest NH4+ removal capacity (mg/g).
Effect of temperature: The effect of temperature on activation of
zeolite was investigated at different temperature values
ranging from 10 to 90 8C. The sodium chloride concentration
and stirring time were kept constant at 1 mol/L and 0.5 h,
respectively. The optimum temperature for the activation of
zeolite was selected as that corresponding to the highest NH4+
removal capacity (mg/g).
2.3. Analysis and characterization
The activated and natural zeolites were characterized by XRD,
SEM, EDX, TG, Zeta potential, chemical analysis and specic surface
area (BET). Identication of mineral species in the zeolite samples
was carried out by XRD pattern using a Germany D8-FOCOS X-ray
diffractometer with Cu Ka (l = 0.154 nm) radiation operating at
40 kV and 40 mA and a step width of 0.058. Semi-quantitative
weight percentages of samples were calculated by using mineral
intensity factors. Textural characteristics of the activated and
natural zeolites were performed using a Japanese Netherlands
FESEM Quanta SU8010 electron microscope, operating at an
accelerating voltage of 15 kV for photomicrographs as well as to
analyze the Chinese-zeolite composition by Energy Dispersion X-
ray Spectrometry (EDS), USA, Apolloxp. The sample was initially
placed in a vacuum chamber for coating with a thin layer (a few
nanometers) of gold (Au). The specic surface area, pore size and
volume of the material were evaluated by the nitrogen gas
556 A. Alshameri et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554564
adsorption method, with a heating rate of 10 8C/min. N2
adsorptiondesorption experiments were performed at 77 K with
an Automatic Volumetric Sorption Analyzer (ASAP2020, TSI,
America), employing multipoint BET isotherm adsorption data
tting. Zeta potential measurements for the natural and activated
zeolites, as a function of medium pH, were determined using Zeta
Plusk equipment (zetasizer Nano ZS 90, Malvern, UK). A 103 mol/L
solution of KNO3 and 60 mg/L of ammonium concentration were
used. The medium pH was controlled by adding HCl (pH < 7) and
NaOH (pH > 7) solutions, separately. The water content and zeolite
decomposed were determined by a Thermogravimetric (TG)
analyzer. TG/DSC analysis was performed on a NEZSCH, STA409-
PC-Germany, and thermal analysis system was in the range 30
1200 8C. In addition, the composition of zeolite was analyzed by
chemical method. Absorbance values of ammonium ion concen-
tration in solution were read using a Chinese-Shimadzu UV-723Vis
spectrophotometer. Quality control testing includes experiments
with blanks and duplicates.
2.4. Adsorption rate, batch sorption studies
All adsorptions in batch experiments were carried out using
stopper conical asks (500 ml), zeolite/liquid ratio of 1 g/100 ml,
magnetic stirring water bath, a stirring rate of 120 rpm and a
temperature at 25 8C. A stock solution (1000 mg/L) was prepared
by dissolving NH4Cl in distilled water.
For determining the optimum time required for ammonium
removal by natural zeolite (NZ) and activated zeolite (ActZ) from
aqueous solution, a weighed quantity of adsorbent (1 g) was added
into solution of 80 mg/L ammonium concentration and was stirred
for 10420 min and 560 min of NZ and ActZ, respectively, at a xed
pH of 7. The effect of initial ammonium concentration in batch
adsorption experiments was carried out by using initial ammonium
concentration in the range of 10240 mg/L and 10400 mg/L for
300 min and 40 min for NZ and ActZ, respectively. The effect of pH on
adsorption was investigated at initial ammonium concentration of
80 mg/L and performed in different pH values (210) at 25 8C. Batch
adsorption was conducted at 300 and 40 min for NZ and ActZ,
respectively. The pH of the solution was adjusted by 1 M HCl or
NaOH solution. For determining zeolites loading effect, zeolite
loading was varied from 0.2 to 2.2 g/100 ml at initial ammonium
concentration of 80 mg/L. The zeoliteliquid was then stirred for 300
and 40 min for NZ and ActZ, respectively, at temperature 25 8C.
Temperature of adsorption isotherms was studied at 25, 35 and
45 8C. A 100 ml of ammonium chloride solution of 80 mg/L
concentration was equilibrated with 1 g zeolite for 40 min for
ActZ. Samples were ltered through a 0.45 mm lter membrane
after adsorption.
The residual concentration of ammonium was determined by
Nesslers reagent spectrophotometry method at 420 nm.
The removal efciency (%) of zeolite and the amount of
adsorbed ammonium ions (qe) were calculated, respectively, using
the following equations:
C0  Ce
Removal efficiency %  100
C0
C0  Ce
qe
M
3. Results and discussion
3.1. Activated zeolite
Due to different results in activation of different zeolite
samples, parameters, such as sodium concentration, stirring time
and temperature, had to be investigated to obtain optimum
activation conditions, and the results are shown in Fig. 1ac. As can
be seen from batch adsorption experiments (Fig. 1ac), the
temperature of 70 8C, stirring time of 30 min and 1 mol/L
concentration of NaCl were the most effective in adsorption of
NH4+ ions on Hulaodu natural zeolite (NZ). The optimum
conditions obtained above for the activation of zeolite using NaCl
were applied on NaOH for the adsorption of NH4+ ions at 100 mg/L
of ammonium concentration, pH 7 and 25 8C. Its NH4+ adsorption
capacity (mg/g) was compared with NaCl activation as shown in
Table 1. The results showed that NaCl-activated zeolite (ActZ) had
a higher NH4+ adsorption capacity value than NaOH-activated
zeolite. This result was conrmed by EDS analysis (Fig. 2a and b)
which showed that the Na+ content of the NaOH-activated zeolite
(1.33%) was lower than that of NaCl-activated zeolite (2.10%).
Higher NH4+ adsorption capacity means higher Na+ content
[3234]. From the above discussion, it can be concluded that ion
exchange promoted by NaCl-activated zeolite (ActZ) is a more
attractive zeolite preparation method than that of NaOH-activated
zeolite. Therefore, NaCl-activated zeolite (ActZ) was selected for
further study.
3.2. Natural and activated zeolite characteristics
SEM and the qualitative composition analysis of EDS obtained
from the grain of natural and activated zeolites are shown in Fig. 2.
Fig. 2c illustrates that the main chemical elements (Al, Si, O, Na, Mg,
K, Ca and Fe) are present in the structure of this natural zeolite, in
agreement with the chemical composition (Table 2). Quantitative
tests were also performed on both zeolites. The results from
elemental analysis by EDS of NZ and ActZ as shown in Fig. 2a and c
indicate that the Na+ content in NZ increased from 0.21% to 2.10%
after activation. Meanwhile, the content of Ca2+, Mg2+ and K+
decreased from 3.44%, 0.81% and 1.53% to 1.08%, 0.58% and 0.76%,
respectively. For this reason, the ammonium capacity of combined
activated zeolite increased sharply in microscale [33,34].
The XRD patterns of NZ and ActZ are shown in Fig. 3a. X-ray
diffraction did not show any changes in zeolite structure after
activation. Mineralogical analysis of the zeolite samples was
carried out using X-Ray Diffraction (XRD). The results showed that
the natural zeolite contained clinoptilolite in the majority 93%, and
small quantity of quartz 7%.
Chemical components of natural zeolite are shown in Table 2.
The Si/Al ratio calculated from these data was found to be 4.8. The
ratio of Si/Al is an important factor in understanding the zeolite
structure. When the ratio is over than 4.0, then the zeolite is a
clinoptilolite-type and as such, the structure would not be broken
easily at high temperature.
This result was conrmed by thermogravimetric (TG) analysis
as shown in Fig. 3b. It shows that the zeolite could stand
temperatures of up to 869.2 8C without being decomposed and that
it only undergoes a weight reduction of 0.07% at this temperature.
It also, shows that the water content of zeolite was lost at 71.2 8C.
The surface analysis of activated zeolite was investigated by
Zeta potential and BET standard method and compared with that of
(1)
natural zeolite. Fig. 3c shows that zeolite surface groups are mainly
negative in the studied pH range and that the ammonium removal
(2) does not interfere much with the Zeta potential measurements,
conrming the theory that the mechanism is not electrostatic
(charge neutralization) but a result of an ion-exchange reaction.
Moreover, the gure shows that activated zeolite is more negative
than natural zeolite.
The BET specic surface area, total pore volume, and average
width pore size of the natural zeolite were measured to be
25.88 m2/g, 0.0032 cm3/g and 8.72264 mm, respectively. How-
ever, these values did not change signicantly after activation of
 A. Alshameri et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554564
Fig. 1. Removal capacity as a function of sodium concentrations (a), stirring time (b)
and temperature (c).
zeolite, 26.7074 m2/g of specic surface area, 0.004167 cm3/g of
total pore volume and 9.64864 mm of average width pore size.
These characteristics of activated zeolite have disadvantages for
physical adsorption, but the results from equilibrium experi-
ments do not match with this fact because the removal
mechanism of ammonium by zeolites follows the ion-exchange
reaction. Therefore, ion-exchange capacities of ammonium
depend on dielectric strength between ammonium as well as
557
Fig. 2. SEM and EDS spectra analyses zeolite grain of NaCl-activated zeolite (ActZ)
(a), NaOH-activated zeolite (b) and natural zeolite (NZ) (c).
their afnities to zeolite. The size of micropores of the natural
zeolite is in the range of 310 A and micropores of the NaCl-
modied zeolite were more developed at the range of 5 A than
other cases. This implies that the NaClzeolite could selectively
remove NH4+ ions which have a specic size. Also, owing to its
small surface area, this zeolite is very stable against heat and
acidity as reported by Tehrani and Salari [29] and Gottardi and
Galli [35] who found that heat and acid activation does not result
558 A. Alshameri et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554564

Table 1
Comparison of NaCl and NaOH in zeolite activation at 100 mg/L of ammonium
concentration, pH 7, 25 8C and stirring time of 24 h.

Sodium ion used for activation Sodium concentration Ammonium removal

(mol/L) capacity (mg/g)

NaCl-activated zeolite 1 5.921

NaOH-activated zeolite 1 4.552

in drastic changes in zeolite structure but increases Si/Al ratio, as

a consequence of heat or acid activation.

3.3. Effect of stirring time

As shown in Fig. 4a and b, the removal efciency of NH4+ ions

increased with increasing stirring time. 40% and 92% of NH4+ ions
removal were completed within 10 min for NZ and ActZ,
respectively, which also conrmed larger adsorption capacity of
ActZ compared to NZ.
The experimental data show that NZ could exceed 78%
percentage removal at 300 min, but then, the removal efciency
plateaus. As to ActZ, the ammonium removal rate exceeds 98%
percentage removal at 40 min and became increasingly slow with
increasing stirring time. This may be attributed to the utilization of
the most readily available adsorption sites of the zeolite that leads
to a fast diffusion and rapid equilibrium attainment .On the basis of
these results, 300 min and 40 min stirring period was selected for
all further studies of NZ and ActZ, respectively. Beyond this level
there is no noticeable increase in the adsorption and it is thus xed
as the equilibrium time. It can be said that the NH4+ ions were
adsorbed by the exterior surface of the adsorbent. When the
adsorption of exterior surface of the adsorbent reached the
saturation point, the NH4+ ions enter the adsorbent pores and
are adsorbed by the interior surface of the particles [34,36,37].

3.4. Effect of initial ammonium concentration

As shown in Fig. 5, the increment of removal efciency was

achieved in the ranges of 1050 mg/L of NH4+ concentrations for
both NZ and ActZ. This result is similar with that reported by
Sarioglu [11] who concluded that the increase in removal
efciency was achieved between 8.8 and 40 mg/L of ammonium
concentrations, indicating that the initial NH4+ concentration plays
an important role in the adsorption of ammonium onto zeolites.
Increasing the initial NH4+ concentration would increase the
mass transfer driving force and therefore the rate at which
ammonium ions pass from the bulk solution to the particle surface
[37]. The result can be generally expected for clinoptilolite having
micropores and macropores [7]. After 50 mg/L NH4+ concentration
of both zeolites, the removal efciency of ammonium decreased
Fig. 3. The XRD of activated and natural zeolites (a), TG of natural zeolite (b) and
with increased initial NH4+ concentration. This is because the high Zeta potential of activated and natural zeolites (c).
initial ammonium concentration provided a greater driving force
[38]. As a result, the NH4+ ion could migrate from the external
surface to the internal micropores of the zeolite within a given 3.5. Effect of solution pH and the mechanism of adsorption
stirring time [32]. The equilibrium was achieved when all the
exchangeable ammonium and cation on the external and internal The pH of the aqueous solution is an important factor
surfaces of the zeolite were reached [31]. Fig. 5 shows that the controlling ammonium adsorption [21]. As shown in Fig. 6, pH
adsorption capacity of the activated zeolite was higher than that of played an important role for NH4+ adsorption of NZ and ActZ. The
natural zeolite at each initial ammonium concentration. removal efciency of both zeolites increased with increasing pH

Table 2
Chemical composition of the natural zeolite (wt.%).

NZ SiO2 Al2O3 TFe2O3 TiO2 MgO Na2O CaO K2O P2O5 MnO H2O L.O.I.

66.34 12.23 0.99 0.16 0.98 0.73 3.17 1.37 0.027 0.026 5.06 13.88
 A. Alshameri et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554564
Fig. 4. Effect of stirring time on NH4+ removal capacity of natural zeolite (a) and activated zeolite (b) (initial NH4+ concentration: 80 mg/L, 25 8C and pH 7).
from 2 to 7 and then it decreased gradually from pH 8 to 10 with
the maximum value being achieved at pH 7. An almost similar
trend has been reported for ammonium adsorption onto zeolite by
different researchers [21,30]. The behavior of ammonium as a
function of waters pH can be explained by considering the change
in density of hydrogen ions, the dominant ionic species of
ammonium and the surface charge of zeolite as a function of
waters pH. The pHzpc of natural zeolite and activated zeolite were
7.7 and 7.8, respectively, implying that the zeolite particles surface
is uncharged at water pH of 7.7 and 7.8 of natural and activated
zeolites; the zeolites particles surface has a positive charge at
water pH below 7.7 and 7.8, and it is negatively charged at water
pH above 7.7 and 7.8. This indicates that the surface of zeolite is
negatively charged at pH of above 7 [39]. For ammonium
adsorption, according to the relation of ammonium dissociation
in water as a function of pH, NH4+ ions is the dominant species of
ammonia nitrogen in water at pH of below 7 while the molecular
form, ammonia (NH3) is dominant at alkaline pH. By considering
the above facts, the increase in adsorption of ammonium with the
increase in waters pH up to the maximum point (pH 7) can be
attributed to a decrease of hydrogen ions in solution corresponding
to an increase in pH, and thus a reduction of the competition
between hydrogen ions and NH4+ ions for adsorption/exchanging
sites onto zeolite particles [6,40]. The decrease of ammonium
adsorption with the increase of waters pH above 7 is related to the
increase in percentage of molecular ammonium, which resulted in
the reduction of ionexchange potential [10].
Fig. 5. Effect of initial ammonium concentration on NH4+ removal capacity of the
ActZ and NZ (stirring time: 40 min and 300 min for ActZ and NZ, respectively, at
25 8C and pH 7).
559
3.6. Effect of adsorbent dosage
As illustrated in Fig. 7, the removal efciency of NH4+ ions by
both zeolites increases with increasing amount of both zeolites.
This effect can be attributed to an increased surface area and
number of adsorption sites [41]. As can be seen in Fig. 7, the
ammonium removal rate of ActZ increases more rapidly than that
of NZ and attains a plateau at 98.73% when the adsorbent dosage
was 1 g indicating that the NH4+ ions removal was negligible at
higher adsorbent dosage. The natural zeolite attains a plateau at
94.5% when the dosage was 1.8 g as shown in Fig. 7. Thus, both of
them reached a balance of approximately 98% when the adsorbent
dosage for ActZ and NZ was 1 g and 1.8 g, respectively. This may be
attributed to a large adsorbent amount which effectively reduces
the unsaturation of the adsorption sites and correspondingly, the
number of such sites per unit mass comes down resulting in
comparatively less adsorption at higher adsorbent amount [37,41].
Hence, when the ammonium is exchanged completely with cations
on the zeolite surface at a certain amount of zeolite loading, the
NH4+ removal reached equilibrium.
3.7. Kinetics of ammonium exchange
To identify the key process controlling the adsorption rate,
several models must be checked for suitability and consistency over
a broad range of the system parameters. Pseudo-rst- and -second-
order and Bangham equations as well as the diffusion-based
Fig. 6. Effect of pH on the removal of NH4+ ions (adsorbent dosage: 1 g/100 ml;
stirring time: 40 min and 300 min for ActZ and NZ, respectively; initial NH4+
concentration: 80 mg/L at 25 8C).
560 A. Alshameri et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554564
Fig. 7. Effect of adsorbent dosage on the removal of NH4+ ion (stirring time: 40 and
300 min for ActZ and NZ, respectively; initial NH4+ concentration: 80 mg/L at 25 8C
and pH 7).
WeberMorris model are used to t the experimental data and can
be summarized as follows.
The linear form of pseudo-rst, pseudo-second order models for
boundary conditions of q = 0 at t = 0 and qt = qe at t = te are as
follows:
The pseudo-first-order Eq: : lnqe  qt ln qe  k1 t
t 1 1 adsorption mechanisms. Langmuir model (LM) and Freundlich
The pseudo-second-order Eq: : t h k2 q2e
qt k2 q2e qe
   
C0 k0 m
Bangham Eq: : log log log a log t
C 0  qt m 230V
The adsorption kinetics of ammonium by ActZ and NZ are
presented in Fig. 8ae. The kinetic data were better tted by the
pseudo second order model than other models as indicated by
higher R2 values (Table 3). Also it shows a higher sorption rate for
ActZ than NZ.
The pseudo second order model indicates that chemisorption
dominated in the adsorption process [42]. The difference in the
adsorbed concentration of adsorbate at equilibrium (qe) and at
time t (qt) is the key driving force for the adsorption, and the
adsorption capacity is proportional to the number of active
adsorption sites on the adsorbent [43]. There are three steps
involved in pseudo second order kinetic model: (i) the ammonium
ions diffuse from liquid phase to liquidsolid interface; (ii) the
ammonium ions move from liquidsolid interface to solid
surfaces; and (iii) the ammonium ions diffuse into the particle
pores [23]. Herein, the diffusion of ammonium ions from aqueous
phase was much faster than the surface and intraparticle diffusion
processes because the adsorption was performed under stirring
conditions [22].
To reveal the relative contribution of surface and intraparticle
diffusion to the kinetic process, the kinetic adsorption data were
further tted with the WeberMorris model using Eq. (6).
WeberMorriss Eq: : qt kid t 1=2 C
Intraparticle diffusion is assumed to be the sole rate-controlling
step if the regression of qt versus t1/2 is linear and the plot passes
through the origin [44]. Our tting results show that the regression
was linearly, but the plot did not pass through the origin (C 6 0).
Therefore, the adsorption kinetics of NH4+ ions on zeolite was
regulated by both surface and intraparticle diffusion processes. As
can be seen from Fig. 8d and e, ammonium exchange by both
zeolites involves two stages. These two stages suggest that the
ammonium exchange process proceeds by surface sorption and
intraparticle diffusion. It has been suggested that the rst one can
be attributed to the instantaneous occupation of most available
surface sites by exchanging NH4+ ions onto zeolites particles. The
surface of zeolites was negatively charged at water pH below 7
(Fig. 6) and its rate is very fast. The second region is due to a gradual
adsorption stage, where the ammonium ions enter into zeolites
particle by intraparticle diffusion through the pores. The values of
intercept C provide information about the thickness of the
boundary layer and the resistance to the external mass transfer
increases as the intercept increases. The constant C was found to
increase from NZ (1.3642 mg/g) to ActZ (3.7406 mg/g) as shown in
Table 3, which indicates the increase of the thickness of the
boundary layer and decrease of the chance of the external mass
transfer and hence increase of the chance of internal mass transfer
[37,41].
Table 3 presents the results of tting experimental data to the
pseudo-rst, pseudo-second-order, Bangham and intraparticle
diffusion models. It can be seen from Table 3 that the correlation
coefcient R2 varies in the order: pseudo-second order >
Bangham > intraparticle diffusion > pseudo-rst order model
under all experimental conditions, which indicates that the
pseudo-second-order model is most suitable in describing the
adsorption kinetics of ammonium on zeolite.
3.8. Ammonium exchange isotherms
(3)
Isotherm tting with model equations is a key issue to explore
(4) model (FM) were evaluated as follows:
LM is based on the assumption that each active site can only
hold one adsorbate molecule. The linear form of LM is expressed
(5) as:
Ce 1 1
Ce (7)
q kqmax qmax
FM endorses the heterogeneity of the surface and assumes that
the adsorption occurs at sites with different energy of adsorption.
It is described as:
1
log q log kF log C e (8)
n
The linear plot of Langmuir isotherm of ActZ and NZ is shown in
Fig. 9a. It is noted that the values of qmax and k were calculated from
the slope and the intercept of the plot using Eq. (7) and are given in
Table 4. It will be seen that applicability of the simple Langmuir
equation for the present isotherm data indicates that the Langmuir
equation was able to properly describe the isotherm of ammonium
on the two zeolites (correlations coefcient >0.97). As shown in
Table 4, the ActZ had much higher ion exchange capacity than NZ. A
comparison with other zeolites from various literature reviews,
Nguyen and Tanner [14] reported a qmax value of 5.76 mg/g
ammonium adsorption on Australian natural zeolite. It has also
been reported that the qmax of ammonium removal using a Turkish
natural clinoptilolite was 8.1 mg/g [8]. Meanwhile a qmax value of
0.085 mg/g was reported by Demir et al. [36].
Fig. 9b shows the linearized Freundlich adsorption isotherm of
(6)
ammonium curve and the Freundlich parameters is presented in
Table 4. The FM of ActZ provides a slightly more consistent t to the
data compared with the FM of NZ. Similar values of 1/n which are
less than 1 have been reported for NH4+ removal using natural
zeolites from different countries [11,36].
To sum up, for the two zeolites, the experimental data are better
tted by the LM than FM as can be seen from the higher R2 in
 A. Alshameri et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554564 561

Fig. 8. Pseudo-rst order (a), pseudo-second-order (b), Bangham kinetic plots (c) and intra-particle diffusion of both zeolites ActZ (d) and NZ (e) for NH4+ removal.

Table 4. In Langmuir and Freundlich equations, coefcients K and 3.9. Thermodynamic study
KF represent the maximum amount that can be sorbed. Both values
for K and KF indicated that the activated zeolite has the higher The effect of temperature on ammonium exchange was studied
sorption capacity than the natural zeolite as shown in Table 4. at 25, 35 and 45 8C. Fig. 10 indicates that the amount of ammonium
exchanged onto zeolite increases with a decrease in temperature. A
Table 3
similar trend was also observed of some adsorbents, including
Kinetic parameters for NH4+ removal using various kinetic models.
Turkish clinoptilolite [8], Turkish zeolite [3], yash and sepiolite
Kinetic model Parameters [40], and NaA zeolite [45]. This may be due to a tendency for the
Pseudo-rst order K1 (min1) qe (mg/g) R2 ammonium molecules to escape from the solid phase to the bulk
Absorbent
phase with the solution temperature increase [3,45]. In contrast,
ActZ 0.0888 0.119123 0.954 increases in the NH4+ adsorption capacity with increasing
NZ 0.0165 2.5126 0.918 temperature have been reported for some other adsorbents
Kinetic model Parameters
[2,9]. Therefore, by comparing the results of the present work
Pseudo-second order
with those of the literature, it can be concluded that the effect of
h (mg/g min) qe (mg/g) R2
temperature on the adsorption of ammonium depends on both the
Absorbent nature of the adsorbent and the selected experimental conditions
ActZ 2.7156 3.821 0.999
[21]. Furthermore, ammonium exchange capacity decreases with
NZ 0.1646 3.28 0.997
increasing temperature due to a weakening of the attractive forces
Kinetic model Parameters between NH4+ and adsorbent sites [41] and when the temperature
Bangham model K0 a R2 increases, solubility of ammonium increases and its adsorption
Absorbent
decreases [37]. The thermodynamic parameters, such as Gibbs
ActZ 201.609 0.0379 0.979 energy (DG8), enthalpy (DH8), and entropy (DS8), for the adsorption
NZ 25.616 0.2981 0.958 of ammonium on zeolites were calculated using the following
equations:
Kinetic model Parameters
Intraparticle diffusion model Kid C R2 qe
K0 (9)
Absorbent Ce
ActZ 0.0102 3.7406 0.957
NZ 0.0977 1.3642 0.966 DG RT ln K 0 (10)
562 A. Alshameri et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554564

Fig. 9. The linearized Langmuir (a), Freundlich (b) of ActZ and NZ and Langmuir (c), Freundlich (d) adsorption isotherm of NH4+ curve at different temperature of ActZ.

Table 5
Change of thermodynamic parameters with temperature.
DG DH  T DS (11) Temperature (8C) K0 DG8 (kJ/mol) DH8 (kJ/mol) DS8 (kJ/mol)
25 2.89 2.8662 49.384 0.1561
DH  DS
ln K 0  (12) 35 2.01 1.3052
RT R 45 0.82 0.224
Eq. (12) represents a mathematical relationship between K0 and
1/T. The values of K0, DG8, DH8 and DS8 parameters are summarized
in Table 5. Change in the standard free energy DG8 has negative the negative value of the standard entropy change DS8 (0.1561 kJ/
values (2.8662 and 1.3052 kJ/mol) at 25 and 35 8C, respectively, mol) suggests that the randomness decreases the removal of NH4+
but positive value (0.224 kJ/mol) at 45 8C. The negative values of ions on the clinoptilolite [47].
free energy change (DG8) indicate that this adsorption process is The linear plot of LM and FM isotherm of ActZ at 25, 35 and
spontaneous; therefore, no energy input to the system is required. 45 8C is shown in Fig. 9c and d. The LM and FM parameters are
The higher negative value reects a more energetically presented in Table 5. The maximum value of K and KF at 25 8C
favorable adsorption [46]. For that reason, more energetically indicates that the NH4+ adsorption process is most effective at
favorable adsorption occurs at 25 8C. Change in the standard 25 8C. Comparing the correlation coefcients in Table 5 reects
enthalpy DH8 indicates a negative value of 49.384 kJ/mol;
therefore, ammonium exchange is an exothermic process. Also,

Table 4
Constants for equilibrium isotherm models of NZ and ActZ.

Isotherm model Parameters

Langmuir Qmax (mg/g) K (L/mg) R2

ActZ
25 8C 9.515 0.444 0.9982
35 8C 9.533 0.313 0.9986
45 8C 9.794 0.123 0.967
NZ
25 8C 3.445 0.1998 0.9772

Isotherm model Parameters

Freundlich KF ((mg/g)/(mg/L)1/n) 1/n R2

ActZ
25 8C 3.5743 0.2992 0.9716
35 8C 3.0634 0.3043 0.9442
45 8C 2.0305 0.3938 0.8867
NZ Fig. 10. Effect temperature on the exchange isotherm of NH4+ on activated zeolite
25 8C 1.252 0.5192 0.7363 (ActZ).
 A. Alshameri et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554564
Table 6
Data about adsorption and regeneration of zeolite.
Cycles
1 2 3 4
Ammonium adsorption 5.633 5.03 4.51 3.78
capacity (mg/g)
that LM yields a much better (R2 = 0.9670.998) t than that of the
FM (R2 = 0.8870.971).
3.10. Desorption and reusability
Accordingly, the ion-exchange and electrostatic adsorptions are
probably the main mechanisms for NH4+ ions removal by zeolite
under the selected conditions, through the following reactions
(Eq. (13)):
Ammoniumremoval : zeoliteNa NH4
! zeoliteNH4 Na
In this study, adsorption experiments were performed using 1 g
zeolite and 100 ml of 60 mg/L NH4+ at 25 8C for 40 min, and
desorption of adsorbed NH4+ onto zeolite was studied using 1 mol/
L NaCl, with zeolite/liquid ratio of 1 g/10 ml for 30 min at 70 8C,
and consecutive adsorptiondesorption cycles were repeated four
times. The results are shown in Table 6. There was a slight decrease
with the increase of cycle times in adsorption efciency from
5.633 mg/g for the rst cycle to 3.11 mg/g for the fth cycle. The
zeolite that was regenerated by four cycles in sodium solution had
high ammonium-removal efciency with its adsorption efciency
of 3.11 mg/g which is close to that of natural zeolite (3.344 mg/g).
4. Conclusion
The characteristics of Chinese (Hulaodu) natural zeolite (NZ),
activated zeolite (ActZ) and their efcacy in removing ammonium
were investigated. The following conclusions were made from the
experimental results:
 1 mol/L of NaCl, stirring time of 30 min and 70 8C were found to
be the optimum activation conditions for the zeolite with
excellent removal of NH4+.
 The highest adsorption capacity was obtained at pH 7 for both
zeolites and the maximum ammonium adsorption was rapidly
attained within 40 min and 300 min for activated zeolite and
natural zeolite, respectively.
 Langmuir adsorption isotherm of both zeolites t well with the
equilibrium adsorption data, and this adsorption process agrees
very well with pseudo-second-order kinetics rate model.
 DG8, DH8 and DS8 values reveal the exothermic and spontaneous
nature of the process and low temperature (25 8C) favors the
NH4+ removal on the zeolite.
 The adsorption capacity of activated zeolite is decreased to
3.11 mg/g which is close to that of natural zeolite (3.344 mg/g)
after being regenerated four times. Based on these results, the
study shows that Chinese (Hulaodu) natural zeolite can be used
as cheap, efcient and ecofriendly adsorbent for removing
ammonium from water and wastewaters.
Acknowledgment
This study was supported by Engineering Research Center of
Nano-Geomaterial of Education Ministry, China University of
Geosciences, Wuhan.
563
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