1.

Removal of ammonium from wastewater using calcium form

clinoptilolite
Zhi-Yong Ji a,b, Jun-Sheng Yuan b, Xin-Gang Li a,c,
a School of Chemical Engineering and Technology, Tianjin University, 300072 Tianjin, PR China
b School of Chemical Engineering and Technology, Hebei University of Technology, 300130 Tianjin, PR China
c National Engineering Research Center for Distillation Technology, Tianjin University, 300072 Tianjin, PR China
Received 16 January 2006; received in revised form 5 June 2006; accepted 8 July 2006
Available online 14 July 2006
2. Experimental
2.1. Preparation of CaY Clinoptilolite samples used in this study were taken from Inner Mongolia
Autonomous Region, China. The chemical composition of the clinoptilolite is shown in Table 1. All chemicals
used in the study were of analytical grade and mainly purchased from Kewei Chemical Reagent Co. (Tianjin,
China). All solutions and dilutions were made using distilled water. The chosen clinoptilolite was ground and
sieved into 0.4250.970mm mesh (between 20 and 40 mesh) particle size and then washed twice with distilled
water (volume ratio of liquid/ solid 3:1) to remove any non-adhesive impurities and small particles. NaY was
gained by treating the samples three times with saturated NaCl solution at boiling point for 2 h, and then
changed into NH4 +-formed clinoptilolite (NH4Y) by washing it with 1 mol/l NH4Cl solution for 20 min at room
temperature. Finally, CaY was prepared through washing the NH4Y with Ca(OH)2 solution at boiling point for
23 h.
2.2. Batch experiments
In the batch studies, the effects of pH and temperature on ammonium removal efficiency by CaY were
examined by using ammonium chloride solution. Experiments were all performed in a column of 7mmin
diameter and 250mmheight and operated in the downflow mode.

Chemical composition of clinoptilolite
Component wt.%
SiO2 68.27 1.23
Al2O3 7.48 0.31
Fe2O3 1.95 0.20
CaO 2.61 0.15
K2O 1.69 0.02
Na2O 0.68 0.03
MgO 1.87 0.15
H2O 6.26 0.52
Loss on ignition at 1000 C 7.86 0.36
2.2.1. Effect of pH value
In order to find out the optimum pH value, a 1000 ml of ammonium chloride solution of 300 mg NH4+-N/L was
prepared. The solutions were adjusted with hydrochloric acid or
calcium hydroxide to pH values ranging from 4 to 9 and were fed into the column system (with approximate 10
g of CaY) at 20.2 ml/min. Preliminary tests had confirmed that 20.2 ml/min was an optimum flowrate. The
outflow was filtrated with a 0.45 _m microporous membrane filter. The samples were analyzed by the standard
Nesslerisation method using the 721-spectrophotometer (Shanghai, China) equipped by glass cuvette with an
optical way length 1 cm. The maximum exchange capacity of NH4 + on the samples was calculated from the
margin between the initial and final ammonium concentrations. All the data reported were the average values
derived from triplicate samples. Being compared with CaY, the equilibrium uptake of ammonium ion onto NaY
was measured at corresponding pH value.

2.2.2. Ion exchange and adsorption isotherms
The ion exchange reaction is a stoichiometric process, where one equivalent of an ion in the solid phase is
replaced by equivalent of an ion from solution. The reaction may be written as
Ca(Z)2+ + 2NH4(S)+ 2NH4(Z)+ + Ca(S)2+ (1)
The subscripts Z and S refer to the clinoptilolite and solution phase, respectively. The ion exchange and
adsorption isotherms characterize the equilibrium of an ion in solid phase with the concentration of
the ion in solution. The CaY and 0.1 mol/l NH4Cl solution were placed in a 250 ml flask and shaken in a
thermostated shaker for 2 h, which was sufficient for reaching equilibrium. Some experiments were done for
different clinoptilolite (g)/solution (ml) ratios. The solid-to-liquid ratio ranged from 1/6 to 1/100. At the
designated time the two phases were separated by filtration through a 0.45_m microporous membrane filter and
the solutions were analyzed for ammonium. Three isotherms were obtained at 20(1), 40(1) and 60(1) C.
In order to determine the performance of CaY, As and Ac of NH4+ were necessary and they were described by
the following equation:
As =CNH4+/C0NH4+(2) Ac =VNH4Cl(CNH4+ C0NH4+) / mQ(3)
where As and Ac are defined as the non-dimensional parameter of NH4+ concentration in the aqueous and solid,
respectively, CNH4+ is the equilibrium NH4+ concentration (mmol/l) and C0NH4+ is the initial NH4+ concentration
in the aqueous phase (mmol/l), VNH4Cl is the volume of NH4Cl solution (l), m is the mass of clinoptilolite (g)
andQis the maximum exchange capacity of the CaY (mmol/g).

2.2.3. Kielland plots and thermodynamic properties
To obtain the Kielland plots, normalized values of Ac were used as suggested elsewhere [18,19]. The
thermodynamic properties were calculated from isotherms data and Kielland plots using the relationship listed
below [20,21]:
The equilibrium isotherms data obtained under known conditionscan be used for determining these
thermodynamic properties. To determine Ka for the examined exchange processed, the integral on the right-hand
side of Eq. (5) was evaluated graphically as the area under the corresponding ln Kc versus Ac curves, the
Kielland plots.

2.3. Desorption and regeneration
A consideration of practical interest with regard to the application of a new exchanger is its desorption and
regeneration ability. Clinoptilolite saturated with ammonium ions was regenerated by 0.2 mol/l Ca(OH)2
emulsion at 100110 C, with an ion exchange reaction happened as follows:
NH4(Z)+ + Ca(OH)2_Ca(Z)2+ + NH4OH (9)
NH4OH NH3 +H2O (10)
This operation went on with generating free ammonia, sosome ammoniated by-products (such as NH4Cl) can be
gained. The mass of the zeolite during the regeneration and the adsorption capacity of the regeneration modified
zeolite for ammonium ions after regeneration were measured, respectively.

2.4. Simulated wastewater treatment
In this investigation, column with an inner diameter of 30mm and height of 5000mm was used. The volume of
the clinoptilolite column was about 320 cm3 and the mass was about 1440 g. Column was filled with fine zeolite
0.4250.970 mm. In this study, some operation parameters and adsorption capacity of zeolite were confirmed.
The simulated wastewater (mainly containing 250 mg/l NH4Cl, 40 mg/l NaCl, 30 mg/l CaCl2, 20 mg/l KCl and
20 mg/l MgCl2) was fed into the clinoptilolite column system at 10, 40, and 70 ml/min flowrates with constant
influent pH of 7. Five liters of samples were taken from the effluent during operation and analyzed for NH4+-N
as previous description. The column was regeneration with Ca(OH)2 emulsion at pH 1112 and at flow velocity
of 5 ml/min. Preliminary tests had confirmed that 5 ml/min flowrate was optimum in regeneration process. The
regeneration solution was passed through the column in the down mode. Another loading cycle was then carried
out when the ammonia in the effluent was absent.


2. Preparation of highly ordered cubic NaA zeolite from halloysite
mineral foradsorption of ammonium ions
Yafei Zhaoa, Bing Zhanga,b,, Xiang Zhanga, Jinhua Wanga, Jindun Liua, Rongfeng Chenb
a School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, PR China
b Henan Academy of Sciences, Zhengzhou 450002, PR China

2. Experimental and methods
2.1. Raw materials
Natural halloysite mineral, used as silicon and aluminium sources in this work, was obtained from clay minerals in Henan
Province, China. The composition of halloysite was analyzed by chemical method. The analysis result indicates it contains
46.15% SiO2, 38.70% Al2O3, 0.033% MgO, 0.192% CaO, 0.05% Fe2O3, 0.03% K2O, 0.04% Na2O, 0.004% TiO2 and 14.60%
loss on ignition. Fig. 1 displays the typical XRD pattern and TEM image of the natural halloysite mineral. Fig. 1a shows that the
diffraction peaks of original mineral can be indexed to the hexagonal structured Al2Si2O5(OH)4, which are in agreement with the
reported values of Halloysite-7 with the lattice constants a = 5.13, c = 7.16 (JCPDS Card No. 29-1487). The diffraction peak (0
0 1) at 12.1 in 2 corresponding to a basal spacing of 0.72 nm, which further identifies the mineral as halloysite-7 . The
significant broadening of the diffraction peaks are ascribed to the very small crystallite size. Fig. 1b shows that the halloysite
particles have a cylindrical shape and contain a transparent central area that runs longitudinally along the cylinder, indicating
that the nanotubular particles are hollow and open-ended. The morphological parameters of the halloysite sample, measured
from the TEM image, are an average length of 0.51_m, a diameter in the range of 2050 nm, and an average pore diameter of
1040 nm. The small crystallite size and hollow structure endow halloysite mineral with a high specific surface area of about
79.62m2 g1, which is favourable for hydro-thermal reaction. Other inorganic chemicals used in the study, such as ammonium
chloride (NH4Cl), sodium chloride (NaCl), sodium hydroxide (NaOH) and hydrochloric acid (HCl) were all analytical grade
reagents. A stock solution (1000mgL1) was prepared by dissolving NH4Cl in distilled water; desired concentrations were
obtained when needed by diluting the stock solution with distilled water. HCl and NaOH solutions were used for pH adjustment.

2.2. Preparation of NaA zeolite
NaA zeolite was prepared using alkaline fusion followed by hydro-thermal treatment method. 2 g of halloysite powder was
placed in a Ni crucible and fused with 2.6 g NaOH powder at 673K for 2 h to promote their reactivity. The fused mass obtained
was cooled and mixed with deionized water (38 mL) by magnetic stirring for 30 min until the reaction gel was homogenized.
The aluminosilicate gelwasaged for 2 hat 313Kinthe sealed Teflon reactor to rearrange the reactant for forming nuclei. After
that, the mixture was crystallized at 363K for 5 h under static condition. Solid powder was filtered-off, washed, dried at 383K for
12 h and the product was obtained.

2.3. Characterization
The as-prepared NaA zeolite was characterized by XRD, FTIR,
SEM and TEM. XRD pattern was obtained using a Philips X Pert-Pro diffractometer with Cu K_ (_ = 0.154 nm) radiation
operating at 35 kV and 25mA and a step width of 0.04. Fourier transformed infrared spectroscopy (FTIR) was recorded on a
Nicolet Nexus 470 FTIR spectrometer in the range 4004000cm1. Field emission scanning electron microscopy (FE-SEM) was
performed using a JSM-6700F SEM (JEOL), operating in backscatter mode at 20 kV accelerating voltage. Transmission
electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) were obtained with a
FEITECNA1G2 electron microscope operating at an acceleration voltage of 120 kV.

2.4. NH4+ adsorption experiments
The batch experiments were carried out in stopper conical flasks containing 50mL varying initial concentration of NH4+ solutions
and adsorbent dose. Then the samples were agitated on a thermostated shaker with a shaking of 180rpm at 288338 K. On
reaching equilibrium the adsorbent was eliminated by centrifugation at 3000rpm and then filtered with 0.45_m membranes. The
initial and final ammonium concentrations remaining in solutions were analyzed using a UV spectrophotometer (Shimadzu, UV-
3000) by monitoring the absorbance changes at a wavelength of maximum absorbance (420 nm). The removal efficiency (R,
%), the amount of ammonium adsorbed at time t (qt, mgg1) and at equilibrium (qe, mgg1) was calculated by using the
following equations, respectively.



3. Improving the ammonium ion uptake onto natural zeolite by using an
integrated modification process
Zhu Liang, Jinren Ni
The Key Laboratory of Water and Sediment Sciences, Ministry of Education, Department of Environmental Engineering, Peking University, Beijing 100871,
PR China


2. Materials and methods
2.1. Raw material
The raw zeolite in this study, with particle size in the range of 1020mm, was obtained from a large deposit in Henan Province
of China. Clinoptilolite was the major component with 55% content. As accessory minerals, feldspars and quartz were in
relatively large quantities with contents of 19% and 18%, respectively (Table 1). According to the chemical composition of the
raw zeolite (Tables 2 and 3), the molar ratio of (Mg + Ca)/(Na +K) was 1.37, and mol percentages of calcium and sodium to the
four cationswere 44.9 and 15.2, respectively, indicating that calcium ionwas the main exchangeable cation and that the
rawmaterial could be classified as Ca-rich zeolite. The raw zeolite was prepared as a starting material for the present
experiment after washing and air-drying.
Table 2
Average chemical composition of the raw zeolite (wt%).
SiO2 65.72
Al2O3 13.50
Fe2O3 1.30
CaO 3.10
MgO 0.63
K2O 3.14
Na2O 1.16
MnO 0.050
TiO2 0.212
P2O5 0.040
LoIa 11.12
Total 99.96
Si/Al 4.13
a LoI represents loss of ignition.
2.2. Reagent
All chemicals used in this study were analytical grade reagents of the highest quality available, including reagents and high-
purity ion-free water. We prepared stock solution of 1000mg NH4+-N/L using ammonium chloride (NH4Cl).

2.3. Experiment setup
2.3.1. Pretreatment
The raw zeolite was firstly ground in a mill with three agateheads (XPM-_120, China) and sieved to obtain samples with
different sizes, and then AIUs of differentsampleswere investigated to select appropriate size. Finally, enough zeolite with
optimumsize was prepared and stored in a vacuum desiccator for future modification. The pretreated zeolite with appropriate
size was namedZ-P.

2.3.2. Individual calcination
Z-P was calcined in a muffle furnace at different temperatures for 2 h, and then the optimal temperaturewas selected on the
basis of AIU performance.

2.3.3. Individual salt modification
The modification consisted of the following three steps:
Step 1: 10.000 g of Z-P was treated with 150mL of 1.5M NaCl solution for 24 h at given temperature in a stirrer with
thermostat. After the mixture was allowed to settle and the supernatant was decanted, another 150mL of 1.5M NaCl solution
was added into the mixture for another 24-h modification under the same
condition.
Step 2: The solid was repeatedly washed with deionized water and centrifugally filtered at 4000rpm for 20 min.
Step 3: The solidwas dried firstly at 45 C for 12 h and then 105 C for 1 h in an oven, and the dried sample was ground in an
agate mortar and sieved with 140-mesh sieve. The produced material with 24-h modification was signed as
once salt modified zeolite (Z-M(1)), and that with 48-h modification was twice salt modified zeolite (Z-M(2)). The effects of
temperature and modification times on AIU were investigated, respectively.

2.3.4. Combined treatment with calcination and salt modification
Effects of two different procedures on AIU, calcination followed with salt modification and salt modification followedwith
calcination, were explored, respectively, and the resulting zeolites were named (Z-C-M) and (Z-M-C), respectively. Finally, the
optimum modification condition and procedure were proposed.

2.3.5. Measurement of AIU and methods of isotherm and kinetic
studies of ammonium ion exchange and adsorption Measurement of AIUwas performed as the following procedure: 1.000 g
material was weighed into 150-mL conical flask, and then aliquot deionizedwater and ammonium stock solutionwere added
so as to obtain mixture with total volume of 100mL and initial NH4+-N concentration of 25 mg/L. After reacting for 2 h in a
shaker at 220rpm at 301 C, the suspension was centrifuged and then filtered with 0.45_mmembrane to remove the zeolite
particles for analysis. AIU (mgNH4+-N/g zeolite)was calculated according to Eq.
(1):
AIU = (C0 Ct )V1000m
Table 3
Mol percentages of Na and Ca of four cations (Na, K, Ca and Mg) and Si/Al ratio for the different zeolite by unit cell composition EDX analyses.
Samplea Z-R Z-M(1) Z-M(2) Z-M(2)-C(400)
Na (mol%) 15.2 56.1 63.8 62.3
Ca (mol%) 44.9 14.0 0 0
(Mg + Ca)/(Na +K) molar ratio 1.37 0.16 0.09 0.10
Si/Al (mol ratio) 4.13 4.17 4.06 3.61
a Z-R, Z-M(1), Z-M(2) and Z-M(2)-C(400) represent the raw, once salt modified at 30 C, twice salt modified at 30 C and modified by twice salt modification
followed with
calcination at 400 C zeolites, respectively.
where C0 and Ct are the concentrations of initial and final NH4+-N in the solution at time t (mg/L), respectively, V is the solution
volume (mL) and m is the weight of raw or modified zeolite (g). The ammonium ion-exchange isotherms and kinetics of different
zeoliteswere evaluated by using Langmuir isotherm model (Eq. (2)) and Bangham adsorption rate equation (Eq.
(3)),respectively:
qe = qmbCe1 + bCe (2)
qt = kt1/m (3)
where qe is the equilibrium adsorption capacity (mgNH4+-N/g zeolite), qm is the maximum adsorption capacity (mgNH4+-N/g
zeolite), b (L/mg) is the equilibrium adsorption constant, and Ce is equilibrium liquid phase concentration (mgNH4+-N/L), qt is the
amount of NH4+-N adsorbed at time t (mgNH4+-N/g zeolite), and k (mg/(g min)) and m are the adsorption rate constants.
In all runs, the pH value of mixed solution was less than 7.1 and it was thus assumed that all ammonia existed in the ionic form
[16] and was available for ion exchange and adsorption, and ionic strength was assumed to be equal to molar concentration
of ammonium ion due to the usage of high-purity deionized water and without addition of other chemicals than NH4Cl.

2.4. Mineralogical and chemical analyses
The mineralogical transformations of the raw and treated zeoliteswere monitored by X-ray diffraction (XRD), using an XPert
Pro MPD diffractometer (Panalytjcal, Netherland) operating at 40 kV and 40mA. A 0.017 (2_) scanning step and 20 s scanning
time per step was used. The diffraction patterns were identified using High-score Plus files. The chemical composition of the
rawzeolitewas determined by X-ray fluorescence spectrophotometer (ARL ADVANTXP+, Thermo Electron Corporation, USA).
Si/Al molar ratio was calculated from the chemical composition. The microstructure of the samples was observed by scanning
electron microscope (SEM) using a Quanta 200FEG microscope (USA), and the unit cell average element composition of
clinoptilolite crystalswas analyzed by energy dispersive X-ray spectrometer. BET surface area, pore volume and pore sizewere
determined by nitrogen adsorption/desorption, using a Micromeritics ASAP 2010 apparatus. According to the standard method
issued by the Environmental Protection Agency (EPA) of China, the concentration of NH4+-N was determined by using the
Nesslers reagent spectrophotometric method with a Unico spectrophotometer (model UV-2102PCS) at the corresponding
wavelength (_ = 540 nm). All experiments wereperformed in duplicate and the average valueswere used for datum analyses.



4. Kinetic and equilibrium studies of the removal of ammonium ions from
aqueous solution by rice husk ash-synthesized zeolite Y and powdered and
granulated forms of mordenite
Alias Mohd Yusofa,!, Lee Kian Keata, Zaharah Ibrahimb, Zaiton Abdul Majida, Nik Ahmad
Nizamb
a Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 Skudai, Johor, Malaysia
b Faculty of Biosciences and Bioengineering, Universiti Teknologi Malaysia, 81310 Skudai, Johor, Malaysia

2. Materials and method
2.1. Materials and chemicals
Zeolite Y in the sodium form was synthesized from rice husk ash as the source of silica via seeding and ageing techniques. The
procedure for the synthesis of zeolite Y and the structure identification are described elsewhere [16]. Naturally occurring
mordenite was obtained from a large deposit in Tasik Malaya, Indonesia. Stock solutions of the ammonium ions were prepared
from analytical grade ammonium chloride, NH4Cl (GCE).

2.2. Characterization techniques
The structure of the zeolite NaY and mordenite samples were examined by a powder X-ray diffraction using a Bruker AXS
GmbH HR diffractometer with Cu K! radiation (! = 1.5418 ) at room temperature provided the structural investigation of the
sorbents with data collected in the range of 550# at a scan rate of 0.05# s1. The elemental analysis of zeolites was performed
by using energy dispersive X-ray (EDX) spectrum of the samples were recorded using a Zeiss Supra 35VP field-emission
scanning electron microscope. The total cation exchange capacity (CEC) of zeolite is the amount of all exchangeable cations
and it is defined by the number of equivalents of fixed negative charges per amount of zeolite [17]. However, it should be noted
that the total CEC does not correspond to the operating exchange capacity which is commonly lower in practise [17,18]. The
total CEC measured by ammonium displacement from the sodium-saturated zeolite samples in this case was determined using
a prescribed method [19]. Sodium-saturated zeolite was prepared by exhaustive exchange of the raw zeolite with pH-buffered
sodium acetate (1.0N) solution. The resulting mixture was washed three times thoroughly with 2-propanol to remove excessive
loosely bound sodium on the zeolite. The total CEC measurement was accomplished by mixing 1.0N ammonium
acetate solution (3 folds) with the sodium-saturated zeolite. The two phases were separated by centrifugation and the washes
mixed together prior to atomic absorption spectroscopy (AAS) analyses on a PerkinElmer, model AAnalyst 400. Total
concentration of sodium in the solution constitutes the total CEC of the zeolite.

2.3. Ammonium removal study
2.3.1. Kinetic studies
Kinetic studies were conducted at room temperature using 400mL of ammonium solution (pH 7) and fixed amounts of
adsorbents (1 g) in a 500mL conical flask. The reaction mixture was stirred using a Teflon-coated magnetic bar driven by a
magnetic stirrer. The two phases of samples taken at the designated times were separated by syringe filtration through a
0.45"m membrane filter or centrifugation. The initial and final ammonium concentrations in the supernatant were analyze by the
standard Nesslerization method using a Hach DR 4000 Spectrophotometer [20,21].

2.3.2. Batch equilibrium studies
Equilibrium study on removal ammonium was carried out in batch system at room temperature with accurately known amount
of 0.1 g of zeolite sample equilibrated with 40mL of ammonium solution in a 50mL polypropylene centrifuge tube. Shaking was
applied by placing the sealed tubes in an orbital shaker with a constant shaking rate of 150 rpm. The shaking time for zeolite Y,
powdered mordenite and granular mordenite were 2 h, 4 h, and 2 d, respectively which was proven through the kinetic studies,
for the equilibrium of exchange to reach. At the end of the sorption experiments, centrifuge tubes were removed from the
shaker and the solutions separated by centrifugation. The final ammonium concentrations remaining in the solutions were
determined using a method described earlier. The adsorption equilibrium data were obtained by varying initial ammonium ion
concentrations while other variables such as the mass of adsorbent, contact time, shaking rate and initial pH were kept
constant.

2.4. Effect of pH on zeolite exchange performance
The effect of pH on adsorption of ammonium onto zeolite samples was investigated at room temperature by varying the initial
pH of 50mgL1 of ammonium solution (40 mL) for a fixed zeolite dosage of 0.1 g. The pH of the solutions was adjusted to within
410 using HCl or NaOH. The clear supernatant solutions were extracted after centrifuge at the end of the equilibrium time. The
initial and final ammonium concentrations remaining in solution were analyzed.


5.Removal of ammonium from municipal wastewater using
natural Turkish (Dogantepe) zeolite
M. Sarioglu
Department of Environmental Engineering, University of Cumhuriyet, 58140 Sivas, Turkey
Received in revised form 15 March 2004; accepted 18 March 2004

2. Experimental
2.1. Preparation and measurements of zeolite samples
Zeolite samples used in this study were taken from Dogantepe (Amasya), Turkey. The mineralogical
composition of zeolite was determined as 45% clinoptilolite, 35% mordenite,
15% feldspar [(Na, K, Ca)AlSi3O8], and 5% quartz [SiO2] [24]. The theoretical exchange capacities of
clinoptilolite and mordenite are 330 and 230 meq. per 100 g, respectively [39]. The theoretical exchange
capacity of zeolite used in this study was calculated as 2.29 meq. g1 by using mineralogical composition. The
samples were ground and sieved to 10 + 20 mesh (12 mm) particle size and then washed with distilled water
to remove any non-adhesive impurities and small particles, and then dried at 105 C for 24 h to remove
moisture. Since NH4+-N ion removal by using natural zeolite wasaimed, preconditioning with NaCl, HCl,
HNO3, H2SO4, and NaOH, etc. solutions was not considered. A few zeolite samples, however, were treated with
HNO3 before usage, justto compare the results obtained from natural and washedsamples.
Chemical composition of zeolitic sample is given in Table 1. The mineral from Dogantepe is a mixture of
clinoptilolite, mordenite, and other phases. This mixture is referred to as zeolite in the following sections. The
mineralogical features of samples were determined using Rigaku D Max IIIC X-ray diffractometer in
Cumhuriyet University.The mineralogical compositions of original and treated samples were determined by
using JCPDS (1990) files [40]. Semi-quantitative weight percentages of samples were calculated by using
mineral intensity factors based on an external standard method [41]. In the experimental studies, the ammonium
ion concentration in the solution was determined by using Nessler method according to standard methods
[42]. Absorbance values were read using a Shimadzu UV-1201V spectrophotometer. In acidic conditions, X-ray
diffraction analyses were done to find out the structural stability of samples for pH 4, 4.5, and natural one. The
experiments were studied by the batch and continuous (column) processes.
Table 1
Chemical composition of Dogantepe (Amasya) zeolite
Oxide (wt.%) Elements ppm
SiO2 70.27 Cr 8
TiO2 0.19 Ni 1
Al2O3 12.90 Co 4
_Fe2O3a 1.38 Cu 13
MnO 0.02 Pb 26
MgO 1.71 Zn 54
CaO 2.05 Rb 106
Na2O 3.21 Ba 137
K2O 1.49 Sr 1470
P2O5 0.04 Ga 15
LOIb 6.57 Nb 7
Total 99.43 Zr 182
Y 16 Th 25
a Total Fe.
b Loss on ignition (1000 C).
M. Sarioglu / Separation and Purification Technology 41 (2005) 111 3

2.2. Batch experiments
In the batch studies, the effects of stirring time and ammonium concentrations on ammonium removal efficiency
by zeolite were examined by using synthetic NH4+-N solutions.

2.2.1. Effects of stirring time and ammonium concentration
In order to find out the optimum stirring time, 1 g zeolite samples (12 mm) were added into 100 ml of 88 mg
l1 ammonium solutions in 250 ml beaker and stirred for 5120 min at a fixed temperature (20 C) and 150 rpm
rate. Then the effect of initial ammonium concentrations (8.8885 mg
NH4+-N l1) on the removal efficiency was investigated at the same working conditions (T = 20 C; 150 rpm).

2.2.2. Adsorption isotherms
The ion exchange reaction is a stoichiometric process, where one equivalent of an ion in the solid phase is
replaced by equivalent of an ion from solution. The reaction may be
written as
Na+(z)+ NH4+(s) Na+(s)+ NH4+(z)
The subscripts z and s refer to the zeolite and solution phases, respectively. The ion exchange isotherms
characterize the equilibrium of an ion in solid phase with the concentration of the ion in solution. Graphical
representation usually shows all possible experimental conditions at a given temperature. Ammonium removal
capacities for zeolite were studied with ion exchange isotherms. For the effective utilization of a natural zeolite
as an ion exchanger, it is essential to have chemical models that help to describe accurately NH4+-N
equilibrium. Empirical equations such as the Freundlich and the Langmuir were fitted to experimental data.
Freundlich and Langmuir isotherms were formulated at 20 min stirring time, 10 g l1 zeolite per solution ratio
and 8.8885 mg NH4+-N l1 concentrations at room temperature (20 C) and 150 rpm stirring Zeolite
speed to main zeolite particles in suspension. Total amount
of adsorbed ammonioum was divided by the dry weight of
zeolite to find out the average amount adsorbed, which was
plotted against effluent ammonium concentrations to show
an isotherm test.

2.3. Column (continuous) experiments
The column loading capacity was determined from the breakthrough curve by using samples taken from
Cumhuriyet University wastewater treatment plants. The composition of wastewater taken from wastewater
treatment plant effluent is as follows (mg l1): NH4-N = 512; chemical oxygen demand (COD) = 18; biological
oxygen demand (BOD) = 10; suspended solids (SS) = 8mg l1; PO4 = 0.03; Na = 12; K = 0.5; Ca = 161; Mg =
16.5. Generally, breakthrough curve is illustrated as S shape for most adsorption processes in water and
wastewater treatment. Some parameters, such as initial pollutant concentration,
pH, flowrate, adsorption mechanism, equilibrium conditions and particle size, conditioning, and column
diameter affect the real shape of breakthrough curve [28,4346]. The main point in column design is
breakthrough analysis. Therefore, in this paper; effects of some factors (flowrate, pH, washing with acid, and
regeneration) on breakthrough capacities were investigated. However, the effect of particle size on breakthrough
capacity was not considered. Based on literature, studies with ammonia removal, particle size was selected in
the range 12 mm. Hlavay et al. [45] found that 0.51mm particle size gave the highest performance. Semmens
et al. [43] concluded that small particle sizes increased the removal efficiency. Milan et al. [47] studied
ammonia removal by ion exchange in columns packed with homioniczeolite with a particle size of 5 mm.
Ratanatamskul et al. [48] used a natural clinoptilolite with a size of 715mm for residual ammonia and
phosphorus removal from domestic wastewater. Baykal and Gven [10] used clinoptilolite with a size of 1-2mm
to remove ammonia from domestic wastewater. As expected, as the particle size decreases, the surface area and
adsorption capacities increase.
Experiments were all performed in a column of 1.20 cm in diameter and 55 cm height and operated in the
upflow mode. The column experiments were conducted at 5 and approximately 12 mg NH4+-N l1. The sample
was filtrated with a filter paper (0.45_m) in order to eliminate inert materials. The experimental setup is
illustrated in Fig. 1. The featuresof setup are given in Table 2.

2.3.1. Effect of flowrate
Flowrates determined contact times were controlled with a pump. Wastewater was fed into the column system at
4, 2, 1, and 0.5 ml min1 flowrates (5, 10, 20, and 40 min contact times) with constant influent pH value as 4.5.
This process continued until zeolite reached saturation (C/Co = 1). For the flowrates of concern, the
breakthrough curves of thesystem were drawn and compared with each other.

2.3.2. Effect of pH
The effect of different pH values ranging between 4 and 7.5 at optimum flowrate (0.5 ml min1) was
investigated. It was observed that the highest removal efficiency was achieved at pH 4, based on the results of
breakthrough curves. Since complete removal of NH4+-N was not possible to achieve at an initial concentration
about 12 mg NH4+-N l1 in column experiments, initial NH4+-N concentration was decreased to 5mg NH4
+-N l1 and the experiment was repeated to observe if 100% removal efficiency could be reached.

2.4. Washing samples with acid
The effect of washing the zeolite sample with acid (0.005M HNO3) at 150 rpm stirring rate was also considered.
Following treatment with acid, it was washed out with distilled water and dried at 105 C for 24 h before using
it in column experiments to create breakthrough curves.

2.5. Regeneration experiments
NaCl solution (1 M) was used for regeneration. The NaCl solution was passed through the column at three
different
Table 2
Characteristics of the experimental system
Water flow rate 0.5, 1, 2, 4ml min1
Column height 55 cm
External diameter 1.20 cm
Internal diameter 1.06 cm
Area 0.88 cm2
Column material Glass
Packet height 20 cm
Bed volume 19 cm3
Ion exchanger
Type Clinoptilolite
Mass 15 g
Size range 12mm
Type of pump Peristaltic pump, Master flex, 100
flowrates (0.3, 0.2, and 0.1 ml min1) and a constant pH of 10 to determine the effect of contact time on
regeneration, and thus, on ammonium removal efficiency. The ammonium removal efficiencies obtained using
regenerated samples were compared with those obtained using natural ones.

2.6. Cation exchange capacity
Cation exchange capacity was measured with a Jenway Model Flame Photometer through analyzing sodium
concentration in the effluent. The details of the method used for the determination of cation exchange capacity
of sample are described by Semmens and Martin [37]. Ten grams of sample was given into column and 2M
NaCl solution was added in order to convert the zeolite to Na+ form. Residual NaCl solution on zeolite surface
was washed with distilled water. Then 100 ml 1M KCl solution was given into column. Since the K+ selectivity
of clinoptilolite is higher withrespect to its Na+ selectivity, saturation with Na+ was first performed. Then, Na+
ion concentration in KCl solution was measured with flame photometer and cation exchange capacity was
calculated.


6. The investigation of mechanism, kinetic and isotherm of ammonia and
humic acid co-adsorption onto natural zeolite
Gholamreza Moussavia,, Sadegh Talebia, Mehrdad Farrokhib, Robabeh Mojtabaee Saboutic
a Department of Environmental Health Engineering, Faculty of Medical Sciences, Tarbiat Modares University, Tehran, Iran
b Department of Environmental Health Engineering, Faculty of Health, Gilan University of Medical Sciences, Rasht, Iran
c Gilan Rural Water and Wastewater Co., Rasht, Iran


2. Materials and methods
2.1. Materials
The natural zeolite used in this study was obtained from a local mine with a huge deposit. The zeolite pieces were initially
crushed and then grinded to size 0.50.6 mm. The zeolite particles were first washed with distilled water to remove the
impurities and debris, and dried, before being used in experiments. The water used in the batch experiment was prepared from
mixing aliquots of ammonia (1000 mg/L) and/or humic acid (100 mg/L) stock solutions with distilled water. The stock solutions
of ammonia and humic acid were prepared by dissolving required amounts of NH4Cl and humic acid, respectively, into distilled
water. All chemicals were of analyticalgrade.

2.2. Adsorption experiments
Batch experiments were conducted in a jar instrument housed in a custom-made cabinet, equipped with a heater and
thermostat to regulate the temperature at the required level. For each batch adsorption experiment, 100 mL of solution
containing a given concentration of target contaminant(s) and with the desired level of pH (regulated with 0.1 N HCl or NaOH)
was first transferred into the beaker. Then a predetermined amount of zeolite was added into the vessel and the content was
stirred at 100 rpm using the paddle-type mixer for a given time. The suspension was finally passed through
a filter (0.45 _m pore size) and the filtrate was analyzed for the target compound(s). The pH, zeolite particle size, initial
contaminant(s) concentration, temperature, cations type, and contact time were the selected variables in this phase of the work.
The experimental runs and the corresponded conditions are given in Table 2. Performance of the batch tests was evaluated as
adsorption efficiency (%) and capacity (mg/g) of the contaminant(s).

2.3. Analysis
The zeolite (both fresh and used) was characterized for the surface morphology, composition, structure, crystallinity, and
surface functional groups. The surface morphology of the zeolite was observed using scanning electron microscopy (SEM)
technique (Philips-XL30 Electron Microscope). X-ray fractionation (XRF) and X-ray diffraction (XRD) techniques using Philips
XPERT were used for analyzing the chemical composition and the crystallinity phase of the zeolite samples. The BET specific
surface area and pore volume were determined by nitrogen gas adsorption analyzer (Micromeretics/Gemini-2372). pH of zero
charge point (pHzpc) of zeolite was determined according to the pH drift procedure. The concentration of ammonia in water
before and after treatment was measured using the Neslerization method as describedin the standard methods [36]. The term
ammonia in this text represents
the sum of non-ionized (NH3) and ionized (NH4+) species. The

Table 2
Experimental runs and conditions.
Run Experiment Experiment Operational conditions
pH Ammonia(mg/L) Humic acid(mg/L) Zeolite (g/L) Mixingtime (min) Temperature (C)
1 Influence of pH of water 210 50 10 5 60 20
2 Influence of zeolite concentration 7 50 10 110 60 20
3 Adsorption kinetic of different concentrations 7 10100 210 5 590 20
4 Influence of temperature at various zeolite concentration 7 100 10 3,5,6 720 2050
5 Adsorption isotherm 7 100 10 110 720 2050

by measuring absorbance at 254 nm [36]. Concentration of sodium, potassium and calcium were measured using a flame
photometer. All tests were carried out twice and the average data are presented.


7.Removal of ammonium ion from aqueous solution using
natural Turkish clinoptilolite
Dogan Karadag a,, Yunus Koc a, Mustafa Turan b,, Bulent Armaganc
a Yildiz Technical University, Civil Engineering Faculty, Environmental Engineering Department, 34349 Besiktas, Istanbul,
Turkey
b Istanbul Technical University, Civil Engineering Faculty, Environmental Engineering Department, 34469 Maslak, Istanbul,
Turkey
c Harran University, Engineering Faculty, Environmental Engineering Department, 63300 Sanliurfa, Turkey
Received 24 October 2005; received in revised form 20 December 2005; accepted 21 December 2005
Available online 25 January 2006
2. Material and methods
Sample of clinoptilolite was obtained from the Esen Foreign Trade Co. in Western Anatolia, Turkey. Samples
were crushed and classified to a size range of 1.01.4 mm. Clinoptilolite was washed to remove the water
soluble residues and other undesirable material, and dried in an oven at 1005 C for 24 h. Chemical and
physical properties of sample was supplied by the producer. Mineralogical content of 85% is clinoptilolite, 10%
is feldspar and 5% is clay. Cation exchange capacity and bulk density of are 0.951.4 meq/g and 9001100
kg/m3, respectively. Chemical properties of the clinoptilolite sample are summarized in Table 1. The ion
exchange of NH4+ ion on clinoptilolite was carried out using a batch method. The batch experiments were
conducted using 0.5 g of adsorbent with 50mL of solutions in the range of 25150 mg/L initial NH4+
concentrations. Synthetic ammonia solutions were prepared by dissolving NH4Cl salt (analytical purity), in
distilled water. The bottles were placed on Gallenkamp orbital shaker at 25, 40 and 55 C and centrifuged at 200
rpm. The equilibrium concentrations of ammonium were determined analyzing samples after centrifugation
in the laboratory with the colorimetric method using the Nessler solution. Distilled and deionized water with a
conductivity value of 2106 mho s/cm was used in all experiments. Ammonium uptake (qe) was calculated
using the following equation:
qe = (C0 Ce)VM (1)
Where qe (mg/g) is the amount of total adsorbed ammonium ions (mg/g), C0 and Ce are initial and equilibrium
concentrations of ammonium in solution (mg/L), respectively. V (L) is the solution volume and M (g) is the
adsorbent weight.