Waste Biomass Valor (2012) 3:6174
DOI 10.1007/s12649-011-9084-4
ORIGINAL PAPER
Preparation of Free-Template Nanometer-Sized NaA
and X Zeolites From Rice Husk Ash
Zahra Ghasemi Habibollah Younesi
Received: 7 September 2010 / Accepted: 18 July 2011 / Published online: 5 August 2011
Springer Science+Business Media B.V. 2011
Abstract The main objective of the present study was to
synthesize nanozeolite NaA by a hydrothermal method
with extracted silica from rice husk ash as source in order
to reduce the mean particle size of zeolite NaA as well as
crystallization conditions by keeping the economic inter-
active in mind. High-grade amorphous silica was extracted
from rice husk ash by an appropriate alkali solution.
Amorphous extracted silica powder was composed of 88%
wt of SiO2. The effects of Na2O/SiO2 ratio in the initial
system, the crystallization condition, crystallization time,
crystallization temperature and shaking conditions (static,
stirring and shaking) on the properties of final products
were investigated. Various techniques including X-ray
diffraction, scanning electron microscope, energy disper-
sive X-ray, N2 adsorption/desorption and Fourier transform
infrared were then applied for characterization of the syn-
thesized products. The results showed that the crystalliza-
tion condition and alkalinity have a significant effect on the
structural properties of the synthesized nanozeolite NaA.
Without adding any organic additives, nanocrystals of Na
A ranging from 40 to 120 nm in size were synthesized at
40C and with 18 h aging, whereby crystals with a specific
surface area of 36.9 m2 g-1 and an average pore diameter
of 10.6 nm (using BJH method) were obtained. NaX
nanocrystals with crystallite size ranging from 70 to
260 nm were obtained from a sodium aluminosilicate
solution at 60C after 2 days in static crystallization con-
dition, whereby crystals with a specific surface area of
Z. Ghasemi  H. Younesi (&)
Department of Environmental Science, Faculty of Natural
Resources, Tarbiat Modares University, P.O. Box: 64414-356,
Noor, Iran
e-mail: hunesi@modares.ac.ir; hunesi@yahoo.com
89.9 m2 g-1 and an average pore diameter of 9.2 nm
(using BJH method) were obtained.
Keywords Rice husk ash  Nanozeolites NaA and X 
Synthesis  Silica
Introduction
In the past decade, the reduction of the zeolite particle size
from micrometer to nanometer scale has received much
attention due to the difference in properties of zeolite
nanocrystals from their micrometer-sized counterparts
[1, 2]. The reduction of the particle size from micrometer to
nanometer scale improves the catalytic selectivity and
reduces coke formation in some petroleum reactions. This is
due to changing the resistance of mass- and heat-transfers in
the catalytic and sorption processes in the nanometer scale
[3]. Moreover, zeolitic membranes and ordered porous
materials can be produced by nanocrystalline zeolites [46].
Rice husk as a major by-product of the rice-processing
industries is abundantly available in rice producing coun-
tries [7, 8]. In Iran, a large quantity of husk (630 thousand
tons) was produced in 2008. Rice husk contains 7085%
organic matter, with the remainder consisting of SiO2. The
combustion of rice husk in air results in the formation of
rice husk ash varying with the variety, climate and geo-
graphic location of growth [9]. After removing the organic
content by combustion, the ash contains silica with a purity
of about 90% [10]. Amorphous silica can be extracted from
rice husk ash by a suitable alkali solution [11]. In many
regions, its disposal as an agricultural waste is an envi-
ronmental issue [7]. As extracted silica source, rice husk is
a practical alternative to purely chemical sources, because
it is cheap, less selective and highly reactive [12] and
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therefore has been used as silica source for the synthesis of
different zeolite types such as A [13], beta [14], ZSM-5
zeolites [15]. Although rice husk ash has been used for
zeolite synthesis instead of pure chemical sources in
aforementioned studies but synthesis of zeolite NaA using
extracted silica from rice husk ash and in nanometer size
has not yet been reported. Also, a variety of organic tem-
plate for zeolite synthesis have used [1618], thus resulting
in the increase of operating cost for the industrial scale
production of nanometer-sized seolite. So far, zeolite L, A
and sodalite nanocrystals have been synthesized without
using any organic additives [1922]. These studies have
revealed that the formed gel plays an important role in the
formation of zeolite L, A and sodalite nanocrystals.
In this study, we also report simple and efficient syn-
thesis routes of nanometer-sized NaX zeolite using a low
cost, abundant and renewable source of amorphous silica
extracted from an agricultural waste. Although rice husk
ash has been used for zeolite synthesis instead of pure
chemical sources in aforementioned studies but synthesis
of NaX zeolite using extracted silica from rice husk ash
and in nanometer size has not yet been reported.
Green chemistry is commonly used in the preparation of
solid-state compounds, where mild temperature conditions
and environmentally friendly procedures are highly desir-
able. In the past decade, decreasing the crystallization time at
a moderate temperature, which favors the nucleation process
since the activation energy of crystal growth is generally
higher than that of nucleation [23, 24], has been successfully
achieved in the preparation of zeolite-type materials [25, 26].
In our previous study, the use of rice husk ash materials
for the synthesis of nanozeolite NaA without template has
been described. Our efforts were also directed toward
reducing crystallization time and achieving nanosize NaA
zeolite with narrow particle size distribution [27]. In the
present study, special attention was paid to the alkalinity,
crystallization time, temperature and shaking conditions on
synthesis of NaX nanozeolite, crystallization conditions
and the Na2O/SiO2 ratio of the initial system which control
the particle size distribution of nanometer-sized NaA and
X zeolites. To best of our knowledge, this is the first
report on the hydrothermal synthesis of nanometer-sized
NaA and X zeolites using extracted silica from rice husk
ash as source of silica, without adding any organic tem-
plates during the whole crystallization process.
Materials and Methods
Silica Extraction From Rice Husk Ash
The amorphous silica source was extracted from rice husk
ash according to Ghasemi and Younesi [27, 28]. In order to
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Waste Biomass Valor (2012) 3:6174
Table 1 The XRF analysis results of ash and extracted silica powder
Composition Ash (wt%) Extracted silica powder (wt%)
Fe2O3 0.10 0.01 0.047 0.003
CaO 0.54 0.03 0.085 0.005
K2O 0.10 0.01 0.12 0.01
SiO2 95.90 4.8 87.90 4.4
Al2O3 0.19 0.01 0.48 0.02
MgO 0.24 0.01 0.077 0.004
Na2O 0.57 0.03
SO3 0.044 0.002
P2O5 0.302 0.015
LOI 2.56 0.13 10.64 0.53
eliminate clay particles, rice husks were washed with dis-
tilled water, filtered and then immersed in HCl (Merck,
37%) solution (1 M) for 8 h. After leaching with HCl, the
husks were washed well with distilled water, dried in air
and calcined at 700C for 6 h. The obtained rice husk ash
was then subjected to dissolving in NaOH (Merck, 98%)
solution (2 M), followed by refluxing for 12 h. Concen-
trated HCl was added to the dissolved rice husk ash for
complete precipitation. The precipitate was filtered from
the solution, washed with distilled water till free from
chloride ions and finally dried in an oven over night.
Table 1 shows the XRF analysis results of the rice husk ash
and extracted silica powder.
Nanozeolite NaA Preparation
The nanometer-sized NaA zeolite was synthesized by
hydrothermal crystallization. In general, Ostwalds law of
successive reactions is followed in zeolite synthesis in this
work [29]. The synthesis mixture was prepared by mixing
freshly prepared aluminate and silicate solutions together
in the molar ratio of xNa2O:0.5Al2O3:SiO2:200 H2O,
where x = 0.7, 7.5 and 11.25. Typically, a synthesis
mixture containing 8.31 g of NaOH (Merck), 1.38 g of
NaAlO2 (Merck), 0.94 g of extracted silica, and 50 g of
H2O was adopted. A specific amount of NaOH was dis-
solved in H2O and then divided into two equal portions.
The silica, extracted from rice husk ash, was completely
dissolved in one portion. The alumina solution was pre-
pared by mixing a specific amount of sodium aluminate
with another portion of the NaOH solution. After clearness
of the solutions was reached, the silicate solution was
slowly mixed into the aluminate solution with vigorous
stirring. The resultant mixture was stored in an oil bath at
40C in sealed polypropylene bottles while subjected to
variable conditions (static and rotating shaking) for 18 h.
The products were separated by centrifugation
(17,000 rpm, 30 min), followed by redispersion in water
Waste Biomass Valor (2012) 3:6174 63

Table 2 Initial composition and heating time for the synthesis of NaA zeolite
Run Molar composition of initial solution Na2O/SiO2 ratio Crystallization condition Product

A1 0.7Na2O:0.5Al2O3:1SiO2:200 H2O 0.7 Static Amorphous

A2 7.5Na2O:0.5Al2O3:1SiO2:200 H2O 7.5 Static NaA
A3 11.25Na2O:0.5Al2O3:1SiO2:200 H2O 11.25 Static Amorphous
A4 7.5Na2O:0.5Al2O3:1SiO2:200 H2O 7.5 Rotating shaking NaA

Table 3 Effect of crystallization time, crystallization temperature

for several times until the pH value of the solution was and crystallization condition for the synthesis of NaX zeolite
\9.0. The products were dried in the oven overnight. The
Run Crystallization Crystallization Crystallization
synthesis conditions are summarized in Table 2. temperature (C) time (day) condition

Nanozeolite NaX Preparation X1 45 1 Static

X2 45 1 Static
The nanometer-sized NaX zeolite was synthesized by 60 1
hydrothermal crystallization [21] with different crystalli- X3 60 2 Static
zation time, temperature and shaking conditions. A series of X4 45 1 Static
experiments has been carried out under the following con- 60 2
ditions: extracted silica from rice husk ash as silica source; X5 45 1 Static
sodium aluminate as source of alumina; 4 silica/alumina 85 1
mole ratio; 47.5 H2O/SiO2 mol ratio; and 1.375 Na2O/ X6 60 4 Static
SiO2 mol ratio. The gel composition of NaX nanozeolite X7 60 2 Rotating shaker
was calculated based on the results of the XRF analysis of (250 rpm)
extracted silica source. Typically, 2.72 g of NaOH was X8 60 2 Magnetic stirrer
(250 rpm)
dissolved in 50 g of H2O and then divided into two equal
portions. An amount of 2.526 g of silica source, extracted
from rice husk ash, was completely dissolved in one portion silica were determined on a PW1800 Philips XPert dif-
of the NaOH solution and the resultant suspension was fractometer using CuKa as radiation. The morphology and
stirred until a clear solution was reached. An aluminate the size of the NaA zeolite was investigated with scanning
solution was prepared by mixing 1.06 g of NaAlO2 (Merck) electron microscopy (SEM, Philips, XL30, operated at
with another portion of the NaOH solution. After that the 30 kV), and the Si/Al ratio of the final nanosize NaA was
solutions got clear, the silicate solution was slowly poured determined by an energy diffraction X-ray (EDX) instru-
into the aluminate solution with vigorous stirring, which ment of aforementioned SEM. Nitrogen adsorption/
resulted in a clear homogenous solution. The resultant desorption isotherms at T = -196C were determined
mixture was stored in an oil bath at different crystallization using a conventional volumetric (BET, Bel Japan, Inc.)
temperature, in a sealed polypropylene bottle while sub- apparatus. The specific surface area was obtained using
jected to variable conditions (static, magnetic stirrer and BrunauerEmmetTeller (BET) method. The micropore
rotating shaker) for different crystallization periods. The volume and the external surface area and the average pore
synthesis conditions are summarized in Table 3. Finally, the diameter were evaluated by the t-plot and BarrettJoyner
solid products obtained in the synthesis were separated by Halenda (BJH) methods, respectively. The Fourier trans-
centrifugation (17,000 rpm, 30 min), followed by redi- form infrared (FT-IR) spectra were recorded on a Shima-
spersion in distilled water for several times until the pH dzo, FT-IR1650 spectrophotometer.
value dropped to 8.5. The products were dried in an oven The LOI (Loss of Ignition) test was carried out fol-
overnight. lowing the SIRIM procedure (ISO 3262-1975). About 1 g
of a dried sample of the extracted silica was placed in a
Characterization Techniques platinum crucible and ignited in a muffled furnace at
1,000C for 30 min to achieve a constant mass, followed
The chemical composition of the extracted silica powder by cooling in a desiccator. The loss of ignition, as a per-
from rice husk ash was determined by X-ray fluorescence centage by mass, is given by the formula:
(XRF, Philips, Spectrometer PW2404). The powder X-ray M0  M1
LOI; %  100 1
diffraction (XRD) patterns of NaA zeolite and extracted M0

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where M0 is the mass of the sample and M1 is the mass of
the sample after ignition.
Results and Discussion
Rice Husk Ash and Extracted Silica Characterization
The XRF analysis results of the rice husk ash and extracted
silica powder are listed in Table 1. The gel composition of
nanozeolite NaA was calculated based on the XRF anal-
ysis results.
The XRD spectra of the ash and the extracted silica are
shown in Fig. 1. The small observed peaks in the XRD
pattern of the ash show that it was crystalline. The organic
matter of rice husk can be removed by heating treatments
at high temperatures, but this usually leads to the crystal-
lization of the amorphous silica [30]. According to XRD
analysis of ash (Fig. 1a) which was heat treated at 700C
for 6 h, the supplied rice husk ash presents its crystalline
phase in the form of cristobalite, tridymite and quartz [14,
17, 31]. As shown in Fig. 1a, The ash sample is crystalline
because of the presence of sharp peaks. On the other hand,
as shown in the leached RHA samples, transformation from
crystalline silica to amorphous sample as the dominant
phase after leaching with HCl, the SiO2 content in these
RHA samples was about 88% while other components
except potassium and alumina decreased to almost below
0.1%. According to XRD analysis, the extracted silica
powder was amorphous (Fig. 1b). A broad peak centered at
2h angle of 22 confirmed further the amorphous nature of
the silica [32]. This amorphous form is an advantage
towards the preparation of silicon based materials like
Fig. 1 The XRD analysis of
a rice husk ash and b extracted
silica powder [29], Symbols C,
T and Q: peak position of
cristobalite, tridymite and
quartz, respectively
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Waste Biomass Valor (2012) 3:6174
zeolites, because the silica is rendered active in its amor-
phous form [33].
XRD Characterization of Synthesized NaA and X
Nanozeolites
The lowering of the crystallization temperature leads to a
significant reduction in the zeolite crystal size. In general,
Zeolite NaA synthesized by hydrothermal crystallization
of clear mixtures at lower temperatures led to smaller
particle sizes at the expense of a considerable decrease in
the crystallization rate. In addition, the crystal growth rate
of the nanocrystalline NaA zeolite could be affected by
the alkalinity and composition of the reaction mixtures
[34].
The effect of Na2O/SiO2 ratio on the nanozeolite NaA
was investigated with the compositions of xNa2O:0.5A-
l2O3:SiO2:200 H2O, where x = 0.7, 7.5 and 11.25. The
results are summarized in Table 2. Samples A1, A2 and A3
were prepared with the Na2O/SiO2 ratios of 0.7, 7.5 and
11.25, respectively, in static conditions and sample A4 was
prepared with the Na2O/SiO2 ratio of 7.5 using a rotating
shaker at speed of 250 rpm. The reaction temperature and
time were fixed at 40C and 18 h, respectively. The Na
cation was added in the form of NaOH, resulting in the
concentration of OH- being controlled simultaneously by
the concentration of cation [35]. The hydroxide ion affects
dissolution and polymerizationdepolymerization reactions
of silicates and aluminosilicates [36].
Figure 2 shows the XRD patterns of three samples A1,
A2 and A3 prepared with extracted silica in the ratios of
0.7, 7.5 and 11.25 Na2O/SiO2, respectively. According to
XRD patterns of the samples obtained, only one sample
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Fig. 2 The XRD patterns of
samples a A1, b A2 and c A3
(A2) was confirmed to be pure form of zeolite A, with no
formation of other types of zeolites. The XRD patterns of
three sample A1 resulted in an amorphous phase of the
final products (Fig. 2a). Peaks at 2h = 7.10, 10.19 and
12.49 [37] show that pure phase of NaA zeolite was
produced with The Na2O/SiO2 = 7.5 (Fig. 2b). The crys-
tallization kinetics of the structural formation of zeolite A
is known to be affected by the alkalinity and composition
of the initial reaction mixture (i.e. SiO2/Al2O3 and Na2O/
SiO2 molar ratios) [38, 39]. The XRD patterns of three
sample A3 resulted in an amorphous phase of the final
products (Fig. 2c).
The Na2O/SiO2 ratio has the most pronounced effect on
the kinetics of the zeolite formation [34]. The increase of
this ratio from 0.7 to 7.5 led to the growth of the zeolite
crystals in 18 h. The Na2O/SiO2 = 11.25 in the system did
not form the zeolite A. The Na2O/SiO2 = 0.7, the minimum
ratio to dissolve this kind of silica source to achieve a clear
solution of silica, resulted in an amorphous phase of the
final products (Fig. 2a). These results indicate that the for-
mation of amorphous phase in sample A1 and A3 might be
due to the Na2O/SiO2 ratio and the ratios of 0.7 or 11.25
were not suitable for crystallization of nanozeolite NaA at
this crystallization temperature. However, it has been found
that the Zeolite NaA was formed under hydrothermal
condition when the solution droped to the metastable phase.
This means that Zeolites are thermodynamically metastable
phases, only crystal growth and no nucleation can be
occured. According to Ostwalds ripening of the crystals, a
65
metastable phase appears first and is successively trans-
formed into thermodynamically more stable phase [29].
Another reason affecting the formation of zeolite phase
could be the silica extracted from rice husk ash (silica
source) in this initial reaction system (Na2O/SiO2 ratio of
0.7) at 40C, which is not reactive towards the formation of
zeolite NaA. An important factor that may control the
crystallite size of the zeolite NaA is the silica source [40].
It was found that the zeolite formation is very sensitive to
the nature of the reactants, in particular to that of the silica
source [34]. The observed fact can be explained that the
different silica source associated with zeolite formation
differs in reactivity and solubility. On the other hand, the
different nucleation and crystallization of zeolites are due
to nature of polysilicate species and their distributions may
control the final crystal size of zeolite [29]. This factor is
important in the crystallization kinetics of nano-crystalline
NaA zeolite [40]. The silica source can influence the solid
phase of the zeolite crystallization, including the kinetics of
crystal growth and the properties of the final product [41,
42]. Moreover, the use of different silica sources and var-
iation of synthesis conditions significantly influence and
change the crystallization process [41].
It was found that different surface areas of the silica
source can influence the crystallization rate, the crystal
size, and the particle size distribution of zeolite NaA.
Silica with high surface area is much more easily dissolved
in basic medium than that with low surface area. These
advantages enhance the crystallization rate in basic
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Fig. 3 The XRD patterns of
samples A2 and A4
solution, which is favorable for the formation of small
particle size with narrow particle size distribution, while
the silica source with low surface area and low solubility
favor the formation of large crystals [29]. The silica source
used in the present study seems not to be reactive towards
the synthesis of zeolite NaA in nanometer size.
As mentioned above, the crystal growth rate of the
nanocrystalline NaA zeolite could be affected by the
alkalinity and composition of the reaction mixtures.
The synthesis temperature in present study was fixed at
40C. In general, hydrothermal synthesis of zeolite NaA
at lower temperatures led to smaller particle sizes at the
expense of a considerable decrease in the crystallization
rate. To obtain zeolite NaA in mild conditions, a highly
alkaline initial system was employed by mixing freshly
prepared aluminate and silicate solutions. A higher alka-
linity increases the solubility of the Si and Al sources,
decreases the polymerization degree of the silicate anions,
and accelerates the polymerization of the polysilicate and
aluminate anions. Consequently, as is observed in the
present study too, the increase of alkalinity will shorten the
induction and nucleation periods and speed up the crys-
tallization of zeolites [36]. Therefore, we could obtain
zeolite NaA in nanometer size by increasing the Na2O/
SiO2 ratio from 0.7 to 7.5. Also, it can be found that the
synthesis of zeolite NaA in nanometer size using extrac-
ted silica and without adding any organic template has an
optimal Na2O/SiO2 ratio of 7.5 in this study and this kind
of zeolite may not be synthesized at higher or lower Na2O/
SiO2 ratios.
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Waste Biomass Valor (2012) 3:6174
As shown in Fig. 3, the XRD patterns reveal that the
zeolite NaA was synthesized in both static and rotating
crystallization conditions (samples A2 and A4). Crystallite
size of the zeolites can be modified by changing the syn-
thetic conditions [26], and we found that the crystallite size
of NaA zeolites could be modified by changing the syn-
thesis conditions.
The effects of reaction temperatures and times on
crystallization of products were studied by XRD technique.
According to XRD patterns of the samples obtained,
samples A2 and A4 were confirmed to be pure form of
zeolite A, with no formation of other types of zeolites
(Fig. 3a, b).
A hydrothermal synthesis method for NaX preparation
was also investigated by using rice husk ash as the only
silica source without any organic additive. The XRD pat-
terns taken after different hydrothermal crystallization
periods and temperatures, are presented in Fig. 4. The
results containing the phase formed and average crystal
size of products is summarized in Table 4. XRD pattern for
samples X1 and X2 (Fig. 4a, b) that the first one was
crystallized at 45C for 1 day and the second one at 45C
for 1 day and then at 60C for another 1 day showed
amorphous phase. It was revealed that the temperatures 45
and 60C for 1 day are not suitable for the synthesis of Na
X nanocrystals. Figure 4c indicates that NaX nanocrystals
are formed after heating for 2 days at 60C (X3). The
existence of peaks at 2h = 6.12, 10.00 and 11.73 [43],
which correspond to the zeolite NaX, confirms the pres-
ence of zeolite NaX. The crystallite size was calculated as
Waste Biomass Valor (2012) 3:6174 67

Fig. 4 The XRD patterns of

samples crystallized at a 45C
for 1 day, b 45C for 1 day and
then at 60C for 1 day, c 60C
for 2 days, d 45C for 1 day
followed by 60C for 2 days,
e 45C for 1 day followed by
80C for 1 day and f 60C for
4 days

*12 nm from the Scherrer equation. The weak and small Table 4 Effects of crystallization time, crystallization temperature
XRD peaks of the Fig. 4c indicate that small zeolite and crystallization condition on the crystallization process of NaX
crystals were formed. In general, the crystallinity increases zeolite
with time. Also, with an increase in the temperature of Run Phase formed XRD average crystal size (nm)
synthesis, the solubility of silicate ions increases, causing
more amounts of SiO2 in the concentration of the liquid X1 Amorphous
phase of the mix to produce NaX zeolite [44]. The con- X2 Amorphous
centration of silicate in the liquid phase of the gel is one of X3 X 12.56
the main controlling factors in the formation of a zeolite. X4 X and NaP1 28.43 and 16.18
The XRD patterns in Fig. 4d, e and f for samples X4, X5 X5 X and NaP1 33.56 and 17.80
and X6 indicate that the NaX and P phase were formed. X6 X and NaP1 12.40 and 13.25
Peaks at 2h = 12.46, 21.67 and 28.10 confirm the exis- X7 NaP1 17.71
tence of P phase. Crystallization at 60C for 2 days gives X8 NaP1 17.90
NaX, whereas the samples crystallized in two stages
(45C for 1 day followed by 60C for 2 days and 45C for the synthesis of NaX zeolite was also reported by Bond-
1 day followed by 80C for 1 day) give a mixture of X and areva et al. [45]. The nucleation rate of P zeolite is slower
P phases. Also, increasing the crystallization time to 4 days than that of NaX, so P zeolite crystallization requires a
at 60C resulted in the formation of a mixture of X and P long induction period. Increasing the crystallization time
phases as shown in Fig. 4f. The reason is that zeolites are favors the formation of thermodynamically more stable P
thermodynamically metastable phases. The formation of zeolite relative to NaX.
metastable phases of zeolites depends on temperature, and To investigate the effect of shaking conditions, a series
then the most stable phase will continue to grow and be of experiments were performed by changing the shaking
detected finally. Not only the temperature, but the crys- condition including static, rotating shaker (250 rpm) and
tallization time also plays an important role on the for- magnetic stirrer (250 rpm) at 60C for 2 days. Figure 5
mation of the specific metastable phase of zeolite. In shows the XRD patterns of X3, X7 and X8 at different
general, a metastable phase appears first and then succes- shaking conditions. In accordance with XRD patterns
sively more stable phases replace it and each other. With a (Fig. 5b, c), Crystallization with shaking or stirring gave
further increase in the crystallization time and temperature, the pure phase of P zeolite. Several studies have shown that
the ultimate product from NaX (FAU) zeolite is zeolite P stirring can effectively modify the formation of different
(GIS) when synthesized in alkaline aluminosilicate gel zeolite phases [46, 47]. In stirred system, zeolite A (LTA)
[45]. It is found that P zeolite is the dominant stable phase and TON were preferred to zeolite X (FAU) and MFI,
at higher temperatures and time. The formation of NaP in respectively.

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Fig. 5 The XRD patterns of
samples crystallized at 60C for
2 days under a static, b rotating
shaking (250 rpm) and
c magnetic stirring (250 rpm)
conditions
However, the formation of zeolites cannot be rational-
ized on a thermodynamic basis alone and the zeolite for-
mation is very sensitive to the nature of the reactants, in
particular that of the silica source [34]. This factor is
important in the nucleation kinetics [40]. The silica source
can influence different aspects of the zeolite crystallization,
including the kinetics of crystal growth and the properties
of the final product [41, 42]. The use of different silica
sources significantly influences the outcome of the syn-
thesis experiments [42]. Studies by Ramli et al. [48] have
shown that zeolites synthesized from less reactive rice husk
ash silica consist of a mixture of zeolite Y and P.
The present study established that the static crystalli-
zation condition was the best shaking condition for the
synthesis of pure phase of nanometer sized NaX zeolite
using extracted silica from rice husk ash as a source of
silica without any organic template. To obtain zeolite Na
X without any organic template, a highly alkaline condition
was applied by mixing freshly prepared aluminate and
silicate solutions as shown above. A higher alkalinity
increases the solubility of the Si and Al sources, decreases
the polymerization degree of the silicate anions, accelerates
the polymerization of the polysilicate and aluminate
anions. The sodium in the system provoked abundant
aggregation of polymerized aluminosilicate species,
resulting in a fairly open gel structure [19, 21, 22]. Con-
sequently, the increase of alkalinity will shorten the
induction and nucleation periods and speed up the crys-
tallization of zeolites.
SEM of Synthesized Products
Scanning electron microscopy images were recorded for
the extracted silica-synthesized zeolitic samples samples
A2 and A4, some of which are shown in Fig. 6. The Fig. 6a
shows the SEM images of prepared nanozeolite NaA in a
static condition, indicating the particle size of synthesized
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Waste Biomass Valor (2012) 3:6174
nanozeolite NaA is fine and within a range of 40400 nm.
Figure 6b indicates that the particle size of synthesized
nanozeolite NaA in a rotating condition (rotating shaking)
is within a range of 150400 nm. According to SEM
images, the crystallite size of zeolite NaA synthesized at
static conditions is smaller than in rotating conditions.
Several studies have shown that smaller crystals are
obtained by stirring. In a stirring condition super-saturation
can be produced rapidly due to the accelerated mass
transfer. Also, stirring modifies the selectivity for entering
into different zeolite phases. For example, zeolite X (FAU)
was replaced by zeolite A (LTA) in a stirred system [36].
In the present study, however, the size distribution obtained
in static condition was wider, extending towards smaller
crystals. It could be due to less homogeneous concentration
conditions, with local discrepancies leading to less homo-
geneous growth rates and then more dispersed sizes. Also
this result can be attributed to the special silica source and
to the rotating shaking instead of a magnetic stirring con-
dition. As mentioned above, silica source is important in
the crystallization kinetics of nano-crystalline NaA zeo-
lite. As extracted silica from rice husk ash was used in this
study, so it may affect the final crystal size. On the other
hand, crystallization under magnetic stirring or rotating
shaking condition can influence the crystal size of final
product. Zhan et al. [26] show that the NaX crystal size
depends on the silicate source and hydrothermal crystalli-
zation conditions. They indicate that magnetic stirring and
rotating shaking conditions would result in different crystal
size of zeolite NaX.
There are some studies dealing with zeolite synthesis
using rice husk ash as an alternative silica source [1318].
Although rice husk ash has been used as an alternative silica
source to synthesize zeolite instead of pure chemical sources
in all the above mentioned studies but synthesis of zeolites
NaA and X in nanometer size using extracted silica from
rice husk ash without adding any organic-template has not
Waste Biomass Valor (2012) 3:6174
Fig. 6 SEM images of samples a A2 and b A4
yet been reported. In present study, the result of XRD and
SEM techniques confirmed synthesis of zeolite NaA with
extracted silica from rice husk ash without adding any
organic-template and in nanometer size in 18 h that has not
yet been reported. The synthesis of nanozeolite NaA at low
temperature favored the nucleation process, since the acti-
vation energy of crystal growth is generally higher than that
of nucleation. This is one key route to synthesize nanozeo-
lites without using any organic additives [22, 26, 34].
Some of the scanning electron microscopy (SEM) ima-
ges recorded for the synthesized zeolite NaX samples are
illustrated in Fig. 7. SEM was utilized to determine the
morphology and size of the zeolite samples. Figure 7a, b
show products in sample X3 where well nano-crystalline
NaX type of zeolite with average size of 70260 nm was
obtained. Results obtained from the XRD patterns confirm
the size distribution of synthesized NaX in this study.
Therefore, the procedure described here can indeed
69
successfully synthesize fine NaX crystals without using
any organic templates.
Figures 7ce show typical crystals of X4, X5 and X6 in
this work. In accordance with XRD result, the SEM
micrographs of the products indicate the presence of two
different zeolite phases of NaX and P, as shown in
Fig. 7ce. Different crystalline shapes existed in these
micrographs are attributed to different types of zeolites
which were produced in mentioned samples. Figure 7d
shows the nanometer-sized NaX and P zeolites with
average sizes of 100200 and 50100 nm, respectively.
Presumably, the larger square particles consist of NaX,
while the smaller, spherical particles consist of zeolite NaP
[2, 46].
There have been some documents encouraging the uti-
lization of rice husk ash as an alternative silica source for
the synthesis of various types of zeolites [1318, 44, 49,
50]. In present study, the result of XRD and SEM analysis
confirmed synthesis of free template zeolite NaX in
nanometer size at 60C after 2 days with extracted silica
from rice husk ash that has not yet been reported.
Also, the zeolite NaX synthesized in nanometer size
from rice husk ash without the assistance of any organic
template has the cost benefits and other advantages.
Approximately one-fifth of the ash is obtained on burning
rice husk in air [51]. About 95 g of silica was extracted per
100 g of rice husk ash (Table 1). In our study, 2.526 g of
extracted silica yielded 1.24 g nanozeolite NaX approxi-
mately. Totally, about 110.45 kg of nanozeolite NaX was
produced per ton of rice husk ash, considering low cost of
rice husk.
EDX Analysis of Synthesized NaA and X
Nanozeolite
Typically, zeolite LTA is synthesized with framework Si/Al
ratio of 1[37]. By using tetramethylammonium cation
(TMA?) as the SDA, the Si/Al ratio of LTA framework
could be increased up to about 3. The Si/Al and Na2O/SiO2
ratios of nanozeolite NaA obtained after 18 h with Na2O/
SiO2 = 7.5 in initial system, were determined by EDX
technique. The Si/Al and Na2O/SiO2 ratios of nanozeolite
NaX obtained at 60C after 2 days in static crystallization
condition were determined by EDX technique. The Si/Al and
Na2O/SiO2 ratios of 1.58 and 0.16 and 1.68 and 0.136 for
nanozeolites NaA and X, respectively. Thus, the zeolites
NaA and X were confirmed by the EDX techniques.
Surface Texture of Synthesized NaA and X
Nanozeolites
The N2 adsorption/desorption isotherm of the prepared na-
nozeolites NaA and X is shown in Fig. 8a, b. The NaA
123
70 Waste Biomass Valor (2012) 3:6174

Fig. 7 SEM micrographs of products crystallized at a and b 60C for 2 days, c 45C for 1 day followed by 60C for 2 days, d 45C for 1 day
followed by 80C for 1 day and e 60C for 4 days

123
Waste Biomass Valor (2012) 3:6174
Fig. 8 The N2 adsorption/desorption isotherm of the prepared
nanozeolite Na a A and b X
nanocrystals were characterized by using N2 adsorption/
desorption measurements to determine their pore volume
and surface area (Fig. 8a). As shown in Fig. 8a, zeolite NaA
in its sodium form does not adsorb the N2 molecule. The unit
cell structure of zeolite NaA has cubic arrangement and its
{100} faces of the unit cell (1.4 A diameter) with large
cavities is located near the centre of the oxygen six-window.
On the other hand, Na? cation partially blocks these win-
dows, in which oxygen but not nitrogen molecules can pass
through the holes in the zeolite NaA [52]. For this reason, in
the nitrogen adsorption/desorption isotherm (Fig. 8a), the
71
amount of nitrogen adsorbed in the sample is very low at low
relative pressures, and substantially increases at high relative
pressures (e.g. P/Po [ 0.8). Indeed, the adsorption/desorp-
tion isotherm of the product was of type II and has sigmoid
shape, typical of nonporous materials. A gentle increase in
the volume of N2 adsorbed at very low relative pressures was
due to the presence of a small amount of micropores, most
probably related to the adsorption of N2 molecules at the
pore openings [34]. On the other hand, dramatic deviations
from its original behavior exhibited. This means that the
isotherm determined on the NaA sample exhibit no hys-
teresis loops indicates that the test sample seems to be non-
porous surfaces. The specific surface area and average pore
diameter of the synthesized NaA nanocrystals were
36.9 m2 g-1 and 10.6 nm (using BJH method), respectively,
which suggests nanometer size particles. The large external
surface of the obtained NaA zeolite was 33.0 m2 g-1 which
further supports NaA nanocrystals having a small crystal-
lite size.
The synthesized NaX nanocrystals were also charac-
terized using N2 adsorption/desorption to determine their
pore volume and surface area. The N2 adsorption/desorp-
tion isotherm of prepared NaX nanozeolite are shown in
Fig. 8b. There is a hysteresis loop starting at P/P0&0.45. It
is an H1 type mainly because adsorption and desorption
branches are parallel. H1 type hysteresis can be explained
by molecular nitrogen condensation in meso spaces (most
likely interparticle voids) [53]. Type H1 hysteresis is often
associated with porous materials consisting of well-defined
cylindrical-like pore channels or agglomerates of compacts
of approximately uniform spheres. In the case of prepared
NaX nanozeolite in this study, the agglomeration of
nanometer-sized crystalline particles causes the production
of interparticle voids which in turn create mesoporous
spaces. The parameters including the BET surface area,
total pore volume, micropore volume and size of microp-
ores obtained from BET equation and t-plot method are
summarized in Table 5. From the t-plot analysis of the
Isotherms, the large external surface of this sample and
average pore diameter were 23.6 m2 g-1 (about 26% of its
specific surface area) 9.2 nm (using BJH method),
respectively, which further supports that prepared NaX
Table 5 Surface texturing data of NaX nanozeolite prepared from
rice husk
Run BET surface Total pore Micropore Size of
area (m2/g) volume volume (m3/g) micropores
(m3/g) (nm)
A2 39.69 0.260 0.042 4.29
X3 89.96 0.222 0.145 3.04
123
72
Fig. 9 FTIR spectra of
prepared nanozeolite Na aA
and bX
zeolite has small crystallite sizes. The specific surface area
and average obtained was 89.9 m2 g-1.
FT-IR Analysis of Synthesized NaA and X
Nanozeolites
FT-IR spectra, in the 4004,000 cm-1 range, for nanoze-
olites NaA and X are shown in Fig. 9a, b. The vibration
results in TO bending mode at 453 cm-1 and the broad-
band at *1,038 cm-1 is assigned to the asymmetric stretch
of TOT (T = Si, Al) [54], and the double-ring vibration
at 569 cm-1 show that the NaA phase is produced
(Fig. 9a). Another broadband at 860 cm-1 can be assigned
to the silanol (SiOH) bending mode associated with the
silicon atoms linked to one hydroxyl group [26, 55].
A sharp peak at *1,650 cm-1 corresponding to the water
deformation mode appears in the spectra. Thus, the zeolite
NaA was confirmed by the FT-IR technique (Fig. 9a).
FT-IR spectra in the 4004,000 cm-1 range for synthesized
NaX nanozeolite is shown in Fig. 9b. The band at
453 cm-1 is characteristic of TO bending vibration of the
SiO4 and AlO4 internal tetrahedral [54, 56]. The well
defined IR bands at 792 cm-1 and that in the 1,038 cm-1
region are assigned to external symmetrical and internal
asymmetrical stretching bands of TOT (T = Si, Al) and
the double-ring vibration at 569 and 684 cm-1 show that
the NaX phase is produced [56]. The band at 3,469 cm-1
are due to the presence of hydroxyl groups (hydrogen
bonded SiOH groups) in the faujasite supercages and
123
Waste Biomass Valor (2012) 3:6174
sodalite cages as the building blocks of faujasite structures
[57]. The well-defined band at 1,650 cm-1 is ascribed to
OH bending vibration since it coexists with OH stretching
vibration positioned at 3,469 cm-1 [56]. Thus, purity of the
NaX nanozeolite was confirmed by the intensities of these
adsorption bands as well as with the interpretation of
obtained XRD results (Fig. 9b).
We have used extracted silica from rice husk ash as an
alternative silica source which reduces the costs of syn-
thesis effectively through utilization of cheap raw mate-
rials considering low cost of rice husk. Therefore,
utilization of this agricultural by-product for nanozeolite
NaA synthesis would result in the conversion of a low
cost raw material into high value added product. Also,
the zeolite NaA synthesized in nanometer size from rice
husk without the use of organic template has the cost and
other advantages. Two synthesis procedures of zeolite
reported so far have been focused mainly for organic
template systems [1618] that may not be feasible for
operations on an industrial scale. Organic templates e.g.,
Tetramethylammonium hydroxide (TMAOH), make 50%
of the production cost and require calcinations which
result in the production of CO2 and NOx pollution
problems [58]. In our environmentally friendly process,
no expensive organic template was used, thus resulting a
decrease in the cost of nanozeolites NaA and X syn-
thesis. Moreover, specialized instruments for burning
excess TMA after synthesis were avoided that result in
lower disposal costs.
Waste Biomass Valor (2012) 3:6174
Conclusion
In this study, the rice husk was calcined completely to
produce carbon-free white ash, which resulted in a weight
loss of more than 70%. Amorphous silica, highly reactive
for nanozeolites NaA and X synthesis, was extracted
from the rice husk ash by a suitable alkali solution.
Amorphous extracted silica powder was composed of
87.99 wt% SiO2. We successfully achieved synthesizing
nanometer-sized NaX zeolite with extracted silica without
using any organic additive. Synthesizing nanometer-sized
nanozeolite NaA with extracted silica at 40C without
using any organic additives was successfully achieved.
Also, the effect of alkalinity and Na2O/SiO2 ratio of initial
system; and crystallization condition on the properties of
the final product was investigated. Zeolite NaA nano-
crystals with crystallite size ranging from 40 to 120 nm
were obtained from a sodium aluminosilicate solution at
40C in 18 h under Na2O/SiO2 = 7.5 conditions. Thus the
aims to lower costs and to shorten crystallization time were
both found possible through the study. NaX nanocrystals
with crystallite size ranging from 70 to 260 nm were
obtained from a sodium aluminosilicate solution at 60C
after 2 days. To best of our knowledge, this is the first
report on the hydrothermal synthesis of zeolite NaA
nanocrystals with rice husk as source of extracted silica,
without using any organic additives during the whole
crystallization process. Our environmentally friendly pro-
cess reduces the costs of synthesis effectively through
utilization of cheap raw materials and also by avoiding
consumption of expensive chemical sources as template.
Acknowledgments This study was supported by a research grant
from Tarbiat Modares University (TMU), Iran Nanotechnology Ini-
tiative Council and SPAG Zeolite R & D Group. The authors wish to
thank Mr. F. Farhadi, Mr. M. Sardari and Mr. I. Sourinejad for their
technical assistance during the experiments, and Ellen Vuosalo
Tavakoli for the final editing of the English text.
References
1. Barrer, R.M.: Hydrothermal Chemistry of Zeolites. Academic
Press, London (1982)
2. Breck, D.W.: Zeolite Molecular Sieves. Wiley, London (1974)
3. Grace, Co: Method of Analysis for Fluid Cracking Catalysts.
Davison Chemicals, Baltimore (1980)
4. Huang, L., Wang, Z., Sun, J., et al.: Fabrication of ordered porous
structures by self-assembly of zeolite nanocrystals. J. Am. Chem.
Soc. 122(14), 35303531 (2000)
5. Boudreau, L.C., Kuck, J.A., Tsapatsis, M.: Deposition of oriented
zeolite A films: in situ and secondary growth. J. Membr. Sci.
152(1), 4159 (1999)
6. Cho, G., Lee, J.-S., Glatzhofer, D.T., Fung, B.M., Yuan, W.L.,
OrsquoRear, E.A.: Ultra-thin zeolite films through simple self-
assembled processes. Adv. Mater. 11(6), 497499 (1999)
73
7. Islam, M.N., Ani, F.N.: Techno-economics of rice husk pyrolysis,
conversion with catalytic treatment to produce liquid fuel. Bior-
esour. Technol. 73(1), 6775 (2000)
8. Fuad, M.Y.A., Ismail, Z., Ishak, Z.A.M., Omar, A.K.M.: Appli-
cation of rice husk ash as fillers in polypropylene: effect of
titanate, zirconate and silane coupling agents. Eur. Polym. J.
31(9), 885893 (1995)
9. Yalcin, N., Sevinc, V.: Studies on silica obtained from rice husk.
Ceram. Inter. 27(2), 219224 (2001)
10. Sun, L., Gong, K.: Silicon-based materials from rice husks and
their applications. Ind. Eng. Chem. Res. 40(25), 58615877 (2001)
11. Kalapathy, U., Proctor, A., Shultz, J.: An improved method for
production of silica from rice hull ash. Biores. Technol. 85(3),
285289 (2002)
12. Ramli, Z.: Rhenium-Impregnated Zeolites: Synthesis, Charac-
terization and Modification Ascatalysts in the Metathesis of
Alkanes. Universiti Teknologi, Malaysia (1995)
13. Nur, H.: Direct synthesis of NaA zeolite from rice husk and
carbonaceous rice husk ash. Indonesian J. Agric. Sci. 1, 4045
(2001)
14. Prasetyoko, D., Ramli, Z., Endud, S., Hamdan, H., Sulikowski,
B.: Conversion of rice husk ash to zeolite beta. Waste Manage.
26(10), 11731179 (2006)
15. Rawtani, A.V., Rao, M.S., Gokhale, K.V.G.K.: Synthesis of
ZSM-5 zeolite using silica from rice-husk ash. Ind. Eng. Chem.
Res. 28(9), 14111414 (2002)
16. Mohamed, M.M., Zidan, F.I., Thabet, M.: Synthesis of ZSM-5
zeolite from rice husk ash: characterization and implications for
photocatalytic degradation catalysts. Microporous Mesoporous
Mater. 108(13), 193203 (2008)
17. Kordatos, K., Gavela, S., Ntziouni, A., Pistiolas, K.N., Kyritsi,
A., Kasselouri-Rigopoulou, V.: Synthesis of highly siliceous
ZSM-5 zeolite using silica from rice husk ash. Microporous
Mesoporous Mater. 115(12), 189196 (2008)
18. Loiha, S., Prayoonpokarach, S., Songsiriritthigun, P., Wittayakun,
J.: Synthesis of zeolite beta with pretreated rice husk silica and its
transformation to ZSM-12. Mater. Chem. Phys. 115(23),
637640 (2009)
19. Valtchev, V.P., Bozhilov, K.N.: Evidences for zeolite nucleation
at the solidliquid interface of gel cavities. J. Am. Chem. Soc.
127(46), 1617116177 (2005)
20. Tsapatsis, M., Lovallo, M., Okubo, T., Davis, M.E., Sadakata,
M.: Characterization of zeolite L Nanoclusters. Chem. Mater.
7(9), 17341741 (2002)
21. Fan, W., Morozumi, K., Kimura, R., Yokoi, T., Okubo, T.:
Synthesis of nanometer-sized sodalite without adding organic
additives. Langmuir 24(13), 69526958 (2008)
22. Smaihi, M., Barida, O., Valtchev, V.: Investigation of the crys-
tallization stages of LTA-type zeolite by complementary charac-
terization techniques. Eur. J. Inorg. Chem. 2003(24), 43704377
(2003)
23. Mintova, S., Valtchev, V.: On the crystallization mechanism of
zeolite ZSM-5: part 1. Kinetic compensation effect for the syn-
thesis with some diamines. Zeolites 13(4), 299304 (1993)
24. Feoktistova, N.N., Zhdanov, S.P., Lutz, W., Bullow, M.: On the
kinetics of crystallization of silicalite I. Zeolites 9(2), 136139
(1989)
25. Mintova, S., Olson, N.H., Valtchev, V., Bein, T.: Mechanism of
zeolite A nanocrystal growth from colloids at room temperature.
Science 283(5404), 958960 (1999)
26. Zhan, B.-Z., White, M.A., Lumsden, M., et al.: Control of particle
size and surface properties of crystals of NaX zeolite. Chem.
Mater. 14(9), 36363642 (2002)
27. Ghasemi, Z., Younesi, H.: Preparation and characterization of
nanozeolite NaA from rice husk at room temperature without
organic additives. J Nanomater. 2011, 18 (2011)
123
74
28. Ghasemi, Z., Younesi, H., Kazemian, H.: Synthesis of nanozeo-
lite sodalite from rice husk ash without organic additives. Can.
J. Chem. Eng. 89(3), 601608 (2011)
29. Yu, J.: Synthesis of zeolites. Introd. Zeolite Sci. Pract. 168,
39103 (2007)
30. Krishnarao, R.V., Subrahmanyam, J., Kumar, T.J.: Studies on the
formation of black particles in rice husk silica ash. J. Eur. Ceram.
Soc. 21(1), 99104 (2001)
31. Chisholm, J.: Comparison of quartz standards for X-ray diffrac-
tion analysis: HSE A9950 (Sikron F600) and NIST SRM 1878.
Ann. Occup. Hig. 49(4), 351358 (2005)
32. Kalapathy, U., Proctor, A., Shultz, J.: A simple method for pro-
duction of pure silica from rice hull ash. Biores. Technol. 73(3),
257262 (2000)
33. Paya, J., Monz, J., Borrachero, M.V., Mellado, A., Ordoez, L.M.:
Determination of amorphous silica in rice husk ash by a rapid
analytical method. Cem. Concr. Res. 31(2), 227231 (2001)
34. Valtchev, V.P., Tosheva, L., Bozhilov, K.N.: Synthesis of zeolite
nanocrystals at room temperature. Langmuir 21(23),
1072410729 (2005)
35. Flanigen, E.M., Lok, B.M., Patton, R.L., Wilson, S.T., Murakami,
Y., Lijima, A., Ward, J.W.: Aluminophosphate molecular sieves
and the periodic table. In: Studies in Surface Science and
Catalysis, pp. 103112. Elsevier, Amsterdam (1986)
36. Yu, J., Cejka, J., van Bekkum, H., Cormma, A, Ferdi, S.:
Chapter 3 synthesis of zeolites. In: Studies in Surface Science and
Catalysis, pp. 39103. Elsevier, Amsterdam (2007)
37. Treacy, M.M.J., Higgins. J.B.: Linde type A, hydrated. In: Col-
lection of Simulated XRD Powder Patterns for Zeolites (fifth),
pp. 252253. Elsevier, Amsterdam (2007)
38. Wang, C.-F., Li, J.-S., Wang, L.-J., Sun, X.-Y.: Influence of
NaOH concentrations on synthesis of pure-form zeolite A from
fly ash using two-stage method. J. Hazard. Mater. 155(12),
5864 (2008)
39. Hui, K.S., Chao, C.Y.H.: Effects of step-change of synthesis
temperature on synthesis of zeolite 4A from coal fly ash.
Microporous Mesoporous Mater. 88(13), 145151 (2006)
40. Kleitz, F., Marlow, F., Stucky, G.D., Schuth, F.: Mesoporous
Silica fibers: synthesis, internal structure, and growth kinetics.
Chem. Mater. 13(10), 35873595 (2001)
41. Hamilton, K.E., Coker, E.N., Sacco, A., Dixon, A.G., Thompson,
R.W.: The effects of the silica source on the crystallization of
zeolite NaX. Zeolites 13(8), 645653 (1993)
42. Jansen, J.C.: Chapter 5A the preparation of oxide molecular
sieves A. Synthesis of zeolites. In: van Bekkum, H., Flanigen,
E.M., Jacobs, P.A., Jansen. J.C. (eds.) Studies in Surface Science
and Catalysis, pp. 175227. Elsevier, Amsterdam (2001)
123
Waste Biomass Valor (2012) 3:6174
43. Treacy, M.M.J., Higgins, J.B.: Tetrapropylammonium ZSM-5.
In: Collection of Simulated XRD Powder Patterns for Zeolites
(fifth), pp. 276277. Elsevier, Amsterdam (2007)
44. Dalai, A.K., Rao, M.S., Gokhale, K.V.G.K.: Synthesis of NaX
zeolite using silica from rice husk ash. Ind. Eng. Chem. Prod.
Res. Dev. 24(3), 465468 (1985)
45. Bondareva, G.V., Ratko, A.I., Azarov, S.M.: Hydrothermal
synthesis of zeolite NaX on porous ceramic supports. Inorg.
Mater. 39(6), 605609 (2003)
46. Hanif, N., Anderson, M.W., Alfredsson, V., Terasaki, O.: The
effect of stirring on the synthesis of intergrowths of zeolite Y
polymorphs. Phys. Chem. Chem. Phys. 2(14), 33493357 (2000)
47. Tanaka, H., Matsumura, S., Hino, R.: Formation process of Na-X
zeolites from coal fly ash. J. Mater. Sci. 39(5), 16771682 (2004)
48. Ramli, Z., Listiorini, E., Hamdan, H.: Optimization and reactivity
study of silica in the synthesis of zeolites from rice husk.
J. Teknologi. 25, 2735 (1996)
49. Panpa, W., Jinawath, S.: Synthesis of ZSM-5 zeolite and silicalite
from rice husk ash. Appl. Catal. B Environ. 90(34), 389394
(2009)
50. Katsuki, H., Komarneni, S.: Synthesis of NaA and/or NaX
zeolite/porous carbon composites from carbonized rice husk.
J. Solid State Chem. 182(7), 17491753 (2009)
51. Liou, T.-H.: Preparation and characterization of nano-structured
silica from rice husk. Mater. Sci. Eng. A 364(12), 313323 (2004)
52. Yusa, A., Ohgushi, T., Takaishi, T.: Application of percolation
theory to ion-exchanged molecular sieves A. J. Phys. Chem.
Solids 38(11), 12331236 (1977)
53. Thommes, M., Cejka, J., van Bekkum, H., Cormma, A, Ferdi, S.:
Chapter 15 textural characterization of zeolites and ordered
mesoporous materials by physical adsorption. In: Studies in
Surface Science and Catalysis, vol. XIII, pp. 495523. Elsevier,
Amsterdam (2007)
54. Flanigen, E.M., Khatami, H., Szymanski, H.A.: Infrared struc-
tural studies of zeolite frameworks. In: Molecular Sieve Zeolites-
I, pp. 201229. American Chemical Society, Washington (2009)
55. Szostak, R.: Molecular Sieves: Principles of Synthesis and
Identification. Van Nostrand Reinhold, New York (1989)
56. Ismail, A.A., Mohamed, R.M., Fouad, O.A., Ibrahim, I.A.: Syn-
thesis of nanosized ZSM-5 using different alumina sources.
Cryst. Res. Technol. 41(2), 145149 (2006)
57. Pedrosa, A., Souza, M., Melo, D., Araujo, A.: Cobalt and nickel
supported on HY zeolite: synthesis, characterization and catalytic
properties. Mater. Res. Bull. 41(6), 11051111 (2006)
58. Vempati, R.K., Borade, R., Hegde, R.S., Komarneni, S.: Template
free ZSM-5 from siliceous rice hull ash with varying C contents.
Microporous Mesoporous Mater. 93(13), 134140 (2006)