J Porous Mater (2010) 17:39–47
DOI 10.1007/s10934-009-9262-y
Hydrothermal conversion of rice husk ash
to faujasite-types and NaA-type of zeolites
Alias Mohd Yusof Æ Nik Ahmad Nizam Æ
Noor Aini Abd Rashid
Published online: 7 February 2009

Springer Science+Business Media, LLC 2009
Abstract The faujasite-type of zeolites (NaX and NaY)
and NaA-type of zeolite were synthesized from rice husk
ash (RHA) via the hydrothermal conditions. The combus-
tion of rice husk at controlled temperature of 600 C for an
hour in open air produce more than 90% of amorphous
silica in the ash which was reactive towards the synthesis
of zeolites. The formation of zeolite NaY from RHA is
metastable and thus, the seeding and ageing effects in the
synthesis of zeolite NaY were investigated to avoid the
formation of zeolite A or P as the impurities in zeolite
NaY. Zeolites NaX and NaA were also successfully syn-
thesized with high purity, absence of impurities and other
phases, and high reproducibility. Thus, the amorphous
forms of silica in RHA can be used as a source of silica for
the synthesis of faujasite-types and NaA-type of zeolites.
Keywords Rice husk ash
Zeolite NaY

Seeding technique
Zeolite NaX
Zeolite NaA
1 Introduction
Rice husk is the natural sheath that forms on rice grains
during their growth and it can be used as a potentially low-
cost biosorbent for heavy metal and dye removal [1]. In
Malaysia, rice husk is produced in abundance after every
paddy harvesting season which amounts to more than
A. M. Yusof (&)
Department of Chemistry, Faculty of Science, Universiti
Teknologi Malaysia, 81310 UTM Skudai, Johor, Malaysia
e-mail: alias@kimia.fs.utm.my
N. A. Nizam
N. A. A. Rashid
Faculty of Biosciences and Bioengineering, Universiti Teknologi
Malaysia, 81310 UTM Skudai, Johor, Malaysia
400,000 metric tones of rice husk generated annually
according to the statistics compiled by the Malaysian
Ministry of Agriculture [2]. The husks are eliminated by
burning them in the field at high temperature leaving
behind a white blackish powder containing the constituents
of silica [3]. Rice husk was also considered as the only
agriculture waste containing maximum siliceous ash and in
dry form [4]. The presence of silica ash causes a number of
environmental problems related to pollution and disposal.
Additionally, at high temperature, the products yield can
cause health hazard to human such as silicosis since the
products might contain crystalline silica, for instance,
quartz and cristobalite [5]. Therefore, useful applications of
the rice husk are desirable to solve this problem. Further-
more, the cheap and low raw material cost for the
production of high value added product can be achieved by
using silica generated from the combustion of rice husk.
Because of the high amount of silica in RHA, it was
used as an alternative source of silica to synthesis morde-
nite for the first time by Bajpal and Rao [6] in India almost
20 years ago. They used RHA as starting materials because
in India, rice husk is obtained in very large quantities as a
by-product at low cost. Four years later, the effort to use
RHA as staring material was carried out by Dalal and Rao
[7] to synthesis zeolite NaX. In Malaysia, since RHA can
be obtained in large quantities, Hamdan and Keat [8] pat-
ented the production of zeolite Y from RHA. Recently, a
group of researchers from Brazil reported the synthesis of
zeolite NaA also from RHA [9]. Besides these zeolites,
ZSM-5 can also be synthesized from RHA without tem-
plate and with seeding technique [5, 10]. There are two
forms of silica; amorphous and crystalline. The combustion
of rice husk under controlled atmosphere and temperature
of less than 800 C will generate the amorphous silica in
the form of white powder and this silica ash which is
123
40
transformed from the husk by complete burning constitutes
15–20% of the total weight of the husk [11]. Above
800 C, the ash contained a crystalline form of silica. In
this study, rice husk was burned at temperature below
700 C to get an amorphous form of silica in the rice husk
ash. Therefore, it is possible to use RHA for the starting
material to synthesis zeolites A, X and Y in this study.
Zeolite is crystalline in nature and consists of hydrated
aluminosilicates of group I and II. Structurally the zeolites
are framework aluminosilicates which is based on an infi-
nitely extended three dimensional network of AlO4 and
SiO4 tetrahedra linked to each other by sharing all of the
oxygen. Synthetic zeolite NaY is synthesized form zeolite
Y with sodium cations neutralizing the framework struc-
ture of aluminosilicates and these materials are in the same
group with zeolite X where both exhibit structure similarity
with naturally occurring faujasite type. Zeolites can be
synthesized using many sources of silica. Silica can be
obtained from sodium silicate, silica gels, silicic acid,
aqueous colloidal silica sols and reactive amorphous solid
silica [12]. Besides, zeolite can also be prepared from
waste materials, such as oil shale ash which is the solid by-
product of oil shale processing [13] and coal fly ash [14].
Machado and Miotto [13] synthesized zeolite NaA and
NaX from the calcined and leached oil shale ash containing
79.66% of SiO2 in crystalline form and 11.01% Al2O3.
Besides, the coal fly ash having 51.1% of crystalline
formed of silica and 15.7% Al2O3 was used by Wu et al.
[14] to synthesis zeolite NaP1.
Since the synthesis of zeolites A, X and Y have been
extensively reported a long time ago, there were many
versions on the synthesis methods for the purpose of pre-
paring highly pure zeolites. The most convenient method is
the Na2O–Al2O3–SiO2–H2O system where the ratio of
Na2O/SiO2, SiO2/Al2O3 and H2O/Na2O depends on the
types of zeolites. To obtain high purity of the desired
zeolites A, X and Y, the chemical composition in the
Na2O–Al2O3–SiO2–H2O system needs to be prepared
having a composition which falls in the ranges shown in
Table 1. The values of these ratios were obtained from
earlier patents reported on the synthesis of these zeolites
from amorphous silica.
There are some problems that occur during the synthesis
of zeolite NaY since the source of material used in this
Table 1 Composition ratio of the synthesis of zeolites A, X and Y
according to the earliest inventors
Zeolites Na2O/SiO2 SiO2/Al2O3 H2O/Na2O References
A 0.8–3 0.5–2.5 35–200 [15]
X 1.2–1.5 3–5 35–60 [16]
Y 0.41–0.61 10–30 20–60 [17]
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J Porous Mater (2010) 17:39–47
synthesis is amorphous silica and also the formation of the
metastable zeolite NaY. It is possible to produce two or
more crystalline phases from the same unreacted gel
components. In the case of the formation of zeolite Y the
initial formation of the desired faujasite phase (NaY)
occurred during the crystallization sequence and was sub-
sequently followed by the evolution of a transient phase,
gmelinite and finally by the production of garronite (Zeo-
lite NaP) [18]. Besides that, other phases identified to
crystallize when the Na2O/SiO2 and H2O/Na2O ratio were
changed are herschelite, noselite and zeolites P and A [19].
In order to avoid such phenomena from occurring and to
yield high purity of zeolite NaY, the seeding and ageing
methods during the synthesis of zeolite NaY from rice husk
ash will be highlighted.
Until present day, there are numerous types of synthetic
zeolites produced on a laboratory scale and they were then
applied for many purposes. Synthetic zeolites are vastly
and enormously used around the world as a catalyst,
adsorbent and ion exchange in many fields such as in
petroleum industry, detergency, water treatment, pharma-
ceutical and cosmetics. Among the synthetic zeolites,
zeolites A, X and Y are the most commercially significant
in market due to their special characteristics especially
their high ion exchange capacity and large pore size spe-
cifically for zeolite X and Y and also because they can be
synthesized at much lower temperature and pressure [20].
Zeolite A (LTA) is widely used in detergent to replace
sodium tripolyphosphate as water softener while zeolite X
and Y (FAU) are extensively used as catalyst mainly in oil
refineries area [21]. According to Vaughn [22], synthetic
zeolites A and X have replaced some of the natural zeolites
that had been worked on extensively since 1940 and sub-
sequent rapid utilization of these synthetic zeolites in the
areas of sorption in catalyst. Zeolites ‘‘A’’, ‘‘X’’ and ‘‘Y’’
are distinguished from other zeolites and silicates on the
basis of their X-ray powder diffraction patterns and certain
physical and chemical characteristics. Thus, the syntheses
of zeolites from economical and inexpensive raw materials
need attention. Besides, the conversion of agricultural
waste to beneficial advanced materials is attractive since
we are facing a global environmental problem.
2 Experimental
2.1 Raw materials
Rice husk was obtained from Bernas (Beras National)
milling, Selangor, Malaysia. Rice husk ash that was used as
a source of silica in the synthesis of zeolite was prepared
through physical combustion in a Plug Flow Combustor
(PFC), located at the Solid State Laboratory, Universiti
J Porous Mater (2010) 17:39–47
Teknologi Malaysia (UTM). Prior to burning, the rice husk
was washed by immersing them in distilled water to elim-
inate undesirable materials such as rice, sand and other
agricultural wastes. The rice husk was then dried under
sunlight for a period of time until the entire rice husk was
completely dried. To study the different between washed
and unwashed rice husk, thermogravimetric analysis (TGA)
for these samples was performed. Then, the dried rice husk
was burnt in the PFC at a constant temperature of 600 C
and constant pressure for an hour to ensure that the product
is in an amorphous silica phase. The product obtained was
white with slightly blackish powder form. The rice husk ash
was ground using a mortar to homogenize and to get a
powdered form of the material. The rice husk ash obtained
from this process was labeled as RHA and it was charac-
terized by X-ray diffraction (XRD) technique, Fourier
Transform-Infrared (FT-IR) spectroscopy, Scanning Elec-
tron Microscopy (SEM), X-ray Fluorescence (XRF)
analysis and Thermogravimetric Analysis (TGA). These
characterization procedures are explained in Sect. 2.3.
2.2 Synthesis of zeolites
2.2.1 Synthesis of zeolite NaY
Three different procedures were used to synthesis zeolite
NaY and the conditions of the syntheses were given in
Table 2. The procedures used for the zeolite NaY from
RHA were similar for every sample except on the ageing
and seeding steps which varied depending on the samples.
The synthesis involved a direct method which is a single
step for NA–NS-Zeo and A–NS-Zeo but for the A–S-Zeo
involved three steps including the preparation of seed gel
(5%), feedstock gel (95%) and overall gel.
The general procedures for the synthesis of zeolite are
described below. Firstly, the sodium hydroxide (NaOH)
solution was added to the sodium aluminate followed by
stirring and heated gently until the mixture became an
apparent solution for the preparation of aluminate solution.
The silicate solution was prepared by mixing the RHA with
the NaOH solution in the polytetrafluoroethane (PTFE)
beaker and subsequently stirred and heated in the water
bath at boiling temperature. The aluminate and silicate
solution were then mixed in a Teflon bottle followed by
Table 2 Condition of the synthesis of zeolite NaY
Samples abbreviation Ageing Seeding Steps
NA–NS-Zeo · · 1
A–NS-Zeo 4 4 1
A–S-Zeo 4 4 3
N Non, A Ageing, S Seeding
41
stirring for half an hour. For the A–NS-Zeo sample, the
mixture in the capped Teflon Bottle was then aged for
1 day before heating in an oven but for NA–NS-Zeo, the
mixture was directly heated for 22 h at 100 C at autoge-
nous pressure without ageing. After the appropriate time in
the oven, the solid and liquid content in the Teflon bottle
was separated by vacuum filtration, followed by washing
with hot deionized water and then dried overnight. For the
synthesis of A–S-Zeo, both gels were prepared by the same
method as in the general procedure for the synthesis of
zeolite which was described earlier but in the last step, the
overall gel was prepared by adding the seed gel slowly into
the feedstock gel. The mixture was then transferred into a
Teflon bottle and capped tightly and left for ageing for
1 day at room temperature before heating in the oven.
2.2.2 Synthesis of zeolite NaX
The composition ratio for the preparation of zeolite NaX
was 6Na2O:Al2O3:5SiO2:315H2O. Since the zeolite NaX is
in the same family with zeolite NaY, the procedure for the
preparation of silicate and aluminate solution in the prep-
aration of zeolite NaX was similar to the previous
procedure for zeolite NaY but with varying amount of raw
materials. After the silicate and aluminate solutions were
mixed, the mixture was stirred for an hour, aged for 1 day
and subsequently, inserted in an oven for 7–8 h at 100 C
at autogenous pressure to allow hydrothermal condition to
take place. The solid product was obtained after the fil-
tration, washing and followed by drying.
2.2.3 Synthesis of zeolite NaA
Among the other zeolites, the synthesis of zeolite NaA was
very simple. The composition ratio for the preparation of
zeolite NaA was 3.165Na2O:Al2O3:1.926SiO2:128H2O.
The preparations of NaOH, silicate, aluminate and alumi-
nate–silicate mixture solutions were the same as used in the
former procedures but with different amount of raw
materials used. The mixture of aluminate and silicate were
inserted in an oven for 6 h at 100 C at autogenous pres-
sure directly after the homogenization. Finally, the mixture
was filtered, washed and dried in oven for overnight to
obtain the dried solid product.
2.3 Characterization techniques
The synthesized zeolites were characterized using X-ray
diffraction and infrared spectroscopy techniques. The
structure identification of the synthesized zeolite was done
using X-ray powder diffraction (XRD) method (Bruker).
XRD patterns were recorded with CuKa1 radiation with
k = 1.5418 Å at 40 kV and 20 mA in the range of
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42 J Porous Mater (2010) 17:39–47

2h = 5–50 at a scanning speed of 0.05/s. The patterns RH-AW: 94.7%

found on the diffractogram were compared with the
existing pattern of materials from the powder diffraction RH-BW: 91.3%
files (PDF). The solid samples were characterized with a 50%
Fourier Transform Infrared (FTIR) Spectrophotometer
(model FTIR-8300, Shimadzu, Japan) using the KBr
method. Approximately 0.001 g of the rice husk ash was 50 150 250 350 450 550 650 750 850 °C
taken as a representative from the overall sample and RH-AW
transferred to the mortar crucible. A little KBr was then RH-BW
added in the ratio of 1:100 (sample to KBr) and mixed 0.005
thoroughly. These two substances were ground together 1/°C
using a mortar. The mixture was then pressed at a pressure
of 7 tonnes for one minute to obtain the KBr sample disk. 50 150 250 350 450 550 650 750 850 °C
Finally, the disk was placed at the sample holder for the
Fig. 1 Thermogravimetric analysis of rice husk before (RH-BW) and
FTIR scanning from 400 cm-1 to 4000 cm-1. The surface after (RH-AW) wash with water
morphology of RHA was investigated from the magnified
images taken by Scanning Electron Microscopy (SEM) proved by the disappearance of DTG peak at around
model JSM-6390LV, JEOL Technics Ltd, Japan. Each 450 C and the lower value of total weight loss compared
sample was coated with a platinum film using a SEM auto to that for the unwashed rice husk.
fine-coater unit model JFC-1600 provided by JEOL Rice husk ash (RHA) was obtained from the combustion
Technics Ltd, Japan. For the XRF analysis, a set of stan- of washed rice husk at 600 C using the rice husk burner.
dard parameter for 10 major elements was set on a fully The X-ray diffractogram pattern of RHA is shown in
automated Phillips PW 1480 Spectrometer. A standard Fig. 2. This diffractogram reveals that the silica present in
calibration method was used, using 10 concentration- RHA was completely amorphous to XRD as indicated by
intensity curves, one for each element, constructed from 22 the featureless pattern and the absence of significant peaks
certified reference materials (CRM) of rocks, minerals, and the appearance of diffuse maximum at 2h = 23 typ-
ores, soils, sediments, bricks, etc. The X-ray intensity of an ical for amorphous silica [11].
element in a sample is compared to the appropriate stan- The infrared spectrum for RHA is shown in Fig. 3. This
dard curve, giving its concentration. For %Loss on Ignition spectrum demonstrates a very strong, intense and broad
(LOI) determination, an accurate weight of 1.000 g sample
was placed in the muffle furnace, subsequently heated at 100
1000 C for an hour. The loss of weight of the sample after
80
Intensity (a.u)

the combustion was compared to the weight of sample

before the combustion to get the value of the %LOI. 60
Thermogravimetric analysis (TGA) of rice husk and RHA 40
was performed by using a Mettler TA4000 TG analyzer
20
(Mettler Toledo, Switzerland). Heating was done through
air from ambient to about 900 C and the heating rate was 0
5 10 20 30 40 50
20.00 C/min. The evaluation of data was carried out using 2θ (degree)
Version 8.00 of the STARe Software.
Fig. 2 X-ray diffractogram of RHA

3 Results and discussion

45

The rice husk was washed with water and dried in sunlight 40
804.3
for the purpose to eliminate undesirable compounds or 35 470.6
%T

substances in rice husk sample prior burning it. The ther- 30

mogravimetric analysis (TGA) curves of rice husk before 3465.8 1192.9
25 1102.2
and after wash with water (Fig. 1) as well as their calcu-
lated weight loss revealed that there were different in the 20
2000 1500 1000 500
sample of rice husk before and after wash with water. After
1/cm
wash, most of the impurities in the rice husk such as sand,
rice, soils and other agricultural residue were eliminated as Fig. 3 Infrared spectrum of rice husk ash

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J Porous Mater (2010) 17:39–47 43

peak at 1100 cm-1 which corresponds to the Si–O–Si Table 3 Chemical composition of rice husk ash from XRF technique
asymmetric vibration and due to the greater ionic character Elements oxide Percentage (%)
of the Si–O group, this band is much more intense than the
corresponding C–O band for ether [23]. This spectrum also SiO2 91.65
exhibits bands at 804 and 470 cm-1 which correspond to TiO2 0.03
the symmetric stretching of SiO4 tetrahedra and Si–O Fe2O3 0.27
bending band vibrations, respectively. This data indicates Al2O3 0.27
that the silica phase found in RHA was completely amor- MnO 0.07
phous due to the absence of bands near 622 cm-1 which is CaO 0.58
identical to tridymite (crystalline phase) that shows the MgO 0.58
presence of the cristobalite phase [24]. This observation Na2O 0.74
also supports the results obtained from XRD that the RHA K2O 0.74
contains the amorphous form of silica. The morphology of P2O5 0.19
RHA was taken using scanning electron microscopy (SEM) LOI 4.88
technique and the micrograph can be seen in Fig. 4. This
figure revealed the amorphous form of silica present in
%
RHA. This SEM image further supported the results from 100 RHA-PFC: 11.7%
XRD and IR which explained the presence of amorphous 90
form of silica in RHA which was due to the combustion 80 RHA-OB: 50.2%
temperature of rice husk which was around 600 C. 70
The composition of major elements present in the RHA 60
50
as analyzed by X-ray fluorescence (XRF) technique is
50 150 250 350 450 550 650 750 850 °C
shown in Table 3. The silica content in RHA is somewhat RHA-PFC
higher because most of the impurities were eliminated
during combustion at that temperature. Vempati [10] and RHA-OB 0.002
his team also found that more than 90% amorphous silica 1/°C
was obtained from the combustion of rice husk at 600 C.
They mentioned that the combustion of rice husk at that 50 150 250 350 450 550 650 750 850 °C
temperature can remove amorphous carbon, non-graphitic
carbon (crystalline form) and the remaining organic com- Fig. 5 Thermogravimetric analysis of RHA from plug flow reactor
ponents presented in rice husk. The different between RHA (RHA-PFC) and open burning (RHA-OB)
prepared here and RHA from the open burning can be seen
from TGA curves depicted in Fig. 5. (Fig. 5), the total weight loss as determined by TGA is
As can be seen in TGA curves for RHA from plug flow around 12% for RHA-PFC and 50% for RHA-OB. It is
reactor (RHA-PFC) and from open burning (RHA-OB) clearly evident that the RHA from open burning composed
of many impurities derived mainly from combustible car-
bon and volatile compounds compared to RHA prepared
using plug flow reactor or furnace. Henceforth, RHA pre-
pared here is suitable to be used as source of silica for the
synthesis of highly pure zeolites A, X and Y.
In order to prevent the formation of other zeolites or
phases during the synthesis of zeolite Y and to get highly
pure zeolite NaY from RHA, the seeding and ageing
techniques were highlighted. As a comparison, the proce-
dure for the synthesis of zeolite NaY from RHA either
without ageing or seeding techniques was carried out and
the products were characterized by XRD technique. This
was done to study the effect of ageing and seeding tech-
niques in the synthesis of zeolite NaY. The preliminary
preparation of zeolite NaY from RHA without ageing and
seeding techniques revealed that the mixture consisted of
Fig. 4 Micrograph of RHA taken by scanning electron microscopy the zeolite Y and A; NA–NS-Zeo (Fig. 6). Besides that, we
(SEM) also prepared the zeolite NaY from RHA with ageing but

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A 1100
1000

Intensity (a.u)
800 700
Intensity (a.u)

600 Y
300
Y
400
A AY YA 0
Y Y AY 5 10 20 30 40 50
A Y
200 Y AA
A 2θ (degree)
0
5 10 20 30 40 50 Fig. 8 X-ray diffraction pattern of synthesized zeolite NaY (A–S-
2θ (degree) Zeo) via seeding and ageing techniques (matched with sodium
aluminum silicate hydrate zeolite Y (Na)–Na2Al2Si4.5O13
xH2O
Fig. 6 X-ray diffractogram of NA–NS-Zeo (A Zeolite A, Y Zeolite pattern from PDF)
Y)

It was proven that zeolite NaY of high purity was suc-

Y
340 cessfully synthesized from RHA by seeding and ageing
techniques without marked presence of impurities, i.e.
zeolite P and A. This result revealed that the seeding and
260 P P
P
ageing techniques will induce the zeolite Y formation. In
Intensity (a.u)

previous reports, Zhao et al. [25] used these seeding and

180
P Y
Y Y P
YY
100 YY
0 from coal ash residue. In the synthesis of zeolite Y, when a
5 10 20
2θ (degree)
Fig. 7 X-ray diffractogram of A-NS-Zeo (P Zeolite P, Y Zeolite Y)
without the seeding technique: A–NS-Zeo (Fig. 7). It is
clear that the main impurity in the synthesis of zeolite Y
without the seeding technique was attributed to the for-
mation of zeolite P.
Figure 8 shows the XRD pattern of the zeolite NaY that
was synthesized via the seeding and ageing techniques (A–
S-Zeo). The diffractogram of the zeolite NaY from the
seeding and ageing techniques (A–S-Zeo) exhibit many
significant peaks from 2h = 5–50 indicating that the
samples are in the crystalline form. Furthermore, when this
pattern was matched up with the peaks corresponding to
the zeolite NaY structure as shown in Fig. 8, it shows that
the product formed from the synthesized zeolite NaY by
seeding and ageing techniques (A–S-Zeo) was highly pure
zeolite NaY because all of the peaks were well matched
with the peaks of zeolite NaY structure from Powder
Diffraction Files (PDF). In addition, the diffractogram also
demonstrates that no other significant peaks correspond to
zeolite A and P emerged, which confirmed the elimination
of the formation of zeolite A and P. There were also no
impurities and other phases formed in the synthesized
zeolite NaY.
ageing techniques to generate zeolite Y with a maximum
crystallinity of 72% from coal fly ash through hydrother-
Y mal treatment. In the absence of seed, zeolite P was found
to be a competitive phase and the main impurity present in
the resulting products. Zeolite P is easy to synthesis even
30 40 50
source of silica is from rice husk ash which is less pure than
the commercial silica, this requires the addition of seeds or
initial solution to provide nuclei, which can selectively
induce the formation of zeolite Y and eliminate the
induction and nucleation processes.
Without ageing, the period of crystallization became
shorter resulting in the formation of zeolite A. The silica-
rich zeolite A appears to crystallize well in a period of 1 h
which is followed by rapid conversion in many instances to
hydroxysodalite [26]. Breck [27] in their early experiment
showed that the synthesized product with 92% of zeolite Y
was produced after ageing for 24 h at room temperature as
compared to the product produced without ageing which
was only 63% of zeolite Y. In addition, Ginter et al. [28]
who studied the effects of gel ageing on the synthesis of
zeolite NaY from colloidal silica also reported that pro-
longed ageing led to incorporation of additional Si into the
aluminosilicate solid and this gave rise to a larger number
of smaller nuclei and resulted in a higher final yield of
Zeolite NaY. They also found that in the absence of ageing,
zeolite phases other than NaY were formed.
Two batches of zeolite NaX was synthesized with dif-
ferent crystallization time which was 7 h (NaX-7) and 8 h
(NaX-8). This was done to study the effect of crystalliza-
tion time in the zeolite product even though the deviation
of the crystallization time was merely 1 h. The X-ray

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1800 50

1400 40
773.4 694.3
Intensity (a.u)

569.9
1000 30 500.5

%T
463.8
600 20
1101.3
1005.8
200 10
0
5 10 20 30 40 1
1300 1100 900 700 400
2θ (degree) 1/cm
Fig. 9 X-ray diffractogram of NaX-7 matched with sodium alumi- Fig. 12 Infrared spectrum of A–S-Zeo
num silicate hydrate zeolite X (Na)–Na2Al2Si2.5O9.6
2H2O pattern
from PDF

500 46

400 38
Intensity (a.u)

300 30 559.44
668.53

%T
1643.32 693.70
200 22 748.44
451.45
100 14
3460.53 975.60
0
0
5 10 20 30 40 4000 2400 1400 600
2θ (degree) 1/cm

Fig. 13 Infrared spectrum of the synthesized zeolite NaX

Fig. 10 X-ray diffractogram of NaX-8 matched with sodalite pattern
from PDF (Na8Al6Si6O24(OH)2(H2O)2)

60
1100
50 667.60 382.84
463.35
1638.46
Intensity (a.u)

40
%T

700
554.80
30

300
0 4000
5 10 20 30 40
2θ (degree)
Fig. 11 X-ray diffractogram of the synthesized zeolite NaA matched
with sodium aluminum hydrate zeolite A (Na) (Na2Al2-
Si1.85O7.7
5.1H2O) pattern from PDF
diffractograms of both samples can be seen in Figs. 9 and
10 for NaX-7 and NaX-8, respectively.
The product obtained from the preparation of zeolite
NaX with the crystallization time of 7 h shows very high
purity and crystallinity of zeolite X as well as the absence
of impurities or other phases in the product. Even though
the crystallization time was extended merely 1 h, the
product would be converted to sodalite structure as can be
seen in Fig. 10. Machado and Miotto [13] also observed the
20
3447.83 1004.45
2400 1400 600
50
1/cm
Fig. 14 Infrared spectrum of the synthesized zeolite NaA
same results where the hydroxysodalite would form when
the period of the synthesis of zeolite X from oil shale ash
was increased. Thus, in order to produce the high purity
zeolite X and the absence of sodalite phase, the crystalli-
zation time must be fixed at about 7 h.
The XRD diffractogram of zeolite NaA is presented in
Fig. 11. The XRD pattern of zeolite NaA was matched
with sodium aluminum silicate hydrate zeolite A (Na)
(Na2Al2Si1.85
5.1H2O) taken from Powder Diffraction
Files (PDF) of the XRD instruments. It was also observed
that there were no impurities present inside the product.

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46
Table 4 Infrared spectra data for the synthesized zeolite NaY, NaX and NaA and the comparison from the reference
a b
Vibration mode Zeo-NaY Zeo-NaY (RHA) Zeo-NaX
Asymmetric 1130 (msh) 1101.3 (msh) 971 (s)
Stretch 1005 (s) 1005.8 (s)
Symmetric 784 (m) 773.4 (m) 746 (m)
Stretch 714 (m) 694.3 (m) 690 (wsh)
668 (m)
Double rings 572 (m) 569.9 (m) 560 (m)
T-O bend 455 (ms) 463.8 (ms) 458 (ms)
Notes: aSiO2/Al2O3 4.87, bSiO2/Al2O3 2.40, cSiO2/Al2O3 1.88 [30]
s strong, ms medium strong, m medium, sh shoulder, vw very weak
The synthesis of zeolite NaA was simpler than the syn-
thesis of Faujasite-type of zeolites.
To support the XRD analysis, the mid infrared (IR)
region of the spectrum was used (400–1300 cm-1) since
this region contained the fundamental vibrations of the
framework (Si,Al)O4 tetrahedra and should expose the
framework structure [29]. The infrared spectrum for the
synthesized zeolite NaY with seeding and ageing tech-
niques is illustrated in Fig. 12. The infrared spectra for the
synthesized zeolite NaY show six significant peaks from
1250 to 400 cm-1, comparable to the spectrum zeolite
NaY which was assigned by Flanigen and Khatami [29,
30]. They explained that the IR spectrum for zeolite NaY in
the region of 1300–400 cm-1, six significant peaks
emerged which is related to zeolite NaY structure. Wright
[29] also studied the infrared spectra in the region of 300–
1200 cm-1 for a series of type X and Y zeolites with
varying Si/Al ratios. They assigned bands near 1140 cm-1
to a symmetric Si–O–Si stretching mode, 1075 cm-1 to a
symmetric Si–O–Al stretching mode, the strongest band
near 1000 cm-1 to both Si–O–Si and Si–O–Al asymmetric
stretching modes. The shoulder near 500 cm-1 was found
in NaY zeolite but absent in NaX, as assigned to an Si–O–
Al out-of-plane bending mode.
The infrared spectra of zeolites NaX and NaA can be
seen in Figs. 13 and 14, respectively. The infrared spectra
data for each zeolites are tabulated in Table 4 and are
compared with the infrared data from the references
(Zeolite NaY having SiO2/Al2O3: 4.87, Zeolite NaX hav-
ing SiO2/Al2O3: 2.40, Zeolite NaA having SiO2/Al2O3:
1.88 [30]).
It can be observed that the infrared data of zeolites
synthesized from RHA were quite identical with the ref-
erences and proved the successful conversion of RHA to
zeolites NaA, NaX and NaY. In addition, there are no
impurities or other phases in the products since no other
peaks emerge in the infrared spectra of each synthesized
zeolites. It can be concluded that the results from infrared
spectroscopy were consistent with the XRD data where the
123
J Porous Mater (2010) 17:39–47
c
Zeo-NaX (RHA) Zeo-NaA Zeo-NaA (RHA)
975.6 (s) 995 (s) 1004.4 (s)
748.4 (m) 660 (vw) 667.6 (vw)
693.7 (wsh)
668.53 (m)
559.4 (m) 550 (ms) 554.8 (ms)
451.4 (ms) 464 (m) 463.4 (m)
synthesized zeolites NaY from seeding and ageing tech-
niques and also zeolites NaX and NaA from RHA were
highly pure with no other phases present.
4 Conclusions
In this study, rice husk ash which contains more than 90%
of the amorphous form of silica was prepared from the
combustion of washed rice husk at controlled temperature
of 600 C. The silica content in RHA was found to be
reactive for the synthesis of highly pure zeolites NaA, NaX
and NaY. Zeolite NaY was successfully synthesized from
RHA with high purity and the elimination of the other
phases by seeding and ageing techniques during the syn-
thesis process. On the other hand, the zeolite produced
from RHA without seeding and ageing techniques consist
of the mixture of zeolite A and Y while the zeolite syn-
thesized by ageing and without seeding techniques is
mainly the mixture of zeolite P and Y. As a conclusion, the
local waste material of RHA which is dangerous and
hazardous to human and environment can be converted to
the beneficial advanced materials of zeolites after the
combustion of the materials at 600 C.
Acknowledgements The authors would like to send our gratitude to
Ministry of Science, Technology and Innovation (MOSTI) for the
financial support and all of the members from the Department of
Chemistry, Faculty Science and from Faculty of Bioscience and
Bioengineering, Universiti Teknologi Malaysia in assisting this
research.
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