Influence of silica resource from rice husk on structure of hzsm-5 zeolite - Le Thi Hoai Nam
HZSM-5 material was successfully
synthesized from rice husk silica. The
characterization results show that the synthesized
material has the crystallinity equivalent to that of
the standard sample. Besides the conventional
pores system exiting in zeolite structure, there is
another pores system having diameters in the
range of 10 - 50 nm (mesoporous system). This is
due to the burning of organic compounds left
remaining in the material during the calcination
process. This mesopours system might increase
the catalytic activity of synthesized material. The
results are opened up a new research way to use
rice husk as the silica source for of catalysts
preparation. The more detailed research results
will be published in the near future
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586
Journal of Chemistry, Vol. 47 (5), P. 586 - 590, 2009
INFLUENCE OF SILICA RESOURCE FROM RICE HUSK ON
STRUCTURE OF HZSM-5 ZEOLITE
Received 10 October 2008
Le Thi Hoai Nam, Nguyen Thi Thanh Loan
Institute of Chemistry, Vietnam Academy of Science and Technology
Abstract
HZSM-5 zeolites were successfully synthesized by hydrothermal treament using silica from
rice husk and glasses water. The samples were characterized by XRD, IR, SEM, TEM, BET and
27Al-NMR methods. Characterization results revealed that HZSM-5 material synthesized from
rice husk silica has crystallinity and acidity as high as HZSM-5 sample synthesized from glasses
water. HZSM-5 material synthesized from rice husk silica not only has the conventional pores
system as shown structure of HZSM-5 sample synthesized from glasses water, but also has
mesoporous system with kinetic diameter in range of 10-50 nm. This multi-porous system is
expected to increase significantly the catalytic activity of synthesized material in the reactions with
the present of large molecules .
Keywords: Rice husk silica, ZSM-5, multi-porous system.
I - INTRODUCTION
ZSM-5 zeolite is one of the most used
catalysts because it has high thermal-hydrothermal
durability and is suitable material for the catalyst,
adsorption processes, especially for the cracking
reaction [1]. ZSM-5 zeolite is synthesized by
many different methods. Silica resource for ZSM-
5 zeolite preparation is plentiful as TEOS, Ludox
which are expensive [ 2]. Moreover, traditional
ZSM-5 zeolite with small pore diameter of 5 – 6
Å is limited in the reactions with large molecules.
Rice husk is the milling byproduct of rice
and is a major waste material of the agricultural
industry. In Vietnam, annual rice husk quantity
is 5 million tons [3]. However, rice husk has
little or no commercial application. Therefore,
the reusing of rice husk with high value is of
great interest of many researchers. Rice husk
main compositions are metal oxides, where the
SiO2 content is over 20% and so considered to
be a very good quality of silica source [3, 4, and
5].
In this study, we report the results of the
synthesis and characterization of HZSM-5
zeolite using silica derived from rice husk and
compared with HZSM-5 zeolite using silica
from glasses water.
II - EXPERIMENT
1. Materials
a) Silica-source preparation
Silica-source for the synthesis of ZSM-5 was
extracted from rice husk by using solution
NaOH 1% at 80oC for 30 minutes.
b) HZSM-5 preparation
Raw materials.
Silica-source: extracted solution from
Vietnamese rice husk, aluminum source:
Al2(SO4)3.18H2O (China), tetrapropylamonium
587
bromua (TPABr) (German), Distilled water
Synthesis
ZSM-5 material was synthesized by
hydrothermal crystallization using TPABr as
template. The obtained gel was crystallized at
170oC for 24 hours. The gained solid product
from crystallization process was washed to 7,
dried at 100oC and calcined at 550oC for 5 hours
to remove all the template. Then, product was
ion exchanged with NH4NO3 2 M, washed,
dried and calcined again to form HZSM-5.
Characterization methods
Infrared spectrum (IR): The sample was
wafered with KBr as ratio of 1mg
(sample)/100mg (KBr) and measured by IR
spectrum using Impact 410 (German)
instrument at room temperature in the range of
400 - 1300 cm-1. XRD pattern was analyzed on
Siemens D500 instrument (German) under the
following conditions: CuKα radiation (λ =
1,5406 Å), U = 30kV, I = 25 mA, Scanning
angle 2θ = 0,10 - 300, Scanning rate: 0,20/minute,
Measurement temperature: 25oC. The presence
of aluminum within the framework has been
disclosed through 27Al Solid state magic angle
spinning (MAS)-NMR method. Spectrum was
obtained with a Bruker MSL 400 spectrometer
for 27Al (at 104.3 MHz). Scanning Electro
microscopy (SEM) was carried out on a Jeol
JSM-7500F, sample was dispersed into ethanol,
dried, mounting on a thin plate and coated by a
flimsy gold layer. High-resolution transmission
electro microscopy (TEM) was performed on a
Philips Tecnai-10 microscope at 100 kV. The
specimens for TEM observation were prepared
by embedding the samples in epoxy resin and
ultramicrotoming and mounting on a copper
grid. Nitrogen adsorption/desorption isotherms:
The BET surface area and pore volume were
measured by Nitrogen adsorption/desorption
isotherms using ASAP 2010 equipment
(Micrometrics-USA). The sample was treated in
vide pressure at 120oC for 4 h and at 350oC for 9h.
III - RESULTS AND DISCUSSION
1. IR spectra of HZSM-5
Figure 1 presents IR spectrum of HZSM-5
synthesized from rice husk silica comparing to
that of HZSM-5 synthesized from glasses water
in the range of 400 - 1300 cm-1. From observed
spectrums, we can see that the IR spectrum of
HZSM-5 synthesized from rice husk silica
sample completely agree with that of one
synthesized from glasses water sample. There is
no stranger phase occurring in the spectrum of
the synthesized material. This result
demonstrates that the synthesized materials have
MFI structure. The peak at 550 cm-1 contributes
to the fluctuation of 5-1 rings in ZSM-5
structure and it is typical for the crystalline
status of the material. According to [8], the
crystallinity of the synthesized material is 100%
if the intensive ratio of 550 cm-1 to 450 cm-1
peaks is 0.8. The calculated value of the
intensive ratio of 550 cm-1 to 450 cm-1 in our
case is 0.8 confirming that the crystallinity of
the synthesized material can reach
approximately 100%.
Fig. 1: IR spectra of ZSM-5 zeolite
(a) synthesized from glasses water;
(b) synthesized from rice husk
2. Powder X-ray diffractional patterns
Figure 2 presents the XRD patterns of
HZSM-5 materials synthesized using different
silica sources. The XRD pattern of materials
indicates that no impurities phase or amorphous
materials were presented. In addition, the
intensity of typical maximum diffractions
occurring at 2θ = 5 - 100 and 2θ = 20 - 250 of
synthesized materials is equivalent to that of
588
ZSM-5 standard sample with typical MFI
structure [6]. From this result, we can consider
that the HZSM-5 material synthesized using
silica from rice husk has very high crystallinity
(approximately of 100%) as HZSM-5 material
synthesized using silica from glasses water. This
conclusion completely agrees to that from IR
method.
2-Theta-scale
Figure 2: XRD patterns of (a) HZSM-5 synthesized from glasses water
(b) HZSM-5 synthesized from rice husk
3. Nuclear magnetic resonance 27Al NMR
method
The exits of Al3+ ion in zeolite framework
relates with the acidity of material (due to Al3+
ion tetrahedrally coordinated in zeolite). From
obtained result, the acidity of material can be
indirectly measured via the determining of Al3+
distribution in the zeolite framework. In order
to determine the distribution of Al3+ ion of
synthesized material, the 27Al-NMR method was
used. Figure 3 shows the 27Al-NMR of HZSM-5
material synthesized from rice husk.
It is similar to HZSM-5 material synthesized
from glasses water, the 27Al-NMR spectrum of
the HZSM-5 material synthesized from rice husk
gives rise to a resonance at 55 ppm with high
intensity due to aluminum in a tetrahedral
environment, which is typical for zeolitic
framework aluminum [7,8]. This proves that
almost of aluminum used in synthesis process are
presented in zeolite framework. However, the
27Al-NMR of HZSM-5 material synthesized from
rice husk shows one resonance at 0ppm with very
low intensity and it is negligible in comparing to
the intensity of resonance at 55ppm. According
to references [7,8], this resonance is attributed to
Al3+ which is not presented in zeolite framework
indicating that almost of used aluminum were
corporated in the zeolite framework. These result
showed that HZSM-5 synthesized from rice husk
have high acidity similar to HZSM-5 material
synthesized from glasses water.
4. SEM and TEM images of HZSM-5
synthesized using silica from rice husk
The SEM image of HZSM-5 is presented in
figure 4 showing that the HZSM-5 crystals
were formed with well ordered size of 0.5 - 0.7
μm. The similar result can be obtained from the
SEM image of HZSM-5 showing that the
synthesized material has well ordered size of 0.5
- 0.7 μm.
589
Fig. 3: 27Al-NMR spectrum
(a) HZSM-5 synthesized from glasses water; (b) HZSM-5 synthesized from rice husk.
Fig. 4: SEM image of HZSM-5 Fig. 5: TEM image of HZSM-5
In addition, there observed a very interesting
feature, i.e., a pore system with disordered size
in the structure of HZSM-5 material having the
pore size in range of 10 - 50 nm. This could be
explained that the carbon presenting in the
treated rice husk is continued to be removed in
the calcination process. The removal of carbon
formed special mesoporous system of the
synthesized material.
5. BET characterization of HZSM-5
synthesized using silica from rice husk
The exits of mesostructure of the “HZSM-5”
sample was also observed by N2
adsorption/desorption isotherms. Fig. 6 shows
appearance of a wide hysteresis loop at P/Po of
0.5. This is a typical shape characteristic of
mesoporous structure [8].
590
Fig. 6: N2 adsorption/desorption isotherms
IV - CONCLUSION
HZSM-5 material was successfully
synthesized from rice husk silica. The
characterization results show that the synthesized
material has the crystallinity equivalent to that of
the standard sample. Besides the conventional
pores system exiting in zeolite structure, there is
another pores system having diameters in the
range of 10 - 50 nm (mesoporous system). This is
due to the burning of organic compounds left
remaining in the material during the calcination
process. This mesopours system might increase
the catalytic activity of synthesized material. The
results are opened up a new research way to use
rice husk as the silica source for of catalysts
preparation. The more detailed research results
will be published in the near future.
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Nghiªn cứu ảnh hưởng của nguồn silic tách từ vỏ trấu tới cấu trúc vật liệu zeolit ZSM-5
Le Thi Hoai Nam, Nguyen Thi Thanh Loan
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