Materials Letters 108 (2013) 243–246

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Synthesis of zeolite NaA from sugarcane bagasse ash

Murilo Pereira Moisés a, Cleiser Thiago Pereira da Silva a, Joziane Gimenes Meneguin b,
Emerson Marcelo Girotto a, Eduardo Radovanovic a,n
a
Department of Chemistry, State University of Maringá, Av. Colombo 5790, CEP 87020-900 Maringá, Paraná, Brazil
b
Department of Chemical Engineering, State University of Maringá, Av. Colombo 5790, CEP 87020-900 Maringá, Paraná, Brazil

art ic l e i nf o a b s t r a c t

Article history: Zeolite NaA was synthesized using sugarcane bagasse as silica source under hydrothermal condition at
Received 29 January 2013 80 1C for 72–160 h. The silicon was extracted by alkaline fusion for 40 min, at 550 1C with an alkali:ash
Accepted 23 June 2013 ratio of 1. Zeolite A was obtained without phase contamination. The ash and synthesized zeolite NaA
Available online 28 June 2013
were analyzed by granulometry, XRD, SEM, FTIR, XRF and TG/DTA. In XRD results, all signals were
Keywords: perfectly indexed to zeolite A. The vibration bands at ca. 557 cm−1 suggested the presence of double-four-
Zeolite A ring (D4R) zeolite A structure. The synthesized material has a potential application as a catalyst, as
Alkaline fusion adsorbent, and as an ion exchanger.
Sugarcane bagasse ash & 2013 Elsevier B.V. All rights reserved.
Crystal growth
Phase transformation

1. Introduction This research demonstrates the potential of SCBA extract to be

Sugarcane bagasse is a hazardous solid waste generated in large
amounts in sugar mills. Combustion of sugarcane bagasse in
boilers, used for steam and electricity generation, produces a great
amount of another solid waste, denominated sugarcane bagasse
ash (SCBA) [1]. Therefore, the development of new procedures for
its productive reuse is relevant. Actually, the accumulation of this
waste, which is quartz-abundant, can be avoided if employed as a
silicon source. By means of an alkali fusion extraction method,
quartz particles can be dissolved and used as silicon source for
synthesizing silica-based materials such as zeolites. Most research-
ers have used coal fly ash as a low cost silicon and aluminum
source to produce zeolites. Different types of zeolites such as X
[2,3], ZSM-5 [4], hydroxysodalite[5], Na–P1 [6–9] and zeolite A
[10,11] were synthesized by applying many synthesis methods.
Therefore, the application of this process using SCBA is an
important procedure to increase the value of SCBA and to avoid
environmental pollution caused by this waste. Due to the thermal
stability of quartz crystal, the alkaline fusion is indicated for the
extraction of silicon from SCBA, making it available for zeolite
synthesis [12].
The purpose of this study was to synthesize zeolite from SCBA
in two steps: silicon extraction method by alkaline fusion and
hydrothermal treatment for the zeolite A crystallization process.
n
Corresponding author. Tel.: +55 44 3011 3653; fax: +55 44 3011 4125.
E-mail addresses: eradovanovic@uem.br,
eradovan@bol.com.br (E. Radovanovic).
used as a reliable silica source for preparing pure zeolite A.
2. Experimental procedure
Sugarcane bagasse ash (SCBA) was collected from sugarcane
industry located in the region of Maringá City, Paraná, Brazil. This
quartz material was placed in a horizontal furnace and heated in
air atmosphere at 20 1C min−1 from room temperature to 600 1C
and kept for 4 h (SCBA600).
For the zeolite synthesis, 30 g of SCBA600 was homogeneously
mixed with NaOH in a 1.5 ratio (45 g of NaOH). Then, the mixture
was heated in a nickel crucible in air atmosphere at 550 1C for
40 min. The resultant fused mixture was dissolved in 1.0 L of
distilled water. Soon after, an amount of 1.0 L of sodium aluminate
solution 0.48 mol L−1 (39 g of sodium aluminate-Sigma-Aldrich-in
1.0 L of distilled water) was added to the silicate solution. The
molar ratio of this solution was 2SiO2:1Al2O3:4Na2O:480H2O. The
mixture (2.0 L of result solution) was transferred to ten polypro-
pylene reactors (0.2 L each) and kept at 80 1C for different crystal-
lization periods of time (1, 3, 6, 16, 25, 44, 72, 96, 136, and 160 h).
Then, the solid was separated by filtration, washed with distilled
water and dried overnight at 100 1C.
Characterization: The raw SCBA and SCBA600 were character-
ized by X-ray fluorescence spectroscopy (XRF) (Rigakum model
ZSX mini II, palladium tube) and granulometric analysis. The
thermal behavior was observed through TGA-DTA (Netzsch, model
STA 409 PG/4/G) in air from room temperature to 900 1C at a
fixed heating rate of 10 1C.min−1. The synthesized zeolites were

0167-577X/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2013.06.086
244 M.P. Moisés et al. / Materials Letters 108 (2013) 243–246

Fig. 1. Granulometric analysis and scanning electron micrograph of SCBA (1A), TGA curves and first derivative of the thermal analysis of sample SCBA (1B), and XRD analysis
of the SCBA and SCBA600 samples (1C).

Fig. 2. XRD diffraction patterns of zeolites synthesized in different periods of time Fig. 3. FTIR spectra showing the evolution of zeolite synthesis for different periods
in hydrothermal process. of time in hydrothermal process.
 M.P. Moisés et al. / Materials Letters 108 (2013) 243–246
characterized by the Fourier transform infrared spectrometry
(Bomem-Michelson MB-100 with a resolution of 4 cm−1 using a
KBr disc method), XRD analysis (Shimadzu, model XRD-6000
X-ray operated at 40 kV and 40 mA, with Cu Kα as the radiation
source, diffraction angle – 2θ – in the range 101–601), and scanning
electron microscopy (SEM) (Shimadzu SSX-550 Superscan).
3. Results and discussion
Fig. 1A shows the scanning electron micrograph and granulo-
metric analysis of SCBA. SCBA is composed of 10 mm–1 mm
particles, with a mean value of ca. 200 mm. Fig. 1B displays the
thermogravimetric and differential thermal analyses (TGA/DTA).
The SCBA thermogram presented a weight loss of 16% which was
assigned to water and the exothermic peak at ca. 500 1C (DTA)
evinces the existence of organic residues. Thus, the treatment up
to 600 1C removes all undesired organic compounds (OC) to the
zeolite synthesis. Fig. 1C shows the XRD patterns of SCBA and
SCBA600, indicating a higher crystallinity of SBCA600 caused by
the calcination process, due to decreasing in the amount of OC and
volatile materials, leading to the crystallization of amorphous
phases in the raw material. These results are in good agreement
Fig. 4. SEM micrograph of zeolites synthesized in different periods of time. Inset of Z-160 h (5 μm): EDS spectrum of Z-160 h.
245
with the thermal analysis. The crystalline phase presented by the
ash is quartz (standard pattern number 02-0458 – ICDD database).
The chemical composition (weight percent) of SCBA found by XRF
was 86.2% SiO2, 2.8% Al2O3, 1.6% P2O5, 2.4% K2O, 1.9% TiO2, 1.5% CaO,
2.9% Fe2O3 and 0.7% of trace elements, and of SCBA600 was 92.0%
SiO2, 1.6% Al2O3, 1.1% P2O5, 1.0% K2O, 0.6% TiO2, 0.8% CaO, 1.5%
Fe2O3, and 1.4% of trace elements. This composition indicates the
potential application of this waste in zeolitization process.
Fig. 2 displays the X-ray diffraction patterns of zeolite synthesis
for each period of time. At 25 h zeolite A was detected and this
transformation coincided with Ostwald's rule of successive trans-
formations [13]. Following the crystallization time, an increasing
zeolitization is observed. After 72 h all diffraction peaks were
perfectly indexed to zeolite A belonging to cubic crystal system
and Pm-3m space group (standard pattern number 71–0784 –
ICDD database and standard pattern of International Zeolite
Association – IZA). The peaks in 171 and 381 found before 44 h
could appear from the impurities of sugarcane bagasse ash.
Fig. 3 presents the FTIR spectra of the zeolites as a function of
hydrothermal process period of time. The existence of zeolite A is
suggested by peaks in the lattice region of 1200–400 cm−1. The
band at 870 cm−1, which can be assigned to T–OH bond (T ¼Si or
Al), was found in the amorphous material precursor of zeolite A.
246 M.P. Moisés et al. / Materials Letters 108 (2013) 243–246
Decottignies [13] noticed that this band disappears as the sample
becomes more crystalline. The broad band centered at 1001 cm−1
is assigned to the internal vibration of (Si, Al)–O asymmetric
stretching (tetrahedrally coordinated). This band is slightly shifted
and become sharper as the amorphous material was transformed
to crystalline zeolite A. The signal centered at 671 cm−1 is assigned
to internal vibration of (Si, Al)–O symmetric stretching, and the
signal at 467 cm−1 is assigned to the internal vibration of (Si, Al)–O
bending. The OH band, related to deformational vibrations of
adsorbed water molecules in zeolite channels also appears at ca.
1655 cm−1 [12]. These results show that FTIR is suitable for
monitoring crystallinity of zeolite A during the hydrothermal
synthesis. The peak intensity changes of the characteristic signals
corresponding to the external double-four-ring (D4R) vibration for
the zeolite framework at 557 cm−1 can be used to study the
progress of zeolite crystallization [14]. After 44 h both signals
level up and then remain constant. These results are in good
agreement with the XRD and microscopy results.
Fig. 4 shows the SEM images of the zeolites synthesized in
different periods of time. A well-defined morphology is observed
from a hydrothermal synthesis of 72 h (Z-72 h), which corrobo-
rates the XRD and FTIR results. For the sample Z-160 the zeolite
showed a particle size of 2.44 70.28 mm and a multifaceted shape.
The chemical composition analysis through EDS indicated a
silicon:aluminum ratio of 1:1, which corresponds to the zeolite A.
4. Conclusions
This work showed that the Brazilian sugarcane bagasse ash can
be successfully used as raw material for the hydrothermal synth-
esis of zeolite A, which have potential applications in adsorption,
catalysis, and ion exchangers. This research contributes to materi-
als and environmental science, suggesting the recycling of a
contaminant solid waste generated in large amount in sugar mills.
Acknowledgements
The authors thank both the COMCAP – UEM for SEM analyses
and Laboratório de Adsorção e Troca Iônica - UEM for XRD
analyses realized in the study.
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