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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
Department of Chemistry, State University of Maringá, Av. Colombo 5790, CEP 87020-900 Maringá, Paraná, Brazil
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

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

0167-577X/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
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) 243–246 245

characterized by the Fourier transform infrared spectrometry with the thermal analysis. The crystalline phase presented by the
(Bomem-Michelson MB-100 with a resolution of 4 cm−1 using a ash is quartz (standard pattern number 02-0458 – ICDD database).
KBr disc method), XRD analysis (Shimadzu, model XRD-6000 The chemical composition (weight percent) of SCBA found by XRF
X-ray operated at 40 kV and 40 mA, with Cu Kα as the radiation was 86.2% SiO2, 2.8% Al2O3, 1.6% P2O5, 2.4% K2O, 1.9% TiO2, 1.5% CaO,
source, diffraction angle – 2θ – in the range 101–601), and scanning 2.9% Fe2O3 and 0.7% of trace elements, and of SCBA600 was 92.0%
electron microscopy (SEM) (Shimadzu SSX-550 Superscan). 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.
3. Results and discussion 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
Fig. 1A shows the scanning electron micrograph and granulo- transformation coincided with Ostwald's rule of successive trans-
metric analysis of SCBA. SCBA is composed of 10 mm–1 mm formations [13]. Following the crystallization time, an increasing
particles, with a mean value of ca. 200 mm. Fig. 1B displays the zeolitization is observed. After 72 h all diffraction peaks were
thermogravimetric and differential thermal analyses (TGA/DTA). perfectly indexed to zeolite A belonging to cubic crystal system
The SCBA thermogram presented a weight loss of 16% which was and Pm-3m space group (standard pattern number 71–0784 –
assigned to water and the exothermic peak at ca. 500 1C (DTA) ICDD database and standard pattern of International Zeolite
evinces the existence of organic residues. Thus, the treatment up Association – IZA). The peaks in 171 and 381 found before 44 h
to 600 1C removes all undesired organic compounds (OC) to the could appear from the impurities of sugarcane bagasse ash.
zeolite synthesis. Fig. 1C shows the XRD patterns of SCBA and Fig. 3 presents the FTIR spectra of the zeolites as a function of
SCBA600, indicating a higher crystallinity of SBCA600 caused by hydrothermal process period of time. The existence of zeolite A is
the calcination process, due to decreasing in the amount of OC and suggested by peaks in the lattice region of 1200–400 cm−1. The
volatile materials, leading to the crystallization of amorphous band at 870 cm−1, which can be assigned to T–OH bond (T ¼Si or
phases in the raw material. These results are in good agreement Al), was found in the amorphous material precursor of zeolite A.

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.
246 M.P. Moisés et al. / Materials Letters 108 (2013) 243–246

Decottignies [13] noticed that this band disappears as the sample Acknowledgements
becomes more crystalline. The broad band centered at 1001 cm−1
is assigned to the internal vibration of (Si, Al)–O asymmetric The authors thank both the COMCAP – UEM for SEM analyses
stretching (tetrahedrally coordinated). This band is slightly shifted and Laboratório de Adsorção e Troca Iônica - UEM for XRD
and become sharper as the amorphous material was transformed analyses realized in the study.
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
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