ARCH. ENVIRON. SCI.

(2011), 5, 46-54

Synthesis and characterization of Na-Y zeolite from coal fly ash and its effectiveness
in removal of dye from aqueous solution by wet peroxide oxidation
Arun Kumar Kondru1, Pradeep Kumar2, Tjoon Tow Teng3, Shri Chand1, Kailas L. Wasewar4*
1
Department of Chemical Engineering, Indian Institute of Technology, Roorkee-247667, India
2
Department of Chemical Engineering and Technology, Institute of Technology, Banaras Hindu University, Varanasi –
221005 India
3
Environmental Technology Division, School of Industrial Technology, University Science of Malaysia, 11800 Minden,
Penang, Malaysia
4
Department of Chemical Engineering, Visvesvaraya National Institute of Technology (VNIT) Nagpur - 440011,
Maharashtra, India
*To whom correspondences should be addressed
E-mail: k_wasewar@[Link]
Received June 8, 2011. Revised manuscript received August 16, 2011, Accepted August 18, 2011

Abstract
Na-Y zeolite was synthesized from coal fly ash by alkali fusion followed by hydrothermal
treatment. Characterization of synthesized Y zeolite was done using X-ray diffraction, scanning
electron microscopy, Fourier transform infrared spectroscopy and BET surface area. The effect of
various factors on the formation of zeolite, such as, fusion temperature, heating rate, ageing time,
crystallization time and treatment with acids etc. were studied and the conditions optimized. The
maximum surface area of the synthesized zeolite was 160 m2/g at 550ºC fusion temperature, 10 h
aging time (at room temperature), crystallization at 100ºC for 17 h. In another set of experiments
the fly ash was pretreated with hydrochloric acid. Formation of Na-P zeolite took place along with
Na-Y and the effect of synthesis parameters on the formation of Na-P zeolite, mullite and quartz
were discussed. Heating rates of 1 and 3ºC/min and fusion temperature of 750ºC gave the maximum
Na-P zeolite formation. Na-Y zeolite after ion exchange with Fe was tested as a catalyst towards its
effectiveness for degradation of Congo red from an aqueous solution.
Keywords: Coal Fly Ash, Na-P Zeolite, Hydrothermal Treatment, Color Removal, Cod Removal
conversion of fly ash to zeolites is one of the
1. Introduction approaches, which has wide applications in
Coal-based thermal power installations in catalysis, ion exchange, as molecular sieves and
India contribute about 65% of the total installed adsorbents [2].
capacity for electricity generation as per the Major composition of fly ash is alumina and
report by Bhattacharjee and Kandpal and silica. Apart from these many oxides are also
Central Pollution Control Board [1]. Indian coal present. Due to the presence of alumina and
has very high ash content. The ash content of silica in excess amounts and constant
coal used by thermal power plants in India compositions irrespective of source prompted
varies between 25 and 45%. As the electricity many research works on synthesis of zeolites
requirement is more, about 461 million tonnes from fly ash [3-7]. Among them Holler and
of coal is necessary to meet the requirement. Wirsching [3] are the first to synthesize zeolites
The fly ash generation in 2001 was 80 million from fly ash by hydrothermal method. Later
tonnes, during 2006-07 it was 116 million tones others synthesized zeolites using various
and expected to reach more than 140 million methods.
tonnes by 2012. As a consequence, a huge Although all the methods of synthesis are
amount of fly ash is generated in thermal power based on hydrothermal alkaline conversion of
plants, causing several disposal-related fly ash, they are classified into four methods.
problems. Classic alkaline conversion methods attempted
Fly ash has other sources like rice husk, combination of different ratios of activation
municipal incinerator, ferro-aluminous, and oil agents/ fly ash with temperature, pressure, and
shale. But fly ash from thermal power plants reaction time to synthesize various zeolites [8].
makes a huge impact compared to other sources. Shigemoto et al. [6,9] and Berkgaut and Singer
Among several methods for utilization of fly ash, [10] introduced an additional fusion stage

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 ARCH. ENVIRON. SCI. (2011), 5, 46-54

before hydrothermal treatment. Park et al. zeolite formation and formation of other phases
[11,12] synthesized zeolites using salt mixtures were discussed.
instead of the aqueous solutions as the reaction
medium. Hollman et al. [13] two-stage synthesis 2. Materials and Methods
method produced > 99% pure zeolite products 2.1. Materials
from solutions containing high-Silica. This
solution was obtained from extracting silica by Raw fly ash was obtained from the cyclone
light alkaline attack of fly ash and adjusting the separator of National Thermal Power
Si/Al ratio (Silicon/Aluminium ratio) to obtain Corporation, Visakhapatnam, India. The
the zeolites. physico-chemical properties of fly ash are
Among these methods for synthesis of shown in Table 1. Commercial Na-Y zeolite
zeolites, alkaline fusion followed by was obtained from Sud Chemie Pvt Ltd, Baroda,
hydrothermal treatment has been successfully India. Hydrogen peroxide (30% analytical
used by many researchers for the synthesis of X, grade), manganese dioxide, sodium hydroxide
Y and A zeolites. Shih and Chang [14,15] pellets (AR) and hydrochloric acid were
studied conventional hydrothermal process obtained from RFCL limited (Mumbai), India.
without/ with fusion and found that the later Congo red was obtained from LOBA CHEMIE
showed better results for the synthesis of X,Y Pvt Ltd Mumbai.
and A by changing reaction parameters. Molina Table 1. EDAX composition of fly ash
and Poole [16] studied both conventional
hydrothermal technique and the combination of Element Wt% At%
alkaline fusion of fly ash with NaOH prior to a C 14.09 22.41
hydrothermal treatment, where the fusion O 40.67 48.54
product is mixed with water. In order to Na 00.15 00.13
optimize the synthesis both processes were Mg 00.29 00.23
evaluated at different conditions of temperature, Al 14.67 10.38
time and proportion of NaOH : PFA : H2O. The Si 23.08 15.69
general reaction scheme described by Ojha et al. P 00.52 00.32
[17] for synthesis of X-zeolite is as follows: S 00.27 00.16
NaOH  xAl 2O3  ySiO2   Na2 SiO3  Na2 AlO2
Fusion K 00.77 00.38
Ca 00.48 00.23
NaOH ( aq)  Na2 Al (OH ) 4( aq)  Na2 SiO3( aq)  
Room _ temperature
Ba 01.11 00.15

[ Na x ( AlO 2 ) y ( SiO2 ) z  NaOH  H 2O ]( gel ) 323 
623K
Ti 00.84 00.34
Mn 00.50 00.17
Na p [( AlO 2 ) p ( SiO2 ) q ]  hH 2O Fe 02.56 00.87
(crystal in suspension) 2.2. Zeolite Synthesis
Hui and Chao [18] proposed step-change of
The fly ash was initially screened to
synthesis temperature during hydrothermal
eliminate larger particles and calcined at
treatment to reduce the overall synthesis time
and maintain a high degree of crystallinity for 80010ºC for 2 h to remove the unburnt carbon
the samples. Zhao et al [19] reported the effects and volatiles. Fly ash and sodium hydroxide (in
of ageing and seeding on the formation of powder form) were taken in the ratio of 0.8 to
zeolite Y from coal fly ash and found that 1.5 (by wt), grinded and mixed to form a
ageing enhances the hydrothermal condition and homogeneous mixture. The mixture was heated
eliminates the processes of induction and at a slow rate to reach 550ºC, and fused at this
nucleation. During hydrothermal treatment both temperature for 1-2 h. The fused mixture was
Si and Al present in the fly ash dissolve into the cooled, grinded and mixed in about 500 ml
solution. distilled water and kept stirred for about 10 h
In the present work Na-Y was synthesized (aging). The resulting (sodium aluminate) slurry
from coal fly ash. The optimized conditions for formed was subjected to hydrothermal
high surface area, crystallinity, Si/Al ratio, Na-P crystallization at 90-100ºC for 17 h. After
crystallization, it was cooled and filtered by
Whatman 1 filter paper, washed with distilled
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 ARCH. ENVIRON. SCI. (2011), 5, 46-54

water to remove excess aluminum and dried in The FTIR spectra of the zeolite samples were
an oven at 50-60ºC. The zeolite formed was recorded on a FTIR Spectrometer (Thermo
powdered for further use. Nicolet, USA, Software used: NEXUS) in the
4000 - 500 cm-1 wave number range using KBr
2.3. Characterization
pellets. The internal tetrahedra and external
The determination of structure of the linkage of the zeolites formed were identified
heterogeneous catalysts were done by X-ray and confirmed by FTIR. The IR spectra data
diffractometer (Bruker AXS, Diffractometer D8, was taken from literature [17] shown in Table 2.
Germany) using Cu-Kα as a source and Ni as a BET surface area of the samples was
filter. Goniometer speed was kept at 1º/min and estimated by using Micromeritics
the chart speed was 1 cm/min. The range of CHEMISORB 2720 instrument.
scanning angle (2θ) was kept at 3-60º. The
intensity peaks indicate the values of 2θ, where 2.4. Analysis
Bragg’s law is applicable. The formation of The amount of the dye present in the solution
compounds was tested by comparing the XRD was analyzed by direct reading TVS 25 (A)
patterns of the present work with that found by Visible Spectrophotometer. The visible range
other researchers as well as using JCPDS (Joint absorbance at the characteristic wavelength of
Committee of Powder Diffraction Standard) the sample at 497 nm was recorded to follow the
files. progress of decolorization.
From the XRD plot the values of the The COD of the dye solution was estimated
intensities were noted for each d-spacing value by the Standard Dichromator Closed Reflux
and compared with the JCPDS powder Method (APHA-1989) using a COD analyzer
diffraction file (PDF). The compound and the (Aqualytic, Germany). The color in Pt-Co unit
composition were identified. The percentage was estimated using a color meter (Hanna
crystallinity was calculated as: HI93727, Hanna Instruments, Singapore) at 470
% Crystallinity = (sum of the peak heights of nm.
unknown material) × 100/(sum of peak heights
of standard material). 3. Results and Discussions
The determination of images and 3.1. Factors Affecting the Synthesis of Na-Y
composition of catalysts were done by Zeolite from Coal Fly Ash
SEM/EDAX QUANTA 200 FEG
(specifications: accelerating voltage from 200 V The effect of various parameters on the
to 30 KV, resolution of 2 mm and magnification synthesis of Na-Y zeolite, like heating rate,
up to 1000KX). Scanning for zeolite samples fusion temperature, mixing time, crystallization
was taken at various magnifications and time and temperature and acid treatment were
voltages to account for the crystal formation and evaluated to optimize % crystallization (based
size. From EDAX, the composition of the on all 35 (JCPDS) peaks), BET surface area and
elements in weight percentage and atomic Si/Al ratio.
percentage were obtained along with the spectra Effect of Heating Rate
for overall compositions and particular local
area compositions. After obtaining the homogeneous mixture of
NaOH and fly ash, it was subjected to fusion.
Table 2. Zeolite IR assignments from FTIR The effect of heating rate on crystallinity is
Internal tetrahedral presented in Fig. 1. It can be seen that by
Asymmetric stretch 1250-950 cm -1 varying the heating rate between 1.5 to 4ºC, the
Symmetric stretch 720-650 cm-1 crystallinity was observed in the range of 55 -
T-O bend 420-500 cm -1 99 %. The maximum heating rate 4ºC / min with
External linkage 61.07 % crystallinity was selected for the study.
Double ring 650-500 cm -1 The effect of heating rate on BET surface
Symmetric stretch 750-820 cm-1 area and Si/Al ratio are described in Fig. 2. It
Asymmetric stretch (Sharp) 1050-1150 cm -1 can be seen that there were no effect of heating
rate on BET surface area and Si/Al. The average
value of BET surface area and Si/Al ratio were

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 ARCH. ENVIRON. SCI. (2011), 5, 46-54

found to be 80 m2/gm and 1.6 respectively. The Si/Al ratio was 1.94 at fusion temperature of
maximum values of 89.2 m2/g of BET surface 750ºC, the Si/Al ratio at 550ºC (1.88) was
area and 1.92 of Si/Al ratio were obtained at comparable to that of 750ºC. At 350ºC, the ratio
heating rates of 1.428ºC/min and 1.33ºC/min. was 1.61. Fusion temperature of 550ºC has also
Figure 1. Effect of heating rate on % been found to be optimum for synthesis of
crystallinity various zeolites including Y zeolite [20-21].
100 Effect of Mixing Time
80 The development of crystal nuclei is related
% Crystallinity

60 to the aging. It is observed from literature that

the aging can considerably reduce the
40
crystallization time at elevated temperatures
20 [22]. The fusion temperature was taken as
0
550ºC. Mixing times of 10 h, 24 h, and 48 h
1 1.5 2 2.5 3 3.5 4 4.5 were investigated. The % crystallinity increases
Heating Rate (oC/min)
linearly with mixing time, attaining 74.96%
Figure 2. Effect of heating rate on BET surface crystallinity after 48 h.
area and Si/Al ratio of zeolite, ♦ - BET Surface The BET surface area increases with mixing
area, ■ – Si/Al ratio time. Maximum value of surface area obtained
100 5 was 78.7 m2/g for the mixing time of 48 h
followed by 75.8 m2/g for 24 h and 74.39 m2/g
BET Surface Area (m2/gm)

80 4
for 10 h. Si/Al ratio initially increases from 1.88
at 10 h, reaching to a maximum of 1.92 at 24 h
Si/Al Ratio

60 3

40 2
and decreasing further to 1.817 at 48 h.
The dissolution of Si and Al is a function of
20 1 mixing time (along with reaction time, heating
0 0 time for hydrothermal method) and temperature.
1 1.5 2 2.5 3 3.5 4 4.5 Murayama et al. [23] explained the relation
Heating Rate (oC/min)
between Si, Al concentration in liquid phases
and reaction time, heating time and heating
Effect of Fusion Temperature temperature. The effect of mixing time on %
crystallinity and Si/Al at room temperature was
The silica and alumina present in the fly ash studied by Koroglu et al. [24] using
when reacted with NaOH form Na salts soluble hydrothermal treatment method and the results
in water. Three fusion temperatures; 350ºC, obtained are similar.
550ºC, and 750ºC were experimented and the
effects studied. The heating rate of 4ºC/min was Effect of Crystallization Time and Temperature
selected for the study. Zeolites X and Y nucleate and crystallize
Effect of fusion temperature on % more readily at lower temperature than those
crystallinity was observed. As the fusion having more complicated structure such as
temperature rises, the crystallinity reaches a mordenite. The recommended crystallization
maximum value of 65.79% at 550ºC and temperature for well developed crystals is
diminishes thereafter. At 350ºC, the % reported as 373 K [2].
crystallinity was 36.87, whereas, at 750ºC, the The aluminosilicate gel formed was
value was 41.59. The optimum BET surface subjected to hydrothermal crystallization for
area obtained at optimum fusion temperature of various crystallization times: 10 h and 17 h and
550ºC was 74.39 m2/g. The surface area rises various temperatures: 90ºC and 100ºC and the
with fusion temperature, reaches a maximum at effects were studied. The combined effect helps
550ºC and thereafter diminishes. The value of to optimize crystal size, structure and formation.
surface area at 750ºC (65.68 m2/g) was identical At 100ºC and 17 h, the crystallinity based on
to that obtained at 350ºC (65.4%). all 35 peaks is less (45.3%) (shows the
The Si/Al ratio increased with rise in fusion beginning of formation of crystals). The
temperature. Though the maximum value of crystallinity at 90ºC for 17 h and 100ºC for 10 h
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 ARCH. ENVIRON. SCI. (2011), 5, 46-54

gave better results. Maximum value of 65.79% Acid treatment of fly ash (before fusion) with
crystallinity was obtained at crystallization acids HCl (6-7 N), H2SO4 (2-3 N), and HNO3
temperatures and times of 100ºC for 10 h and (6-7 N) for 17 h at 100ºC were experimented to
also at 90ºC for 17 h. XRD pattern for the effect remove unwanted materials like Fe and other
of crystallization time and temperature is shown oxides located mainly in the outer part of the
in Fig. 3. Nugteren et al. [25] reported that an ash particles [26] which hinder the catalytic
incubation period of 3 h was necessary during activity and dealuminate the fly ash in order to
which the nucleation of zeolites takes place. increase the activity, acidity and thermal
Following nucleation, the crystallization yield stability for the improved performance as
increases progressively up to 24 h. catalyst. Acid treatment is also required to leach
Figure 3. XRD pattern for effect of some amount of Al2O3. It helped in increasing
crystallization time and temperature on Na-P the SiO2 content of the reaction mixture. After
formation treating fly ash with acids, the fly ash is washed
thoroughly with water so that no residual acid
was present in fly ash or the pH was nearby 7. If
any acid is present, it affects the pH of the
solution. pH of the solution has direct effect on
crystallization [27]. Table 3 shows that acid
treatment increases the crystallinity and is
maximum for HCl treated fly ash synthesized
zeolite. Maximum value of crystallinity was
53.17% for HCl followed by HNO3 (47.19%)
and H2SO4 (46.37%).
Table 3 shows that the HCl treatment gives
the maximum surface area of 160.43 m2/g
which is followed by HNO3 (145.37 m2/g) and
The BET surface area value at crystallization
H2SO4 (140.49 m2/g). Si/Al ratio was also more
time and temperature of 100ºC and 10 h was
for HCl treated fly ash (shows that HCl
74.39 m2/g and at 90ºC and 17 h was 73.22 m2/g.
dealuminates the fly ash more) followed by
Zeolite at 100ºC and 17 h crystallization time
H2SO4. Maximum Si/Al of 1.61 was obtained
and temperature resulted in maximum surface
with HCl treatment.
area of 133.85 m2/g indicating the formation of
The % purity was estimated to see that the
a perfect crystal. Effect of crystallization time
final crystals are free from other oxides (other
and temperature on Si/Al ratio of zeolite showed
than Na, Al and Si). This was done through
an identical pattern as that with BET surface
EDAX. Table 3 shows that % purity was
area. A maximum value of 1.88 was obtained
maximum with H2SO4 treated (purity 84.38%).
for crystallization temperature of 100ºC for 10 h.
This shows that H2SO4 removes other oxides
Si/Al ratio for 90ºC for 17 and 100ºC for 17 h
and impurities in the fly ash more than that by
were 1.51 and 1.46 respectively.
HNO3 (purity 82.1%).
Acid Treatment

Table 3. Effect of acid treatment

Treatment % Crystallinity Surface area (m2/g) Si/Al ratio % purity Fe present
NO 45.3 133.85 1.463 74.48 3.28
H2SO4 46.37 140.49 1.583 84.38 1.31
HCl 53.15 160.43 1.61 78.85 1.29
HNO3 47.19 145.37 1.486 82.1 1.44

Iron present on the surface of fly ash affects impurities. EDAX was used to find iron content.
the properties of zeolites like ion exchange and Table 3 shows that iron removal is with H2SO4
binding capacity [28]. The acid treatment showing the removal of other oxides and
conducted was aimed at removing iron impurities in the fly ash more than that with

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HNO3. SEM and FTIR images of fly ash, h, number of peaks formed were 10 and 11
commercial and HCl treated, are shown in Figs. respectively. XRD pattern for the effect of
4 and 5 respectively. crystallization time and temperature is shown in
Fig. 3.
3.2. Formation of Na-P Zeolite, Other Phases in
HCl, H2SO4 and HNO3 were used to treat fly
Na-Y and Iron Exchange of Na-Y
ash. The P-zeolite peaks in XRD were found to
When EDAX compositions were compared be 11 peaks in each case.
with the (JCPDS) PDF results, it was found that
a little variation is occurring in the compositions. Phases and Their Presence in Na-Y Zeolite
When investigated it was found that in the The dominant crystalline components in the
formation of Na-Y zeolite from fly ash, Na-P untreated fly ash are quartz (SiO2) and mullite
zeolite, a competitive phase is also formed [19]. (M, Al6Si2O13). These phases are still present
The effect of various parameters affecting the but to a lower level after synthesis of Na-Y
formation of P-zeolite like heating rate, fusion zeolite. The quartz peaks disappeared due to its
temperatures, mixing time, crystallization time phase conversion and the major crystalline
and temperature and acid treatment of fly ash phase present is zeolite Y. Other crystalline
were studied. The formation of P-zeolite was phases that are observed are trace zeolite P and
confirmed by XRD analysis. unreacted mullite. These results indicate that
The variation in heating rate did not show a most of the crystalline quartz can be effectively
particular relationship with the amount of Na-P converted to zeolite Y, but not the mullite. Zhao
formed (identified by the number of Na-P peaks et al. [19] observed similar phenomenon with
in XRD and intensity of the peaks). For samples the phases present. The XRD pattern is shown
prepared at heating rates of 17, 10, 4, and in Fig. 6 and the presence of these phases are
2ºC/min (7 peaks in each identified), the P shown in XRD identified by PDF (JCPDS).
zeolite formation is less compared to others. For
Exchange of Zeolite with Fe Ion
samples of 3 and 1.33ºC/min, more number of
peaks were identified (12 peaks) leading to Both the commercial and synthesized
greater formation of Na-P zeolite. catalysts are compared before and after
The Na-P zeolite formation slightly decreases exchange with Fe. From the EDAX results
with fusion temperature. For highest fusion (Table 4), it is clear that higher amount of iron
temperature 750ºC, the number of peaks formed is exchanged in synthesized catalyst. The XRD
in XRD is least (9). For 350ºC and 550ºC, the results (Fig. 7) also support the same.
number of peaks formed were 11 and 10 Due to the iron present after the exchange
respectively. process, the Y peaks diminished along with the
It has been found that the zeolite prepared at rise in Fe peaks. Similar phenomena has also
various mixing times 10, 24, and 48 h do not been reported by Yee and Yaacob [29] who
have significant difference. The number of obtained zeolite iron oxide by adding NaOH and
peaks in XRD found are 10, 8, and 9 H2O2 (drop wise) at 60ºC to Na-Y zeolite. XRD
respectively. pattern (Fig. 7) showed diminishing zeolite
Amongst three different samples, sample peaks along with evolution of peaks
crystallized at 90ºC for 17 h showed less zeolite corresponding to y-Fe2O3 with increasing NaOH
P formation (5 XRD peaks). For samples concentration.
crystallized at 100ºC for 10 h and 100ºC for 17
Figure 4. SEM images of fly ash, HCl treated synthesized Na-Y and commercial Na-Y

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 ARCH. ENVIRON. SCI. (2011), 5, 46-54

Figure 5. FTIR of fly ash, HCl treated synthesized Na-Y and commercial Na-Y

Figure 6. Phases in fly ash and synthesized comparison to the synthesized one. After 1 h of
zeolite reaction time, the % dye removal obtained were
80% and 43.1% with commercial and
synthesized catalysts, respectively.
Figure 8. Comparison of dye removal by Fe
Na-Y commercial and Fe Na-Y synthesized
zeolites, Temperature = 90ºC, pH0 = 7, 1ml
H2O2/ 350 ml solution and 1 g/l catalyst

Figure 7. XRD pattern of Iron exchanged

commercial and synthesized Na-Y zeolite

The rate of removal is also very high for

commercial catalyst (shown by the slope of the
curve) compared to synthesized catalyst. After 1
h, the activity of synthesized catalyst did not
change, whereas the commercial catalyst was
active giving around 97% dye removal after 3 h
period.
The Effectiveness of both the catalysts
towards color removal has been reported in Fig.
9. The maximum color removal by Fe Na-Y
3.3. Effectiveness of the synthesized zeolite as
commercial zeolite catalyst was 100% after 3 h
catalyst for the removal of dye
and by Fe Na-Y synthesized zeolite it was 50%
The effectiveness of the synthesized catalyst after the same time. Color removal using
was tested for the degradation of azo dye synthesized catalyst is nearly 50% after 3 h of
(Congo red) by catalytic wet peroxide oxidation reaction time, whereas for commercial catalyst,
using iron exchanged catalysts (commercial as 100% removal was attained in 3 h. The rate of
well as synthesized Y zeolite). The operating color removal is higher for commercial catalyst
conditions are evaluated and optimized. The in comparison to the synthesized catalyst i.e. the
optimum parameters obtained are 90ºC, initial color removal was 50% in 5 min and 70% in 30
pH (pH0 = 7), 1 ml H2O2/350 ml solution and 1 min for commercial catalyst whereas it was 10%
g/l catalyst. Fig. 8 shows % dye removal as a in 5 min and 20% in 30 min for synthesized
function of time for both the catalysts. It can be catalyst.
seen that % dye removal performance of iron
3.4. Effectiveness of Fe-Commercial Na-Y and
exchanged commercial catalyst is better in
Fe-Synthesized Na-Y on COD Removal

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The results have been shown in Fig. 10. The 17 h. In another set of experiments the fly ash
maximum COD removal by Fe Na-Y was pretreated with hydrochloric acid.
commercial zeolite catalyst was 50% after 3 h Formation of Na-P zeolite took place along with
and by Fe Na-Y synthesized zeolite it was 36% Na-Y and the effect of synthesis parameters on
after 3 h. The rate of removal was comparable the formation of Na-P zeolite, mullite and
for both commercial catalyst and the quartz were discussed. Heating rates of 1 and
synthesized one. 3ºC/min and fusion temperature of 750ºC gave
Figure 9. Comparison of color removal by Fe the maximum Na-P zeolite formation. Na-Y
Na-Y commercial and Fe Na-Y synthesized zeolite after ion exchange with Fe was tested as
zeolites, Temperature = 90ºC, pH0 = 7, 1ml a catalyst towards its effectiveness for
H2O2/350 ml solution and 1 g/l catalyst degradation of Congo red from an aqueous
solution.
References
[1] Bhattacharjee U, Kandpal TC. (2002)
Potential of fly ash utilisation in India,
Energy;27:151-166.
[2] Breck DW. (1974) Zeolite molecular sieves,
John Wiley and Sons, New York.
[3] Holler H, Wirsching U. (1985) Zeolite
formation from fly ash, Fortschr.
Mineral.;63:21-43.
Figure 10. Comparison of COD removal by Fe [4] Hemni T. (1987) Synthesis of hydroxy-
Na-Y commercial and Fe Na-Y synthesized sodalite zeolite from waste coal ash, Soil Sci.
zeolites, Temperature = 90ºC, pH0 = 7, 1ml Plant Nutr.;33:517-521.
H2O2/350 ml solution and 1 g/l catalyst [5] Mondragon F, Rincon F, Sierra L, Escobar C,
Ramirez J, Fernandez J. (1990) New
perspectives for coal ash utilization:
synthesis of zeolitic materials, Fuel;69:263-
266.
[6] Shigemoto N, Shirakami S, Hirano S,
Hayashi H. (1992) Preparation and
characterization of zeolites from coal ash,
Nippon Kagaku Kaishi;5:484-492.
[7] Park M, Choi J. (1995) Synthesis of
phillipsite from fly ash, Clay Sci.;9:219-229.
[8] Querol X, Umana JC, Plana F, Alastuey A,
4. Conclusions Soler AL, Medinaceli A, Valero A, Domingo
Na-Y zeolite was synthesized from coal fly MJ, Rojo EG. (2001) Synthesis of zeolites
ash by alkali fusion followed by hydrothermal from fly ash at pilot plant scale: Examples of
treatment. Characterization of synthesized Y potential applications, Fuel;80:857-865.
zeolite was done using X-ray diffraction, [9] Shigemoto N, Hayashi H, Miyaura K. (1993)
scanning electron microscopy, Fourier Selective formation of Na-X, zeolite from
transform infrared spectroscopy and BET coal fly ash by fusion with sodium hydroxide
surface area. The effect of various factors on the prior to hydrothermal reaction. J. Mater.
formation of zeolite, such as, fusion temperature, Sci.;28:4781-4786.
heating rate, ageing time, crystallization time [10] Singer A, Berkgaut V. (1995) Cation
and treatment with acids etc. were studied and exchange properties of hydrothermally
the conditions optimized. The maximum surface treated coal fly ash, Environ. Sci.
2
area of the synthesized zeolite was 160 m /g at Technol.;29:1748-1753.
550ºC fusion temperature, 10 h aging time (at [11] Park M, Choi CL, Lim WT, Kim MC, Choi
room temperature), crystallization at 100ºC for J, Heo NH. (2000) Molten-salt method for

53
 ARCH. ENVIRON. SCI. (2011), 5, 46-54

the synthesis of zeolitic materials I. zeolite [25] Nugteren HW, Hollman GG, Janssen-
formation in alkaline molten-salt system, Jurkovicova M. (1995) Proceedings of
Microporous Mesoporous Mat.;37:81-89. international ash utilization symposium
[12] Park M, Choi CL, Lim WT, Kim MC, Choi (Lexington: University of Kentucky), 224.
J, Heo NH. (2000) Molten-salt method for [26] Natush DFS, Taylor DR. (1980)
the synthesis of zeolitic materials II. Environmental effects of western coal
characterization of zeolitic materials, combustion: part IV, Duluth M N:
Microporous Mesoporous Mat.;37: 91-98. Environmental Research Laboratory.
[13] Hollman GG, Steenbruggena GMJ. (1999) [27] Stepto RFT, Szostak R. (1998) Molecular
A two-step process for the synthesis of sieves: principles of synthesis and
zeolites from coal fly ash. Fuel;78:1225-1230. identification. Springer, PP.79.
[14] Chang HL, Shih WH. (1998) A general [28] Rayalu SS, Udhoji JS, Munshi KN, Hasan
method for the conversion of fly ash into MZ. (2001) Highly crystalline zeolite A from
zeolites as ion exchangers for cesium, Ind. flyash of bituminous and lignite coal
Eng. Chem. Res.;37:71-78. combustion, J Hazard. Mater.;88:107-121.
[15] Chang HL, Shih WH. (2000) Synthesis of [29] Yee M, Yaacob II. (2004) Synthesis and
zeolites A and X from fly ashes and their ion characterization of iron oxide nanostructured
exchange behavior with cobalt ions, Ind. Eng. particles in Na–Y zeolite matrix, Mater. Res.
Chem. Res.;39:4185-4191. Soc.;19:930-936.
[16] Molina A, Poole C. (2004) A comparative
study using two methods to produce zeolites
from fly ash, Miner. Eng.;17:167-173.
[17] Ojha K, Pradhan NC, Amarnath S. (2004)
Zeolite from fly ash: synthesis and
characterization, Bull Mater. Sci.;27:555-564.
[18] Hui KS, Chao CYH. (2006) Effects of step-
change of synthesis temperature on synthesis
of zeolite 4A from coal fly ash. Microporous
Mesoporous Mat.;88:145-151.
[19] Zhao SX, Lu GQ, Zhu HY. (1997) Effects
of ageing and seeding on the formation of
Zeolite Y from coal fly ash, J Porous
Materials;4:245-251.
[20] Fan Y, Zhang FS, Zhu J, Liu Z. (2008)
Effective utilization of waste ash from MSW
and coal co-combustion power plant: Zeolite
synthesis, J. Hazard. Mater. 153:382-388.
[21] Rayalu S, Labhasetwar NK, Khanna P.
(2000) Process for the synthesis of flyash
based zeolite-Y, US Patent 6027708.
[22] Tatic M, Drzaj B. (1985) Zeolites (eds),
Drzaj B, Hocevar S, Pejvonik S. Amsterdam:
Elsevier Science Publishers.
[23] Murayama N, Yamamoto H, Shibata J.
(2002) Mechanism of zeolite synthesis from
coal fly ash by alkali hydrothermal reaction.
Int. J. Miner. Process;64:1-17.
[24] Koroglu HJ, Sarioglan A, Tather M,
Erdem-Senatalar A, Savascı OT. (2002)
Effects of low-temperature gel aging on the
synthesis of zeolite Y at different alkalinities,
J. Crystal. Growth;241:481-488.

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