Bull. Mater. Sci., Vol. 27, No. 6, December 2004, pp. 555–564. © Indian Academy of Sciences.

Zeolite from fly ash: synthesis and characterization

KEKA OJHA, NARAYAN C PRADHAN* and AMAR NATH SAMANTA
Department of Chemical Engineering, Indian Institute of Technology, Kharagpur 721 302, India

MS received 20 May 2004; revised 22 September 2004

Abstract. Coal fly ash was used to synthesize X-type zeolite by alkali fusion followed by hydrothermal
treatment. The synthesized zeolite was characterized using various techniques such as X-ray diffraction,
scanning electron microscopy, Fourier transform infrared spectroscopy, BET method for surface area mea-
surement etc. The synthesis conditions were optimized to obtain highly crystalline zeolite with maximum BET
surface area. The maximum surface area of the product was found to be 383 m2/g with high purity. The crys-
tallinity of the prepared zeolite was found to change with fusion temperature and a maximum value was ob-
tained at 823 K. The cost of synthesized zeolite was estimated to be almost one-fifth of that of commercial 13X
zeolite available in the market.

Keywords. Fly ash; NaX zeolite; hydrothermal treatment; X-ray diffraction; scanning electron microscopy;
BET surface area.

1. Introduction ture within the range of 333–573 K (Henmi 1987a,b;

Mondragón et al 1990; Yang and Kirkpatrick 1990; Shige-
The amount of coal fly ash generated by coal-based ther- moto et al 1992; Lin and Hsi 1995; Park and Choi 1995;
mal power plants has been increasing at an alarming rate Shin et al 1995; Chang and Shih 1998). Henmi (1987a,b)
throughout the world. The disposal of such a huge quan- synthesized hydroxy-sodalite by conventional hydrother-
tity of ash has become a pressing issue. In India, more mal process in the temperature range 353–363 K for 3–
than 90 million tons of fly ash is being generated annu- 24 h. He succeeded in converting about 30% of the origi-
ally with more than 65,000 acres of land being occupied nal fly ash to hydroxy-sodalite with high cation exchange
by ash ponds. Several approaches have been made for capacity compared to the original fly ash. However, major
proper utilization of fly ash, either to reduce the cost of attempts on zeolitization of fly ash have been made from
disposal or to minimize the environmental impact. One of 1990 onwards.
the approaches is the conversion of fly ash to zeolites, Mondragón et al (1990) investigated on possible uses
which have wide applications in ion exchange, as mole- of coal fly ash, in general and synthesis of zeolitic mate-
cular sieves, catalysts, and adsorbents (Breck 1974). The rial from it, in particular. But like most other investiga-
present study is concerned with the synthesis of zeolite tors, they also tried the hydrothermal method. Adsorption
from coal fly ash and its characterization using various property of the treated fly ash was reported to be similar
techniques. to that of commercial 13X zeolite. Shigemoto and co-wor-
Fly ash is mainly composed of some oxides derived kers (1992) also synthesized zeolite by using a similar
from inorganic compounds, which remain after combus- method. They have developed fusion followed by hydro-
tion of the coal. The amounts of the main components of thermal treatment method to synthesize low silica NaX-
ash viz. SiO2 and Al2O3, show few variations with the type zeolite from fly ash (Shigemoto et al 1993). Fusion
type of coal. The similar chemical composition of fly ash of the alkali–fly ash mixture facilitates the formation of
and some volcanic rocks prompted several research groups highly active Na-aluminate and silicates, which are readily
to attempt making zeolite from fly ash (Höller and Wir- soluble in water and enhance zeolite formation. Using
sching 1985; Henmi 1987a; Mondragón et al 1990; Shi- fusion followed by hydrothermal process, the investiga-
gemoto et al 1992; Yang and Kirkpatrick 1990; Lin and tors developed low silica, X-type zeolite selectively. Addi-
Hsi 1995; Park and Choi 1995; Shin et al 1995). In gene- tion of sodium aluminate to the fly ash before fusion
ral, zeolite synthesis processes involve the addition of a brought the success in obtaining Na–A zeolite also.
caustic agent to the fly ash slurry at higher temperatures. Lin and Hsi (1995) extensively investigated effects of
In 1985, Höller and Wirsching utilized fly ash as the raw the hydrothermal reaction parameters such as tempera-
material for synthesis of zeolite using hydrothermal me- tures, molarity of caustic reagents and reaction time on
thod. After that, a number of researchers have used this the properties of the treated fly ash and also optimized
process successfully, varying the hydrothermal tempera- the reaction parameters to obtain best quality product.
They carried out experiments in open as well as in closed
*Author for correspondence systems at elevated pressure (500 psi) and temperatures
555
556 Keka Ojha, Narayan C Pradhan and Amar Nath Samanta

as high as 473 K. The synthesis of zeolite was also stu- they described fusion method to synthesize zeolites X, Y
died with fly ash of varying chemical composition, which and A. They also showed the capability of fusion method
was not investigated in previous works. to synthesize a specific zeolite selectively by varying the
Shih and Chang (1996) investigated the effects of cur- reaction parameters.
ing temperature and chemical composition on formation Park and co-workers (2000) developed a new method
of two types of zeolites, zeolite A and faujasite, from Class for synthesizing zeolite under molten conditions without
F fly ash at lower temperature (only 311 K). But, the treat- any addition of water. However, complete zeolitization of
ment time required for synthesizing zeolite A by them fly ash could not be accomplished by this molten salt
was longer enough, more than 3 days. Yoshida and Inoue method, probably due to low temperature and insufficient
(1986) synthesized a similar type of zeolite A at 363 K and contact of NaOH with raw materials. The molten salt pro-
they observed that at higher temperature zeolite A began duct was of irregular morphology, in which zeolites could
to disappear and zeolite P started to form. not be identified by their characteristic morphological sha-
Querol and co-workers (1997a) used KOH and NaOH pes. On the other hand, well-developed polycrystals were
as activators to synthesize zeolite using both open and observed in the hydrothermal product. These results indi-
closed system. They have carried out experiments from cate that the crystal growth in molten-salt state is some-
fly ashes of varying compositions, collected from different what limited compared to that in hydrothermal products.
power plants. Their results have shown higher conversion Based on the above discussion, it can be concluded
efficiency of NaOH than that of KOH solutions; even at that alkali fusion followed by hydrothermal treatment is
higher KOH concentrations (1⋅0 M and 473 K), quartz and the most reliable method of obtaining faujasite (Na–X
mullite could not be dissolved substantially and remained and Na–Y) type zeolite selectively from fly ash of diffe-
in the fly ash. Higher pH of the solution also showed bet- rent compositions. It was, therefore, thought desirable to
ter zeolite synthesis efficiency. Mainly zeolite NaP1, NaP convert fly ashes from some of the Indian thermal power
derivatives and Phillipsites have been synthesized by plants to zeolites, which could be used as catalysts for
NaOH and KOH activation. some industrially important reactions, by alkali fusion fol-
Querol et al (1997b) reported microwave-assisted method lowed by hydrothermal treatment.
for zeolite synthesis from coal fly ash. Yields and zeolite
types obtained from the microwave and conventional ex-
2. Experimental
periments have been reported to be very similar, but the
activation time has been drastically reduced by using
2.1 Materials
microwaves (from 24–48 h to 30 min).
Chang and Shih (1998) established the alkali fusion The main raw material, coal fly ash samples were collec-
followed by hydrothermal treatment as a general method ted from electrostatic precipitators of three different Indian
for synthesis of a particular type of zeolite from different thermal power plants, Kolaghat Thermal Power Station
sources of fly ash. They have also compared their results (KTPS) and Durgapur Thermal Power Station (DTPS),
with simple hydrothermal treatment (without fusion) and West Bengal and National Aluminium Company (NALCO),
have concluded that the fusion approach is a better pro- Orissa, India. The samples contained both amorphous
cess which can be applied to fly ash of wide composition (mainly SiO2, Al2O3) and crystalline components (mainly
ranges. In the year 2000, the same research group pub- quartz and mullite). Table 1 presents the physico-che-
lished another paper (Chang and Shih 2000) in which mical properties of the fly ash samples used in the pre-

Table 1. Physico-chemical properties of fly ash samples obtained from

different Indian thermal power plants.

Composition (wt %) of fly ash obtained from

Components KTPS DTPS NALCO

Na2O 2⋅12 1⋅14 0⋅70

Al2O3 30⋅01 27⋅86 29⋅19
SiO2 55⋅19 60⋅03 55⋅60
K2O 1⋅40 0⋅00 1⋅09
CaO 0⋅77 0⋅54 3⋅69
TiO2 2⋅74 4⋅27 2⋅03
Fe2O3 4⋅58 4⋅08 4⋅95
BaO 1⋅28 0⋅21 0⋅00
MgO 1⋅91 1⋅87 2⋅75
Surface area (m2/g) 2⋅9 1⋅4 3⋅5
Mean particle size (µm) 24⋅90 26⋅08 13⋅94
 Zeolite from fly ash: synthesis and characterization 557

sent investigation. As can be seen from this table, the fly tion pattern (Szostak 1976). The major peaks were selec-
ash samples used were of ‘Class F’ type with SiO2, Al2O3 ted specifically because they are least affected by the
and iron oxide as the major constituents. Commercial 13X degree of hydration of samples and also by others. The
zeolite was purchased from SRL Pvt. Ltd., Mumbai, India. percentage crystallinity was taken as the sum of the peak
Sodium hydroxide was procured from Glaxo Laboratories heights of the unknown materials divided by the sum of
(India) Ltd. the peak heights of a standard material that has been assu-
med to be 100% crystalline i.e.

2.2 Zeolite synthesis % Crystallinity = (sum of the peak heights of

unknown material) × 100/(sum of peak heights
Before any treatment, the raw fly ash samples were first of standard material).
screened through a BSS Tyler sieve of 80-mesh size to
eliminate the larger particles. The unburnt carbon (4–6%) 2.3b Morphological analysis by scanning electron micro-
along with other volatile materials present in fly ash were scope (SEM): The morphological structure of the raw fly
removed by calcination at 800 (± 10) °C for 2 h. Fly ash ash, treated fly ash and synthesized zeolitic materials were
samples were further treated with hydrochloric acid to obtained by using scanning electron micrograph (Jeol,
increase their activity in zeolite formation. The acid treat- JSM 5800). The bulk composition was also estimated from
ment helped to dealuminate the fly ash and removed iron SEM/EDXS by indirect method. The elemental composi-
to a certain extent, thereby increasing the activity, thermal tion of the samples was first determined from the SEM/
stability and acidity of the zeolite, all aiming for better EDXS, and from these data, the percentages of oxides
catalytic applications.
Mixture of sodium hydroxide and fly ash (calcined and
HCl treated) in a pre-determined ratio, was milled and
fused in a stainless steel tray at different temperatures
ranging from 500–650°C for 1 h. The sodium hydroxide
to fly ash ratio (by weight) was varied from 1⋅0–1⋅5. The
resultant fused mixture was then cooled to room tempera-
ture, ground further and added to water (10 g fly ash/100 ml
water). The slurry thus obtained was agitated mechanically
in a glass beaker for several hours. It was then kept at
around 90°C for 6 h without any disturbance. The flow
diagram of the synthesis process is shown in figure 1.
The resultant precipitate was then repeatedly washed with
distilled water to remove excess sodium hydroxide, fil-
tered and dried. The sodium hydroxide added to the fly
ash not only works as an activator, but also adjusts the
sodium content in the starting material. Mullite and α-
quartz present in the fly ash are the sources of aluminum
and silicon, respectively, for zeolite formation. The syn-
thesis conditions used with different samples are presen-
ted in table 2.

2.3 Characterization

2.3a X-ray diffraction: The X-ray (powder) diffraction

(XRD) patterns of different fly ash samples and synthetic
zeolitic materials were obtained using a Philips X-ray dif-
fractometer (Philips BW1710). Operating conditions invol-
ved the use of CoKα radiation at 4 kV and 30 mA. The
samples were scanned from 10–50° (2θ, where θ is the
angle of diffraction). Various crystalline phases present
in the samples were identified with the help of JCPDS
(Joint Committee on Powder Diffraction Standards) files
for inorganic compounds. Quantitative measure of the
crystallinity of the synthesized zeolite was made by using Figure 1. Process flow diagram for synthesis of zeolite from
the summed heights of major peaks in the X-ray diffrac- fly ash.
558 Keka Ojha, Narayan C Pradhan and Amar Nath Samanta

Table 2. Zeolites designations and their synthesis conditions.

Zeolite synthesis condition

Hydrothermal treatment
Zeolite Source NaOH/fly Fusion Aging
designation of fly ash ash ratio temp (K) time (h) Temp (K) Time (h)

ZOP-21 KTPS 1⋅2 823 12 363 6

ZOP-30 KTPS 1⋅3 823 24 363 6
ZOP-31 KTPS 1⋅3 823 18 363 6
ZOP-53 DTPS 1⋅3 823 18 363 6
ZOP-57 NALCO 1⋅3 823 18 363 6

KTPS: Kolaghat Thermal Power Station, West Bengal, India; DTPS: Durgapur Thermal
Power Station, West Bengal, India; NALCO: National Aluminium Company Ltd., Orissa,
India.

were calculated. The results were further verified by X-ray

fluorescence (XRF) data.

2.3c Particle size and surface area: The average parti-

cle sizes of various samples were determined by particle
size analyser (Malvern Instruments M7). BET method
was used to measure specific surface area of the samples
(Flowsorb-II, Micromeritics).

2.3d Fourier transform infrared (FT-IR) spectra: Infra-

red spectroscopic analysis of different materials was car-
ried out to study their structural features and acidity.
Infrared spectroscopic analysis of the prepared zeolite
samples was performed with a Nicolet Magna (Series II)
spectrometer with a DTGSBr detector and KBr as beam
splitter with 100 scans for wave number range of 400–
4000 cm–1.

3. Results and discussion

3.1 Mineralogical properties

Figure 2. XRD patterns of fly ash, synthesized zeolite (ZOP-30)
and commercial 13X zeolite.
The coal fly ash contains mainly SiO2, Al2O3 and some
amount of Fe2O3 and the oxides of Mg, Ca, P, Ti etc. The
chemical compositions of fly ash samples used in the INDEX to the POWDER DIFFRACTION FILE (1967)
present study are given in table 1. The X-ray diffraction and data files compiled in the book by Szostak (1976).
patterns of original fly ash, zeolite synthesized from fly The diffractograms show that the original crystalline pha-
ash (ZOP-30) and commercial 13X zeolite are shown in ses of fly ash, quartz and mullite, are mostly absent in the
figure 2. The XRD pattern of original fly ash mainly repre- zeolitic materials after reaction. The XRD patterns of the
sents the presence of crystalline quartz and mullite. Besides treated fly ash (KTPS fly ash is taken as the representa-
some crystalline phases (quartz, mullite, hematite etc), ash tive, figure 2) exactly matched with that of the X-type
is primarily composed of amorphous material. The partial zeolite (Charnell 1971).
hub seen in the background at lower diffraction angle is The scanning electron micrographs (SEM) of the origi-
responsible for the amorphous phases. The full hub is not nal fly ash, treated fly ash (synthesized zeolite) and com-
visible as the scanning was started from 10° and not from mercial zeolites are shown in figure 3. The absence of the
the origin. spherical particles in treated fly ash (as evident from the
Fly ash, after treatment gives several sharp diffraction SEM) indicates high conversion of fly ash to crystalline
peaks, which are different from those present in the un- zeolite on hydrothermal treatment. The crystal structure of
treated one. Different crystalline zeolitic phases present the synthesized zeolite was determined to be distorted octa-
in the treated fly ashes were identified using INORGANIC hedra (Charnell 1971; Bogomolov and Petranovsky 1986).
 Zeolite from fly ash: synthesis and characterization 559

3.2 Structural feature from infrared spectroscopy spectroscopy can yield information concerning structural
details of the material. In general, the IR spectrum can be
Although X-ray powder diffraction data and adsorption split into two groups of vibrations: (i) internal vibrations
measurements are the widely used techniques for identi- of framework TO4 units, which are insensitive to the
fication of zeolite structure and types, other techniques also structural vibrations; and (ii) vibrations related to the
give useful structural information as well. Infrared (IR) external linkage of the TO4 units in the structures. The
latter is sensitive to structural vibrations (Szostak 1976).
In general, each zeolite has a characteristic infrared pat-
tern. However, some common features are observed, which
include the asymmetric and symmetric stretch, double
ring vibrations, T–O bending modes, and possibly pore
opening modes. The frequency regions where different
kinds of vibrations are located in zeolites are summarized
in table 3.
The IR spectra of the original fly ash and treated fly
ash are shown in figure 4. The two most intense bands for
zeolites usually occur at 860–1230 cm–1 and 420–500 cm–1,
which are shown more clearly in figure 5. The first is assig-
ned to an asymmetric stretching mode and the second one
to a bending mode of the T–O bond. All these bands are
more or less dependent on the crystal structure. The mid-
infrared region of the spectrum contains the fundamental
framework vibration of Si(Al)O4 groupings. The IR spec-
tral data for Na–X type zeolites from the literature (Flani-
gen et al 1971) and that of the synthesized zeolite are
presented in table 4. The absorbance band in between the
wave numbers 980–1320 cm–1 in the IR spectrum of fly
ash and treated fly ash represents the presence of substi-
tuted Al atoms in the tetrahedral forms of silica frame-
works. All these observations confirm the formation of
X-type zeolites on alkali and hydrothermal treatments of
fly ash.

3.3 Alkali requirement for fusion of fly ash

Alkali fusion is a conventional method for chemical ana-

lysis to decompose materials containing silicon and/or alu-
minum. The sodium hydroxide present in the reaction
mixture acts as an activator during fusion to form soluble
silicate and aluminate salts, which further takes part in zeo-
lite formation during hydrothermal process. Na+ cation
also plays an important role in zeolitization. Sodium ions
are known to stabilize the sub-building units (specially

Table 3. Zeolite IR assignments (common for all zeo-

lites).

Internal tetrahedral:
Asymmetric stretch 1250–950
Symmetric stretch 720–650
T–O bend 420–500

External linkage:
Double ring 650–500
Pore opening 300–420
Symmetric stretch 750–820
Figure 3. Scanning electron micrographs of (A) fly ash, (B)
Asymmetric stretch 1050–1150 (Sharp)
synthesized zeolite (ZOP-30), and (C) commercial 13X zeolite.
560 Keka Ojha, Narayan C Pradhan and Amar Nath Samanta

six member ring) of zeolite frameworks and usually are cies, a structure consistent with its incorporation into zeolite
required for zeolite synthesis under hydrothermal condi- framework during hydrothermal treatment. The general
tions. The effects of NaOH to fly ash ratio on SiO2/Al2O3 reaction scheme describing the zeolite synthesis process
as well as on Na/Al ratio of the prepared zeolite were stu- is as follows:
died by varying the ratio from 1⋅0–1⋅5. It can be seen from Fusion
figure 6 that the SiO2/Al2O3 (w/w) ratio in the bulk phase NaOH + xAl2O3⋅ySiO2 Na2SiO3 + Na2AlO2
changed from 1⋅68–1⋅98 as the NaOH/fly ash ratio was room-temperature
varied from 1⋅0–1⋅2, attained a maxima at 1⋅2 and then NaOH (aq) + Na2Al(OH)4 (aq) + Na2SiO3 (aq)
started to fall. The sodium to aluminum (atomic) ratio of
[Nax(AlO2)y(SiO2)z⋅NaOH⋅H2O] (gel)
323–623 K
the treated ash was also found to increase with the increase
in NaOH content of the mixture during fusion as shown Nap[(AlO2)p(SiO2)q]⋅hH2O (crystal in suspension)
in figure 6. The higher the sodium contents in the reac-
tant mixture during fusion, the higher is the production
of water-soluble sodium silicates. Increased formation of
sodium silicates again enhances the yield of zeolitic mate- 3.4 Effect of fusion temperature
rials produced in subsequent stages.
Crystallization of the zeolitic materials occurs through The properties of synthesized zeolitic materials are also
nucleation reaction and crystal growth. Nucleation again affected by fusion temperature (FT). The effect of fusion
depends upon the alkalinity. Thus, crystallinity of the temperature on SiO2/Al2O3 ratio was studied in the tem-
resultant products is a function of the alkalinity of the perature range 773–923 K. Figure 8 shows the variation
reaction mixture. The effect of NaOH/fly ash ratio on crys- of SiO2/Al2O3 ratio with fusion temperature. As seen from
tallinity is shown in figure 7. Crystallinity of synthesized this figure, the ratio first increases with fusion tempe-
zeolite increases with increase in NaOH/fly ash ratio up rature, attains the maximum at around 823 K and then
to a certain value after which it shows a decreasing trend. decreases. During fusion, the silica and alumina present
As mentioned earlier, alkali present in the fusion mixture in the fly ash react with the alkali and form Na-salts solu-
reacts with the silica and alumina present in the fly ash ble in water.
and form silicate and aluminate salts. The mineralogical The crystallinity was also found to change with fusion
study indicated the presence of mullite and quartz as major temperature and the maximum value was obtained at 823 K
reactive phases during zeolite synthesis from fly ash after as shown in figure 8. With increase in temperature beyond
alkali activation. Hematite (Fe2O3) was not affected by this point, the crystallinity of the synthesized zeolite was
the activation. However, separation of iron oxides prior found to decrease.
to zeolite synthesis resulted in an increase in conversion
efficiency as described in the acid treatment section. Sili- 3.5 Effect of aging time
cate anions react readily with Al (III) precursors to form
aluminosilicate compounds. In alkaline solutions, alumi- The influence of aging at room temperature on the cha-
num gives negatively charged tetrahedral [Al(OH)4]– spe- racteristics of the synthesized zeolite was investigated in

Figure 4. IR spectra of fly ash and zeolite from fly ash (ZOP- Figure 5. IR spectra of synthesized zeolite in 1250–400 cm–1
30). wave number region.
 Zeolite from fly ash: synthesis and characterization 561

Table 4. Infrared spectral data for Zeolite X.

Wave number (cm–1)

→
Parameter ↓ Synthesized zeolite Na–X (Flanigen et al 1971)

Double ring 565 mb 560 m

Asymmetric stretching 1061 msh 980 s 753 w 1060 msh 971 s 746 m
Symmetric stretching 670 w 690 wsh 668 m 690 wsh
T–O bending 470 ws 458 ms
Pore opening 414 ms 406 w 365 m

s = strong; ms = medium strong; m = medium; mw = medium weak; sh = shoulder; b = broad;

w = weak.

the present work. The aging is related to the development

of crystal nuclei. It is observed from previous studies that
the aging can considerably reduce the reaction time for
crystallization at elevated temperatures (Tati… and Drñaj
1985).
The effects of aging time on SiO2/Al2O3 ratio as well
as on crystallinity of the synthesized zeolite were shown
in figure 9. As seen from this figure, the SiO2/Al2O3 ratio
of the zeolite increases first and then decreases after
attaining a maximum of 1⋅72 for an aging time of 18 h.
The crystallinity of the synthesized zeolite, however, increa-
ses with aging time up to about 24 h and then becomes
almost independent of it as observed from the same fig-
ure. Therefore, an aging time was optimized at 18 h to get
highly crystalline zeolite with high silica/alumina ratio.

Figure 6. Effect of NaOH content of reaction mixture on 3.6 Effect of hydrothermal treatment time
SiO2/Al2O3 and Na/Al ratios of synthesized zeolite (Conditions:
aging time, 18 h; hydrothermal treatment time, 6 h; fusion tempe- During hydrothermal treatment, the aluminosilicate salts
rature, 823 K).
crystallize as various zeolitic materials. Previous studies
reported that zeolites could be synthesized at any tempe-
rature in the range 333–573 K. The faujasite like zeolites
(types X and Y) nucleate and crystallize more readily at
lower temperature than those having more complicated
structure such as mordenite. The recommended crystalli-
zation temperature, which gives a reasonable rate and well
developed crystals, is about 373 K (Breck 1974). In the
present study, the hydrothermal treatment temperature was
kept at 363 K for the above-mentioned reasons. Hydro-
thermal treatment time was found to influence the surface
area of the synthesized zeolite as shown in figure 10.
From the figure, it is clear that the surface area of the pre-
pared zeolite increases gradually with increase in hydro-
thermal treatment time up to 6 h and then decreases.
Hydrothermal treatment time was, therefore, optimized at
6 h. In their publication on zeolite synthesis from fly ash,
Nugteren et al (1995) reported that there is an incubation
period of 3 h during which the nucleation of zeolites
Figure 7. Effect of NaOH/fly ash ratio on crystallinity of syn- takes place. Following nucleation, the crystallization yield
thesized zeolite (Conditions: aging time, 18 h; hydrothermal treat- increases progressively up to 24 h. After this second stage,
ment time, 6 h; fusion temperature, 823 K). there is only a minor increase of zeolitization with time.
562 Keka Ojha, Narayan C Pradhan and Amar Nath Samanta

In the present study, no improvement in the crystal growth applications of zeolites. Some of these unwanted mate-
was observed after 6 h. This observation is also in good rials could be removed by acid treatment. In the present
conformity with the findings of Tati… and Drñaj (1985). study, HCl was used to reduce the concentration of iron
Furthermore, the zeolite X was found to be transformed and alkali oxides present in fly ash, which were located
to the more stable phillipsite phase when it was kept in mainly in the outer part of the ash particles (Natush and
contact with its mother liquor for a longer period of time. Taylor 1980) and also to leach some amount of Al2O3.
Thus, it helped in increasing the SiO2 content of the reac-
tion mixture. On acid treatment, iron oxide present in the
3.7 Effect of acid (HCl) treatment
original fly ash was removed to some extent.
Addition of Na-silicate to the fly ash before hydrother-
Alongwith SiO2 and Al2O3, fly ash contains several other
mal treatment is known to increase the SiO2/Al2O3 ratio,
components that are undesirable in synthesized zeolites.
but no improvement was observed in our experiment on
Some of these components act as poison during catalytic
addition of Na-silicate (table 5).

3.8 Thermal stability of the prepared zeolite

Crystalline zeolites are more resistive to heat than amor-

phous materials, the main reason being the geometrical
structure of the crystalline framework. However, the effects
of silica/alumina ratio and level of cations exchange on
thermal stability also cannot be denied. The commercial
zeolites having high SiO2/Al2O3 ratio can resist much
higher temperature. The zeolite presently prepared was
observed to lose its crystallinity beyond 973 K and the
crystalline structure was mostly collapsed above 1073 K
(figure 11).

3.9 Comparative study on fly ashes collected

from different sources
Figure 8. Effect of fusion temperature on SiO2/Al2O3 ratio and
crystallinity of synthesized zeolite (Conditions: hydrothermal There are more than 80 thermal power plants in India,
treatment time, 6 h; (1) NaOH/fly ash ratio, 1⋅0; aging time, 18 h; which use coal from different mines. Usually, the charac-
(2) NaOH/fly ash ratio, 1⋅3; aging time, 18 h; (3) NaOH/fly ash
ratio, 1⋅3; aging time, 12 h).

Hydrothermal treatment time (h)

Figure 9. Effect of aging time on SiO2/Al2O3 ratio and crystal- Figure 10. Effect of hydrothermal treatment time on surface
linity of synthesized zeolite (Conditions: NaOH/fly ash ratio, area of synthesized zeolite (Conditions: NaOH/fly ash ratio, 1⋅3;
1⋅3; fusion temperature, 823 K; hydrothermal treatment time, 6 h). fusion temperature, 823 K; aging time, 18 h).
 Zeolite from fly ash: synthesis and characterization 563

Table 5. Variations of SiO2/Al2O3 and Na/Al ratios of the synthesized zeo-

lite with different treatments.

Material SiO2/Al2O3 Na/Al

1. Fly ash + NaOH 1⋅70 0⋅642

2. Fly ash + Na-silicate + NaOH 1⋅44 0⋅803
3. Fly ash treated with HCl before fusion + NaOH 1⋅82 0⋅250
4. Commercial 13X zeolite 1⋅51 0⋅491

Conditions: NaOH/fly ash ratio, 1⋅3; fusion temperature, 550°C; aging time,
18 h; hydrothermal treatment time, 6 h.

Table 6. Physico-chemical properties of zeolites synthesized from fly ash of different sources.

Composition (wt %) ZOP-21 ZOP-30 ZOP-31 ZOP-53 ZOP-57 Commercial (13X)

SiO2 50⋅81 47⋅8 48⋅03 42⋅19 40⋅82 48⋅26

Al2O3 27⋅97 27⋅4 27⋅20 31⋅66 25⋅60 31⋅87
Fe2O3 2⋅11 2⋅9 3⋅57 5⋅41 1⋅73 3⋅00
Na2O 13⋅21 17⋅6 15⋅57 8⋅94 15⋅22 15⋅67
CaO 1⋅14 1⋅0 1⋅47 2⋅67 4⋅16 0⋅37
K2O 0⋅68 0⋅6 0⋅77 0⋅0 0⋅75 0⋅07
TiO2 2⋅54 1⋅4 2⋅12 5⋅15 1⋅24 0⋅08
MgO 0⋅69 0⋅6 0⋅49 0⋅52 0⋅96 0⋅00
BaO 0⋅85 0⋅7 0⋅78 0⋅0 0⋅90 0⋅00
Surface area (m2/g) 350 383 376 296 320 478
Mean particle size (µm) 5⋅35 5⋅69 5⋅60 14⋅15 5⋅20 1⋅57
Crystallinity (%) 75⋅64 125⋅93 84⋅55 30⋅47 40⋅80 100

teristics of the fly ash produced are also varied depending

on their sources. Synthesis of zeolites was studied with
fly ash samples from three different Indian thermal power
plants. Along with other parameters, initial composition
of fly ash affects the properties of the end products. As
stated earlier, fly ash samples were collected from the
KTPS, DTPS and NALCO and zeolites were synthesized
from these samples. The synthesis conditions were opti-
mized with respect to the silica/alumina ratio from the
detailed study with the KTPS fly ash (ZOP-31). The opti-
mum conditions are: FT = 823 K, NaOH/fly ash = 1⋅3 (w/w),
aging time = 18 h, HTt = 6 h, HTT = 363 K. Zeolites were
also synthesized from DTPS (ZOP-53) and NALCO (ZOP-
57) fly ash using the optimum conditions. Physico-che-
mical properties of these samples were determined apply-
ing various techniques as listed in table 6. From the table,
it is observed that zeolite synthesized from KTPS fly ash
(ZOP-30) is most crystalline and also possesses the maxi-
Figure 11. Thermal stability of synthesized zeolite (ZOP-30).
mum surface area. DTPS fly ash contains more iron oxi-
des, which might poison the synthesized zeolitic material
for use as catalyst. Crystallinity of ZOP-53 is least com- of synthesized zeolite was estimated to be less than one-
pared to the other two. Crystallinity of ZOP-57 is mode- fifth of that of 13X zeolite available in the market.
rate, but presence of CaO possibly hinders formation of
X-type zeolite. 4. Conclusions
The production cost of the synthesized zeolite was cal-
culated by taking into account the costs of chemicals and Zeolite of X-type was synthesized from fly ash by alkali
utilities for all the steps involved in the process. The cost fusion followed by hydrothermal treatment. The main
564 Keka Ojha, Narayan C Pradhan and Amar Nath Samanta

crystalline phase of fly ash, quartz, could be converted to Chang H L and Shih W H 2000 Ind. Eng. Chem. Res. 39 4185
pure X-type at suitable treatment conditions. The proper- Charnell J F 1971 J. Cryst. Growth 8 291
ties of zeolitic material formed strongly depended upon Flanigen E M, Khatami H and Szymanski H A 1971 Advances in
the treatment conditions and concentrations of the raw Chemistry Series 101 (Washington: American Chemical Society)
pp 201–229
materials. Zeolites of varying surface area, silica/alumina
Henmi T 1987a Clay Sci. 6 277
ratio, and crystallinity were obtained by changing the reac-
Henmi T 1987b Soil Sci. Plant Nutr. 33 517
tion parameters. The crystallinity of the prepared zeolite Höller H and Wirsching U 1985 Fortschritte der Mineralogie
was found to change with fusion temperature and a maxi- 63 21
mum value was obtained at 823 K. Lin C F and Hsi H C 1995 Environ. Sci. Technol. 29 1109
The best quality, in terms of surface area and crystal- Mondragón F, Rincón F, Seirra L, Escobar J, Ramierez J and
linity, Na–X zeolite was obtained at the following condi- Fernández J 1990 Fuel 69 263
tions: NaOH/fly ash ratio, 1⋅3; fusion temperature, 823 K; Natush D F S and Taylor D R 1980 (Environmental effects of
aging time, 24 h and 6 h of hydrothermal treatment. western coal combustion: part IV) (Duluth M N: Environ-
Maximum yield of Na–X zeolite was also obtained at the mental Research Laboratory)
above conditions with distorted octahedral crystal structure, Nugteren H W, Hallman G G and Janssen-Jurkovicova M 1995
Proceedings of international ash utilization symposium (Lex-
confirmed by XRD patterns and scanning electron
ington: University of Kentucky) p. 224
micrographs, and FT–IR studies. The cost of synthesized
Park M and Choi C J 1995 Clay Sci. 9 219
zeolite was estimated to be almost one-fifth of that of Park M, Choi C L, Lim W T, Kim M C, Choi J and Heo N H
commercial 13X zeolite available in the market. The pre- 2000 Microporous Mesoporous Mater. 37 91
sent result is, therefore, very much useful in opening up a Querol X, Plana F, Alastuey A and Lopez-Soler A 1997a Fuel
way to synthesize zeolite at low cost with useful applica- 76 793
tions. Querol X, Alastuey A, Lopez-Soler A, Plana F, Andrews J M,
Juan R, Ferrer P and Ruiz C R 1997b Environ. Sci. Technol.
31 2527
Acknowledgement
Shigemoto K, Shirakami K, Hirani S and Hayasi H 1992 Nip-
pon Kagaku Kaishi 484
This work is partly supported by the Ministry of Human
Shigemoto K, Hayasi H and Miyaura K 1993 J. Mater. Sci. 28 4781
Resource Development (MHRD), Govt. of India (Grant Shih W H and Chang H L 1996 Mater. Lett. 28 263
No. F26-1/2002 TS.V). Shin B S, Lee S O and Kook N P 1995 Korean J. Chem. Eng.
12 352
References Szostak R 1976 Molecular sieves: Principles of synthesis and
identification (New York: Van Nostrand Reinhold)
Bogomolov J F and Petranovsky V P 1986 Zeolite 6 418 Tati… M and Drñaj B 1985 Zeolites (eds) B Drzaj, S Hocevar, S
Breck D W 1974 Zeolite molecular sieves (New York: John Wiley Pejvonik (Amsterdam: Elsevier Science Publishers)
and Sons) Yang W H A and Kirkpatrick R J 1990 Am. Miner. 75 1009
Chang H L and Shih W H 1998 Ind. Eng. Chem. Res. 37 71 Yoshida A and Inoue K 1986 Zeolites 6 467