World Journal of Civil Engineering and Construction Technology

Vol. 1(1), pp. 002-0011, March, 2014. www.premierpublishers.org ISSN: 1936-868X x

WJCECT

Review

Utilization of fly ash byproduct in synthetic zeolites

Chintan Y. Pathak*1, Debananda Roy2 and Sumanta Das3
1*,2

Department of Environmental Science and Engineering. Faculty of Engineering, Marwadi Education Foundation,
Rajkot, Gujarat.
3
Department of Civil Engineering, Faculty of Engineering, Marwadi Education Foundation, Rajkot, Gujarat.
The amount of fly ash generated has been increasing at an alarming rate throughout the
world. It is the finely divided mineral residue resulting from the combustion of coal in thermal
power plants. It consists of inorganic, incombustible matter that has been fused during
combustion into a glassy, amorphous structure. The typical thermal power plant will burn
pulverized coal in a furnace with a boiler. The combustion products include fly ash, bottom
ash and a boiler slag and flue gas desulfurization (FGD) materials, which creates serious
danger if released into environment. This has attracted more attention within a context of
progressively more stringent regulation of hazardous air pollutants (viz. fly ash) discharge
from thermal power station. The disposal of such a huge quantity has become a pressing
issue. Several approaches have been made for proper utilization of fly ash, either to reduce
the cost of disposal or to minimize the environmental impact. This study presents the wide
variety of utilization of this industrial byproduct - fly ash and its application in the field of an
environment. One of the major ways out is the conversion of fly ash to zeolites, which has
wide applications in the field of an environment.
Keywords: Environment, digestion, hydrothermal, microwave, fly Ash, synthesis

INTRODUCTION
The increasing requirements in the sphere of
environmental protection have induced search for more
effective, inexpensive and ecologically safe solutions
for valuable conversion of an industrial byproduct fly
ash. Given that, the fly ash micro-porous solids known
as molecular sieves and have absorptive and ionexchange properties; the most important pollution of
hydrocarbon (HC) (viz. petrochemical spills), may find
applications in the removal of oil spill, using
hydrophobic - oleophilic - high-silica content - hydro
thermally
stable

alumino-silicates;
while,
simultaneously providing a solution to other
environmental problems. The discussion will be
applicable in wide variety of environmental pollution
control applications to sensitize current trend of
technocrats for some valuable conversion of these
waste fly ash. As a challenging task, the authors have
investigated the literature for current researches done
on fly ash. Studies have been carried out in the recent
past and are still being continued to understand and
utilize the concept for synthesis of fly ash for better
economical and technical applications. Attempt has

been made to present the researches carried out on fly

ash utilization particularly for zeolite synthesis
(Berkgaut and Singer (1996); Curtiss et al. (1998);
Xavier et al. (1999); Abu-Sarma (1975); Kuss (1992);
Criado, M.; Fernndez-Jimnez et al. (2007); Smith and
Arsenault (1996); Jha and Singh (2011); Holler and
Wirsching (1985)). Before a fly ash can be used for a
certain application, it is necessary to characterize, to
see if it has the desired properties for particular
application. If not, another synthesis method should be
used to meet the specifications. Fly ash fusion,
alteration, classification and appliance thus are strongly
related. Fly Ash Material Science has broadened and
deepened by a number of interrelated and
simultaneously occurring developments such as:

*Corresponding author: Chintan Y. Pathak, Department of

Environmental Science and Engineering. Faculty of
Engineering, Marwadi Education Foundation, Rajkot,
Gujarat. E-mail: drchintanpathak@gmail.com

Utilization of fly ash byproduct in synthetic zeolites

Pathak et al.

002

diversification of the composition outside aluminosilicate, particularly the crystalline alumino-phosphates

and Ga, Fe, B, Ti containing structures, growing
number of framework structures, increasing insight in
crystallization mechanisms, development of postcrystallization modification procedures, development of
powerful characterization techniques.
Hydrothermal Activation Method
A number of technologies have been developed for
gainful utilization of fly ash. Coal combustion byproducts production in USA is estimated in around 115
million tons per year. A large portion of this production
is accounted for the CFA. Cement and concrete
manufacturing consumes most of the CFA produced.
Zeolite synthesized from CFA is a minor but interesting
product, with high environmental applications. Zeolite
may be easily obtained from CFA by relatively cheap
and fast conversion processes (Fernandez-Pereira,
2002). Synthesis of fly ash zeolite by alkali fusion
followed by hydrothermal treatment was investigated by
several researchers. The synthesis conditions were
optimized to obtain highly crystalline zeolite. The cost of
synthesized zeolite was compared with the commercial
zeolite available in the market (Ojha et al. (2004)). By
varying the composition of the reaction mixture at a
given temperature and time; it was being achieved to
control the type of zeolite and simultaneously being
investigated its crystal structure, surface structure and
cation exchange capacity (Vucinic et al. (2003)). It has
been investigated that the synthesizing capability of
zeolite from fly ash has a positive impact on utilization
of wastes coming from solid fuel combustion by
converting the fly ash into valuable raw material and,
simultaneously,
accomplishing
the
lithosphere
protection effect (Fukui. et al. (2005); Terzano et al.
(2005); Park et al. (2000); Adamczyk and Biaecka
(2005)).
In March 1954, the structure of zeolite A was being
achieved by the (Reed et al. (1956); Breck et al.
(1958)). In mid 1954, they also completed the
structures of X and faujasite, with the help of single
crystal X-ray data on faujasite. The iso-structural zeolite
with ratios above 3 and up to 6 were named and
patented as zeolite Y and evaluated as a catalyst
(Beck, 1964). In February and March of 1954, Breck
and Milton prepared hydrogen exchanged X with
greater than 60 % of the sodium cations replaced, both
by direct exchange with acid and by exchange with
ammonium ions followed by heating to drive off
ammonia (Milton and Breck,1956). A patent application
was filed on March 13, 1956 on the catalytic cracking of
hydrocarbons with hydrogen X in the names of Milton
and Beck. By mid 1954, Breck and Milton had
developed methods for dispersing metals on the inner
surfaces of the A, X and Y zeolite and had initiated
catalytic studies with them (Breck and Milton,1961);
Milton (1965; 1966)). In 1953, Breck et al. (1956) had
made a total of 20 crystalline zeolite including erionite,

gmelinite and 14 with no know natural counterparts.

Jones (1950) co-inventor of the first major application of
molecular sieves (Jones et al. (1957)). By mid 1950,
Milton had discovered how to routinely make pure
zeolite X (Milton (1959)). Chabazite was synthesized in
late 1950 and by mid 1951, Milton made three new
zeolites in the potassium-alumino-silicate system
(Milton ,1961). In 1949, F.G. Straub and R.M. Barrer
(Milton ,1961; Straub 1963) started synthesis using
relatively insoluble forms of silica and alumina in mildly
alkaline solutions (pH 8-11) at temperatures of 200o
300 C. In some reactions analcime or small pore
mordenite had formed. By end 1949, R.M. Milton
(Barrer ,1948; Milton,1961) had developed a new and
widely applicable method for synthesizing zeolite
simultaneously with the discovery of zeolite A, zeolite B
(gismondite), zeolite C (sodalite) and a crystalline
impurity zeolite X. Cronstedt Christened formed a frothy
mass and discovered the hydrated alumino-silicate
minerals zeolite. Because of limited availability of
material, research was sparese for next 200 years.
Efforts to achieve hydrothermal synthesis of analogs of
natural zeolite were date back to 1845, although the
elevated temperatures pressures employed and the
lack of proper identification techniques precluded a high
degree of success.
In 1985, Holler and Wirsching (Holler and
Wirsching,1985) utilized fly ash as the raw material for
synthesis of zeolite using hydrothermal method. After
that, a number of researchers have used this process
successfully, varying the hydrothermal temperature
within the range of 333-573 K (Henmi,1987 a,b; Lin and
His,1995; Park and Choi,1995; Park et al. (2000); Shin
(1995); Chang and Shih,1998). Previous researchers
have been utilizing the conventional hydrothermal
method for alkali activation of fly ash (Chang and
Shih,1998). A typical experimental set up for the closed
reflux system is similar to an autoclave where both
pressure and temperature can be varied as per the
desired experimental conditions. In general, zeolite
synthesis processes involve the addition of alkali agent
to the fly ash slurry at higher temperatures. Miyake
(Kumar et al.,2008) re-utilized the main components
(SiO2 and Al2O3) and unburned carbon from the Coal
Fly Ash (CFA); it was successfully converted into
composite materials consisting of zeolite (NaX and/or
NaA) and activated carbon using NaOH fusion
treatment with a NaOH/CFA ratio of 2, followed by
hydrothermal treatment. Preparation of synthetic zeolite
from CFA using hydrothermal treatment with NaOH
activation at low temperature was studied by Sulaiman
(Sulaiman,2008). It has been found out that the
crystallinity of zeolite P increases with increase in
temperature and reaction time. The formation of
synthetic zeolite P with a high Cation Exchange
Capacity (CEC) is possible using this method. C.
Belviso et al. (Belviso et al. (2007)), synthesized zeolite
from coal fly ash by hydrothermal process with aid of
salt and distilled water. It reveals that the zeolitization at
low temperature, using industrial by-products like fly

Utilization of fly ash byproduct in synthetic zeolites

World J. Civ. Engin. Constr. Technol.

ash, represents potential applications for reduction of

heavy metals in contaminated areas in an economical
way.
th
In the beginning of 20 centuary, it has been observed
that the zeolite may be easily obtained from CFA by
relatively cheap and fast conversion processes (Querol
et al. (2007)). The conventional alkaline conversion
processes emphasized on the experimental conditions
to obtain high CEC zeolite. A potential application of
different zeolite products for waste water and flue gas
treatment is also given with one of the main potential
application of this material is the uptake of heavy
metals and ammonium from polluted wastewaters.
Some of the zeolite synthesized may be also used as
molecular sieves to adsorb water molecules from gas
streams or to trap SiO2 and NH3 from low water
gaseous emissions. Fukui et al. (Fukui et al. (2003)),
investigated the effects of NaOH concentration on the
crystal structure and the reaction rate of the zeolite
synthesized from fly ash with a hydrothermal treatment
method. Fly ash and co-disposal filtrates provide a rich
source of SiO2 and Al2O3 as feedstock for zeolite
synthesis, which can be successfully converted into
faujasite, sodalite, and zeolitic material. The type of
zeolite formed was dependent on the fly ash source,
because it was also contributing to the physical and
chemical characteristics of the resulting zeolite.
Moreover, the synthesis of zeolite P (zeolite belonging
to the Gismondine series) and zeolite X (zeolite
belonging to the Faujasite series) was observed for the
first time directly in soil in the presence of organic
matter (2.4 % C) and several mineral phases (Terzano,
2005); Park et al. (2000). Correlations between Si/Al
molar ratio in solution, curing temperature and the type
of synthesized zeolite were found. Si/Al ratio lower than
1 and higher curing temperatures favored the synthesis
of zeolite P, while a Si/Al higher than 1 and lower curing
temperatures drove the synthesis preferentially towards
zeolite X. Zeolite from fly ash was synthesized and
characterized by Ojha et al. (2004). Synthesis of X-type
zeolite by alkali fusion followed by hydrothermal
treatment was studied and characterized. Hydrothermal
reaction was carried out in various alkali solutions to
clarify the mechanism of zeolite synthesis from coal fly
ash (Vucinic et al. (2003); Murayama et al. (2002)).
All the studies by Iler and Engelhardt shows that as a
general rule, the formation of more highly polymerized
species is favored by decreasing pH at constant silica
concentration and increasing silica concentration at
constant M2O/SiO2 ratio. Mooler et al. studied the
solubility of alumino-silicates in alkaline medium. This is
related to the chemical behavior of aluminum. At pH
larger than 11, this element exists solely as tetrahedral
Al(OH)4- ions. The host-guest relationship is described
by Barrer (Barrer,1960); Barrer et al. (1984)) is one of
the most important in the chemistry of porous crystals
because, without the zeolitic guest, microporous
crystals could not be synthesized. The guest is required
only during synthesis and is thereafter removed before
the porous crystals are put to use. The study of alkaline

003

silicate and aluminosilicate solution is of fundamental

importance for a better understanding of the
mechanism of zeolite synthesis (Barrer et al. (1959);
Zhdanov (1980)). Flenigen learned how to make zeolite
x with silica/alumina ratio between 4-5.7. It is clearly
established that the silicon is in tetrahedral coordination
(Breck and Flnigen,1968; Breck and Flnigen,1968). The
simplest form of silica in solution is the monosilicic acid
Si(OH)4. Polymerization results from the condensation
of two silanol groups with the elimination of a water
molecule. A whole series of silicate anions, of various
polymerization and ionization degrees are thus
connected
through
dynamic
equilibrium.
The
equilibrium is governed by the normal chemical
parameters, namely the silica concentration, the pH
and the cation type (Fortnum and Edwards,1956).
In one of the sorption study, materials were measured
and widespread for adsorption purification of water from
petroleum and oil products by Sirotkina and
Novoselova, 2005 (Sirotkina and Novoselova, 2005).
Sorbent used both for elimination of oil outflow and for
purification of oil-containing wastewater are considered.
Natural (plant and mineral based), artificial and
synthetic sorbent were studied. Querol et al. (Querol et
al. (2000)) worked on the methodologies for zeolite
synthesis from coal fly ash and a conventional alkaline
conversion processes, with special emphasis on the
experimental conditions to obtain high CEC zeolite.
One of the main potential application of this material is
the uptake of heavy metals from polluted waste waters
and also for the uptake of ammonium from polluted
waters. Some of the zeolite synthesized may be used
as molecular sieves to adsorb water molecules from
gas streams or to trap SO2 and NH3 from gaseous
emissions. It has also been found out that the
optimization of synthesis yields have to be specific for
each fly ash due to differences in mineralogical and
chemical compositions. Consequently, the products
obtained have an important potential application in the
wastewater treatment technology.
Microwave Irradiation Method
In recent years, increasing efforts have been directed
towards the development of new crystallization
methods which allow the synthesis of zeolite for
practical utilization. Based on the findings of previous
researchers, it can be opined that hydrothermal
activation of fly ash by alkali is time consuming as it is a
slow process (Breck et al. (1956); Jones and
Milton,1957; Milton, 1959; 1961); Barrer,1948).
Traditionally, chemical synthesis has been achieved
through conductive heating with an external heat
source. Heat is driven into the substance, passing first
through the walls of the vessel in order to reach the
solvent and reactants. This is a slow and inefficient
method for transferring energy into the system because
it depends upon the thermal conductivity of the various
materials that must be penetrated. This process can
take hours. Microwave heating, on the other hand, is a

Utilization of fly ash byproduct in synthetic zeolites

Pathak et al.

004

very different process. The microwaves couple with the

molecules those are present in the reaction mixture,
leading to a rapid rise in the temperature. Because the
process is not dependent upon the thermal conductivity
of the vessel materials, the result is an instantaneous
localized superheating of anything that will react to
dipole rotation or ionic conduction, the two fundamental
mechanisms for transferring energy from microwave to
the substance being heated. Microwave heating also
offers facile reaction control. It can be described as
instant on-instant off (Das et al. (2001)). Microwave
belongs to the portion of the electromagnetic spectrum
with wavelengths from 1 mm to 1 m with corresponding
frequencies between 300 MHz and 300 GHz. Within
this portion of the electromagnetic spectrum there are
frequencies that are used for cellular phones, radar,
and television satellite communications. For microwave
heating, two frequencies, reserved by the Federal
Communications Commission (FCC) for industrial,
scientic and medical purposes are commonly used for
microwave heating. The two most commonly used
frequencies are 0.915 and 2.45 GHz (FernandezPereira et al. (2002)). A microwave is a form of
electromagnetic energy that falls lower frequency end
of the electromagnetic spectrum and is defined in the
300 to about 300,000 MHz frequency range. Within this
region of electromagnetic energy, only molecular
rotation is affected, not molecular structure. Out of four
available frequencies for industrial, scientific or medical
applications, 2450 MHz is preferred because it has the
right penetration depth to interact with laboratory scale
samples and there are power sources available to
generate microwaves at this frequency. Microwave
energy consists of an electric field and a magnetic field,
though only the electric field transfers energy to heat a
substance. Magnetic interactions do not normally occur
in chemical synthesis (Adamczyk and Biaecka, 2005).
Microwave move at the speed of light (300,000
km/sec). The energy in microwave photons (0.037
kcal/mol) is very low relative to the typical energy
required to cleave molecular bonds (80-120 kcal/mol);
thus, microwave will not affect the structure of an
organic molecules.
In addition, repeated treatment/activation process is
required to synthesis fly ash zeolite. In the last decade,
the use of closed vessel microwave assisted digestion
method under high temperature and pressure has
become increasingly popular. Compared to the more
traditional method, this procedure allows shorter
digestion times and good recoveries. Furthermore, it
requires smaller amount of acids, reduces risk to
external contamination, which in turn, results in
improved detection limits and the overall accuracy.
Microwave digestion inherited some disadvantages
from open air digestion; most of these problems,
however, are associated with usage of HF. So far,
researchers attempted to optimize the method in many
different ways; some research has been done to
determine the need for HF. It has been found that for
digestion of coal addition of HF is not necessary and its

absence will not result in poorer recovery of trace

elements However, for fly ash, addition of HF proved to
be necessary. Microwave-assisted digestion method
provides several advantages over traditional hot plate
method and most of them come from the fact that this
method is performed under higher temperatures and
pressures as well as under close vessel conditions.
Ashing step prior to digestion is not necessary when
microwave was used. Microwave system constantly
monitors the temperature of reference vessel
throughout the digestion procedure and automatically
increases it when necessary. For example, if at some
point during the digestion of sample an exothermic
reaction occurs, spike in temperature will be observed.
In that case instrument will cut the energy supply in
order to lower the temperature to the set value. This
ensures more constant and repeatable conditions
compared to conventional digestion. This condition
provides the advantage of performing more complete
digestion under higher temperature and pressure
without loss of more volatile elements. Lastly, the time
needed for digestion is significantly reduced when
microwave digestion system is used (Milton,1961;
Barrer,1948). The two main types of conditions used for
chemical reactions, those run in the presence of solvent
and those run in a solvent less environment are equally
important and both can benefit from microwave heating.
The Microwave synthesis technique offers the potential
for convenient and often rapid sample preparation,
usually affording products of high crystallinity. There is
also the possibility of genuine selectivity. In the
microwave synthesis of zeolite Y, crystallization of
undesired phases is suppressed, even at an unusually
high synthesis temperature (150C). Such selectivity is
largely attributable to the high heating rates attainable
in microwave syntheses and their effect upon the rival
rates of nucleation and growth of competing phases (in
this case, zeolites Y and P). Similarly, in colloidal
silicalite synthesis, the different rates of temperature
rise achievable by microwave and thermal heating
made it possible to distinguish between the crystal
population nucleated during the heating process and
that arising from proto-nuclei generated during the
room temperature aging of the precursor sols. A very
rapid (3 min) microwave crystallization of ZSM-5
probably reflected a contribution from the interfacial
superheating of nanocrystal seeds. However, under
near-equilibrium conditions, there was no significant
difference between the crystal linear growth rates in
thermally and microwave heated reactions, the growing
crystals acting in this case as a form of internal
thermometer (Herod et al. (1999)).
Savic studied the recent development of microwave
systems designed for digestions under extreme acidic
conditions and high temperatures and pressures, which
has shifted focus toward more rapid and precise
microwave assisted digestion of samples. A number of
papers have been published involving research efforts
toward development of quantitatively satisfying
digestion methods. However, there is still no published

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World J. Civ. Engin. Constr. Technol.

ASTM or EPA method for microwave-assisted digestion

of coal and coal combustion products. The goal of this
research is compare the recoveries obtained by using
hot plate method with results obtained by microwaveassisted digestion, as well as to attempt to optimize
method conditions for latter (Nadkarni,1974). Hu et al.
have studied the microwave digestion method of fly ash
using NaOH. For the silicate sample, the digestion time
was 210 s in the proposed method, which was much
less than that in the traditional alkali melting method
and the acid soluble method. The method had
signicant advantages of being simple, time-saving and
energy-saving, etc. It could be applied in the
pretreatment and rapid analysis of silicate samples.
Compared to the microwave acid soluble method, the
adding of HF was avoided (Jha and Singh, 2011).
Therefore, the process to add excessive H3BO3 for
eliminating HF could also be omitted. Additionally, the
obtained solution from microwave digestion could be
used to determine contents of SiO2, Al2O3, CaO, MgO
and TiO2, etc. in the silicate sample, which solved the
long-term problem the traditional microwave digestion
technique whereby it was difficult to determine the
contents of components directly in the silicate sample
by using chemical analysis and photometric analysis.
More research will be done in the near future. The
ordinary microwave oven had advantages of being
cheap, time-saving, etc., but safety was a potential
problem. The major advantage of the closed microwave
digestion technique is the high heating efficiency which
can be obtained. Heating causes an increase in
pressure, due to the evaporation of digestion acids and
the gases evolved during the decomposition of the
sample matrix. This is beneficial by increasing the
boiling-point of the reagents, which aids the breakdown
of the sample matrix. However, the excessive build-up
of pressure, especially during the digestion of samples
with a high organic content, can lead to the rupture of
sealed vessels. For this reason, most digestion bombs
are fitted with pressure relief valves, designed to open
when the pressure becomes too great, and thus
maintain safety. If venting does occur, sample losses
are likely and owing to the reduction in acid vapours a
less active digestion may result. Considerable research
has therefore been undertaken to find ways of
controlling or reducing pressure build-up during the
digestion process (Walker et al. (2003)). One method of
avoiding excess pressure is to pre-digest the sample,
and thus enable the gases evolved from the
decomposition of easily oxidized organic matter to
escape before commencing the closed digestion
procedure. This may be carried out by leaving the
samples to predigest at room temperature. In many
cases, to attain complete digestion the use of HF is
necessary to decompose resistant minerals, in addition
to strong oxidizing reagents such as nitric acid and
sometimes perchloric acid to break down organic
matter. In the literature, there is evidence to suggest
that a number of elements such as Cd, Cu, Hg, Pb and
Zn can be easily released after digestion with just nitric

005

or hydrochloric acid. This is because in many cases

they are sorbed on clay minerals or are in other readily
decomposed phases, rather than within the resistant
framework-lattice silicates. However, other elements
are more strongly bound, either as part of resistant
minerals or associated with other minerals, and so in
such cases the use of HF may be required (Rayalu et
al. (2006)). The need for HF is very much dependent on
the nature of the minerals present in the samples.
Because real samples will vary in composition from that
of the certified reference materials used for validation of
a procedure, it would seem prudent to suggest that for
the determination of all but the most weakly bound
elements in sediments, digestion with HF is
recommended. The choice of sample preparation
method may, however, be influenced by a number of
practical considerations in addition to the type of
sample and elements to be determined. These may
include the number of samples to be analyzed, method
of analysis, safety aspects, capital and operating costs
of equipment, operator skill and the degree of accuracy
and precision required.
The method of final analysis is an important factor,
influencing the extent of the digestion required, e.g., for
electro analytical techniques complete breakdown of
the organic components is necessary, whereas ICPAES can tolerate dissolved solid contents of up to 1
2%. Also, the addition of certain reagents during the
reaction can be considered (ASTM). ICP-AES suffers
from a number of interferences, particularly polyatomic
ion interferences. Hence, the presence of a number of
acids, including hydrochloric and sulfuric acid, in the
final solution is not recommended for the determination
of some elements. Therefore, adapting a digestion
method for analysis by a different technique to that
originally intended may not prove successful. When
considering the speed of a particular procedure, it is not
just the time for the actual digestion that should be
considered. Other factors should also be taken into
account, e.g., sample preparation before analysis,
including grinding and slurry formation; pre-digestion
and cooling times, including those necessary between
reagent additions/heating cycles; and the washing of
digestion vessels. These factors are often over looked.
For batch digestions, many closed digestion
procedures are developed in terms of heating at a
particular power setting for a certain period of time,
usually optimized to maximize energy input without
causing venting of the vessels. These procedures are
therefore operational, i.e., specific to the particular
microwave system and bomb design used. Adaptation
for use in a different laboratory may not be
straightforward unless the same equipment is used, as
re-optimization of the original power settings and
heating times may be necessary. The optimum power
and time settings may also vary considerably according
to the exact nature of the sample owing to the amount
of organic matter present, which influences the amount
of gaseous products evolved during the reaction. It has
been shown that direct temperature and pressure

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Pathak et al.

006

measurements during the course of the digestion are

possible. Such measurements can then be fed to a
computer controlling the magnetron to achieve a preset temperature or pressure program. This technology
offers the potential to produce far more reproducible
and controllable procedures, reducing the possibility of
venting of digestion vessels. In closed systems it
enables the system to be operated to its full digestion
potential. A mechanism of crystal growth is proposed;
extensive heterogeneous nucleation occurs during
formation of the highly supersaturated gels. Crystal
growth in the solid phase then proceeds by a series of
depolymerization-polymerization reactions, catalyzed
by excess hydroxyl ion. There is no significant solution
of the solid phase during crystallization. Growth of the
crystal proceeds through a type of polymerization and
de-polymerization process which involves both the solid
and liquid phases. The solid phase, however, appears
to play the predominant role. The hydroxyl ion behaves
as a type of catalyst by breaking and remaking Si, Al-OSi, Al bonds but does not lead to a significant
dissolution of the solid phase of the gel. The formation
of crystalline zeolite phases from reactive aluminosilicate gels apparently represents an unusual system
for crystal growth. It differs considerably in complexity
and mechanism from the more classical crystallization
methods. HNO3, HCl, HF and mixtures have been
tested as digestion acids. The combination of HNO3
and HF has been found to be efficient for the digestion
of ash samples. In coal-fired power plants, a major part
of the particles, i.e. fly ash, is precipitated by means of
electrostatic precipitators or fabric filters. A small
fraction is released into the atmosphere as airborne
particles along
with
the vaporous fraction.
Environmentally harmful trace metals are to a great
extend associated with the particulate phase in the flue
gases leaving coal combustion.
During the last few years, microwave digestion has
become more and more popular partly due to the
reduction in digestion times. The digestion of fly ash
was first carried out without any filter material, to find
out which acid or acid combination is required to
quantitatively dissolve the metals, and to obtain
preliminary information on how trace elements are
bound in the ash particles. In a second stage, the effect
of commonly-used quartz fiber filter material on the
determination of trace metals in fly ash materials was
studied. The comparison with certified values for
reference materials showed that a number of factors
must be considered when choosing which one is the
more suitable digestion technique: (1) the acid attack
must include hydrofluoric acid to dissolve the silicateenriched ash matrix completely since, except for Se
and As, none of the other elements studied here is
completely extracted from the matrix by HNO 3 alone;
(2) the loss of volatile elements has to be expected
during the open vessel acid digestion and an alternative
preparation, involving closed vessels such as in the
microwave attack, is often preferable for these
elements (As and Se); (3) the final solutions must be

suitable for the ICP-AES instrument (total dissolved

solid kept low and possible interferences mainly due to
the use of HCl or HClO4 avoided); the total solid to final
solution dilution factor has to be kept minimal to allow
the determination of some elements present in coal at
very low level. For the small sample size of 10 mg, a
dilution factor of 1000 has proved necessary to quantify
several elements (Ni, Cu, Mo, Sb and to some extent
Zn). There are numerous ongoing research efforts
focused on optimization and improvement of sample
preparation. Most of them are concerned with
completeness of digestion procedure, length and time
consumption, pretreatment conditions, and use of
hydrofluoric acid. Das S. (Das and Chakraborty,2001),
studied the microwave processing has been emerging
as an innovative sintering method for many traditional
ceramics, advanced ceramics, specialty ceramics and
ceramic composites as well as polymer and polymer
composites. Ceramic and metal nanopowders have
been sintered in microwave. Furthermore, initiatives
have been taken to process the amorphous materials
(e.g. glass) by microwave heating. Besides this,
attempt has been made to study the heating behavior
of materials in the electric and magnetic fields at
microwave frequencies. The composition of fly ash was
investigated by chemical sequential extraction and
modified microwave digestion method. Effects of
process time, container materials, aging time and salt
contents were also discussed. The major elements of
fly ash are Ca, Cl, Na, Si, K, Al, Mg, and Zn, and the
metal species, Zn, Cr, Pb, Ca, and Cu, are mainly in
the oxide phase. Under microwave processing, the fly
ash was sintered into a glassceramics and the
leaching concentrations of heavy metals were
restrained. The stabilization efficiency increased with
an increase in processing time in most of the cases.
Better stabilization efficiency of fly ash was discovered
by using the SiO2 or Al2O3 container than by using the
Figureite plate/SiC plate. The presence of salt in the fly
ash could enhance the sintering and stabilization of fly
ash. During the aging time of 030 days, negligible Pb
in the sintered fly ash was leached out, and the
leaching concentration was lower than the criterion.
Fukui et al. (Fukui. et al. (2009).) utilized NaCl for
phillipsite synthesis from fly ash by hydrothermal
treatment with microwave heating. The coal fly ash was
treated hydrothermally with the mixture of NaOH
aqueous solution and NaCl aqueous solution at 373 K,
using the microwave heating and the conventional
heating in order to clarify influences of the NaCl
concentration in the hydrothermal solution on the
growth rate and the crystalline phase of synthesized
zeolite attains to the vessel by way of the wave guide.
Hassan, et al. (Hassan et al. (2007)) used several
different standard reference materials, namely urban
particulate matter, to examine and modify US EPA
method 3051 for microwave assisted digestion of
sediments, sludges, soils, and oils which specifies a 10
min total digestion time and a sample mass of up to
500 mg combined with 10 mL nitric acid. They found

Utilization of fly ash byproduct in synthetic zeolites

World J. Civ. Engin. Constr. Technol.

that recoveries of all elements improved by increasing

the digestion time and by decreasing the sample mass
to acid volume ratio recommended by US EPA method
3051 (Adamczyk and Biaecka, 2005). In a separate
study, Ohki, et al. (Ohki et al. (2007)) performed
microwave-acid digestion followed by ICP-AES,
Figureite Furnace Atomic Absorption Spectrometry
(GFAAS), and Hydride Generation Atomic Absorption
Spectrometry (HGAAS) were examined the extraction
of various elements in coal and CFA. The effect of
microwave irradiation on the zeolite formation was
investigated with emphasis on the change in yield of
zeolite during the reaction (Inadaa et al. (2005)). The fly
ash was mixed with 2 M NaOH solution and heated by
oil bath or microwave for 2 h. Zeolite Na-P1 formed
after the conventional treatment using oil bath, but no
zeolitic product was obtained by microwave heating.
When microwave was applied in the course of
hydrothermal treatment, zeolitization was promoted by
the early-stage irradiation. This is due to the stimulated
dissolution of SiO2 and Al2O3 from coal fly ash. On the
other hand, the microwave irradiation in the middle to
later stage retarded the crystallization of zeolite. The
microwave is effective to produce the zeolite from coal
fly ash in a short period by control of irradiation
schedule in the early stage. Because of few limitations
in the earlier researches, it was not accurately
explained the reaction mechanism of zeolite dissolution
in hydrochloric acid solutions as a function of pH. Ojha
(Ojha et al. (2004), synthesized X-type zeolite from coal
fly ash by alkali fusion method followed by
hydrothermal treatment. 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 quartz present in the fly ash are the sources
of aluminum and silicon, respectively, for zeolite
formation. Cresswell studied the use of microwave
ovens in research field. The relationship between
microwave power applications and spectroscopic
measurements in the microwave region seems also to
be an exciting area for future development. Das (74)
developed a microwave assisted digestion procedure
for dissolution of fly ash samples prior to the inductively
coupled plasma-mass spectrometric determination of
their elemental composition. Gdanski concluded that
the possible precipitation during the secondary reaction
can adversely affect treatment success, especially in
formations with high K-feldspar content or temperatures
above 300 F. Herod et al. (78) performed an
evaluation of two digestion methods used to extract 17
elements (Be, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, As, Se,
Mo, Cd, Sn, Sb, Ba and Pb) from coal and coal ash,
obtained as standard reference materials. An acid
digestion method in open vessels using sulfuric,
hydrofluoric, perchloric and nitric acid was compared
with a sealed microwave digestion method using nitric
acid only. They found that the microwave method with
nitric acid only cannot break down silicates, which
harbor many trace elements, but can extract As and Se
quantitatively.

007

The efficiency of different digestion methods (six

microwave decomposition methods and a wet acid
digestion method) in the solubilisation of six metals (Cr,
Ni, Cu, Pb, Cd, Zn), for their determination in fly ashes,
was compared by Morabita. The fundamentals of
electromagnetic theory, dielectric response, and
applications of microwave heating to materials
processing, especially fiber composites, are reviewed in
this article (Thostenson,1999). A major concern in
laboratories performing trace element determinations is
sample contamination. Sensitivity can be enhanced for
trace elements by using larger samples, but this
approach may increase the risk of contamination due to
the need for more involved preparation techniques.
With the isolation of the sample from the laboratory
environment, the potential for contamination is greatly
reduced during sample decomposition. In this
investigation, an Environmental Evaporation Chamber
(EEC) placed in a microwave digestion system was
used for predigestion of biological and botanical
samples prior to closed-vessel digestion. Ellin studied
application of a commercially available, microwaved
digestion system of hydrofluoric acid digestion of rock
samples for palynological analysis allows considerable
savings of time, laboratory space, chemical costs and
waste disposal costs. The system offers several
advantages in terms of workplace safety and
environmental hazard over existing rapid silicate
digestion techniques. The reaction kinetics of silicon
etching in HF solution was studied experimentally. The
etch rates were measured with varying HF
concentrations, agitation speed, reaction temperature
and time. At low HF concentration, the etch rate
maintains low value and increases very
slowly
because of insufficient hole concentration for etching
reaction. The acceptance of microwave digestion
technique is based on procedures successfully carried
out for most different kinds of samples (Kuss,1992). It
is not only the knowledge of the mechanisms how
microwaves interact with the material scientists deal
with but more the experimental procedures for the
most efficiently reagents attack. The goals of this
paper are to gather all information concerning
applications of microwave digestion methods for
elemental analysis and to review the results obtained
by selecting several groups of materials digested
(Nadkarni NS,1974).
RESULTS AND DISCUSSION
It has been well thought-out by previous researchers to
utilize the industrial byproduct fly ash for some
valuable product to reduce the load of pollutants in our
environment (Jones, R.A. and Milton, R.M.,1957;
Milton, R.M.,1959, 1961; Straub, F.G.,1936; Barrer,
R.M.,1948). In line with the objectives and to recycle
reuse the industrial byproduct fly ash, in some
valuable product (viz. zeolite), which can be applicable
for oil spill clean-up; has been experimented thoroughly

Utilization of fly ash byproduct in synthetic zeolites

Pathak et al.

008

Table 1. A summary of the Methods employed for Synthesis of Fly Ash Zeolites

Method

L/S

Reagents

Conventional
hydrothermal

NaOH,
KOH,
Na2CO3

Microwave
assisted
hydrothermal

10

NaOH

Fusion
and
hydrothermal

10

Molten salt

NaOH/or
Sodium
Aluminate
Water
KOH
KNO3
NaOH
NaNO3
NH4F
NH4NO3

(81)

(t: activation time, Temp.: temperature)

T
(h)

Zeolite

Remarks

90-150

24-96

Chabazite, Na-P1,
Phillipsite, Sodalite,
Zeolite KH, 4A, A, P,
Zeolite X, Y

Low yield, Low purity,

Structuralheterogeneity

100

0.25-2

Na-P1

Synthesis time very

Less

500650

1-2

90-100

Faujasite
Na-A,
Na-X or
zeolite X

350

3-6

Sodalite

Temp.
(oC)

in this study. In addition, the applicability of these

synthesized zeolite for oil spill clean-up has also been
strategically discussed. The scope of this work was to
prepare novel zeolite using both existing and novel
methods. One objective of this work was to reuse and
recycle industrial byproduct fly ash to synthesize
zeolite by using microwave digestion technique.
Another objective was to evaluate the feasibility of
commercial production of zeolite. A further objective
was to characterize the zeolite using ICP-AES and
XRD. Moreover, the study of the properties of oil-water
mixture was also focused to evaluate the possibility for
pollution control. The research was to establish the
applicability of fly ash synthesized zeolite in wide
variety of environmental pollution control application. It
is useful to work out new techniques for separation of
waste oil from water using zeolite treatment. It helps in
establishment of the safe method for disposal for waste
(residue) and to optimize the processes for oil spill
clean-up.
Although, the alkali dissolution of fly ash can be
accelerated by fast heating and attack of active water at
molecular level. However, it has been found that the
end product is of low yield, which has not been
explored further (Fernandez-Pereira et al. (2002);
Nadkarni,1974). In addition, no efforts have been made
for understanding the effects of the physical variation of
the fly ash particles on the quality of final products.
With this in view, an optimization of the temperature
and time of microwave heating of aqueous matrix of
different type of samples collected from various
sources, needs to carried out. A critical review of the
literature available on synthesis of fly ash zeolite
reveals that
microwave irradiation method for
activation of the fly ash with acid treatment, controls the

More yield

No addition of water
Irregular
morphology

zeolitisation. Although, the changes in the overall

physical properties (viz., particle size, pore size,
specific gravity, void volume and surface area), has not
been studied in detail and hence proper attention is to
be given on the effect of various parameters like
temperature, time, HF concentration and Si/Al
necessitate to be experimentally studied. With this in
view, synthesis of zeolite has been tried by microwave
with acid digestion method. Although, not much has
been explored about the important parameter (viz.
temperature, time, Si/Al and HF concentration) and
their effect on the products. As step ahead, the
researchers have further explained the synthesis
process to maximize the consumption of acidity in silica
dissolution and zeolitization in comparison with
hydrothermal method to produce zeolite in less time
with more yield and better properties. With this in view,
the change in the mineral phase of fly ash, during its
varying degree of thermal decomposition and hence
acid fly ash interaction in various stages of microwave
activation needs to be optimized to better understand
the superiority of this method with a special focus to the
mechanism of zeolitization.
With all these as a challenge ahead, thorough
investigations are required to establish for the physicochemical,
mineralogical
and
morphological
characteristics of synthesized products obtained after
each cycle of synthesis. In order to investigate the
zeolitization potential of fly ash and its activated phase
produced and the dissolution of silica and alumina in
the solution, thorough characterization needs to be the
matter of concern for the researchers. However, it has
been opined by previous researchers that the highest
release of SiO2 in the solution indicates the lowest
formation of zeolites, although; the slowing down of

Utilization of fly ash byproduct in synthetic zeolites

World J. Civ. Engin. Constr. Technol.

dissolution can lead to higher zeolitization (Fukui, K.

et al. (2009)). It has been reported that the dissolution
of Al, Fe and other trace elements are found to be
below average as compared to the Si. The critical
review of literature, shown in Table 1, aimed at
application potential of various fly ash zeolites, their
stability parameters in case of high temperature
thermal exposure and their characteristics in acidic
medium, remains unexplored in case of synthesis
products of different methods except few. In addition,
not many efforts have been made in the past to
devise a simple and viable technique for large-scale
conversion of fly ash to zeolitic materials for their
consistent industrial applications and that too with
less energy consumption.
The zeolitization would recycle in small fraction of
coal fly ash production, but the product would have a
higher added value than current applications. Today,
oil spill responders try to optimize net environmental
benefit when considering how to deal with an oil spill.
This simply means that the effects on the environment
of whatever clean-up techniques are to be used are
weighed against the damage to the site. Sometimes
the decision is made not to clean up if an assessment
shows that the clean-up itself will be intrusive. In the
same way, the effects of the various clean-up
techniques are also assessed and the least intrusive
technique is chosen for a particular site. The
microwave-assisted digestion method for fly ash
provided comparable or better results than the
conventional hydrothermal digestion method. The
variations in weight of sample, temperature, and time
resulted in improved recoveries of several elements.
In addition, preparation and time needed for digestion
was significantly reduced with this method. The
microwave-assisted method for fly ash did work better
than hydrothermal digestion method. There is
however, scope for more improvement in future
research. The use of hydrofluoric acid was absolutely
necessary for digestion of fly ash because fly ash
primarily consists of silicates and oxides. Most of the
elements in ash were successfully extracted with
hydrofluoric acid. In addition to this, the nonbiodegradability of these materials is a major
disadvantage since landll disposal is environmentally
undesirable and incineration is very expensive. It is
suggested that use of zeolites may prove very
economical, technically feasible and environmentally
acceptable for application in oil spill clean-up
technology. Hydrophobic, oleophilic, high- SiO2
content, hydro thermally stable zeolites, particularly
those prepared cheaply from fly ash, aluminium
refining wastes and other solid waste materials
containing silica and alumina may find application in
the removal of oil spills while simultaneously providing
a solution to other environmental problems. The
synthesizing capability of zeolites from fly ash has a
positive impact on utilization of wastes coming from

009

solid fuel combustion by converting the fly ash into

valuable
raw
material,
and
simultaneously
accomplishing the lithosphere protection effect.
ACKNOWLEDGMENT
I would like to thank the Director General, Pandit
Deendayal Petroleum University, Gandhinagar,
Gujarat and the Dean, Marwadi Education
Foundations Group of Institutions, Rajkot, Gujarat; for
their continuous support and motivation to complete
the work.
List of Abbreviations
ASTM
American Standards for Testing of
Materials
CEC
Cation Exchange Capacity
CFA
Coal Fly Ash
HF
Hydrofluoric Acid
ICP-AES
Inductive Coupled Plasma-Atomic
Emission Spectroscopy
SEM
Scanning Electron Microscopy
XRD
X-ray Diffraction
XRF
X-ray Fluorescence
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Citation: Pathak CY, Roy D, Das S (2014). Utilization
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Engin. Constr. Technol. 1(1):002-0011.

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Utilization of fly ash byproduct in synthetic zeolites