1 s2.0 S0360128509000604 Main PDF

Progress in Energy and Combustion Science 36 (2010) 327363
Contents lists available at ScienceDirect
Progress in Energy and Combustion Science

journal homepage: www.elsevier.com/locate/pecs
A review on the utilization of y ash

M. Ahmaruzzaman*
Department of Chemistry, National Institute of Technology Silchar, Silchar-788010, Assam, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 8 August 2009
Accepted 10 November 2009
Available online 28 December 2009
Fly ash, generated during the combustion of coal for energy production, is an industrial by-product which
is recognized as an environmental pollutant. Because of the environmental problems presented by the y
ash, considerable research has been undertaken on the subject worldwide. In this paper, the utilization of
y ash in construction, as a low-cost adsorbent for the removal of organic compounds, ue gas and
metals, light weight aggregate, mine back ll, road sub-base, and zeolite synthesis is discussed.
A considerable amount of research has been conducted using y ash for adsorption of NOx, SOx, organic
compounds, and mercury in air, dyes and other organic compounds in waters. It is found that y ash is
a promising adsorbent for the removal of various pollutants. The adsorption capacity of y ash may be
increased after chemical and physical activation. It was also found that y ash has good potential for use
in the construction industry. The conversion of y ash into zeolites has many applications such as ion
exchange, molecular sieves, and adsorbents. Converting y ash into zeolites not only alleviates the
disposal problem but also converts a waste material into a marketable commodity. Investigations also
revealed that the unburned carbon component in y ash plays an important role in its adsorption
capacity. Future research in these areas is also discussed.
2009 Elsevier Ltd. All rights reserved.
Keywords:
Fly ash
Adsorption
Wastewater
Heavy metals
Dye
Organics
Zeolite
Construction
Contents
1.
2.
3.
4.
5.
6.
7.
8.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
Properties of coal fly ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
2.1.
Physical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
2.2.
Chemical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
Properties of biomass ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
Fly ash utilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .331
Adsorbents for cleaning of flue gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .331
5.1.
Sulphur compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
5.2.
Adsorption of NOx . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
5.3.
Removal of mercury . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
5.4.
Adsorption of gaseous organics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 333
Removal of toxic metals from wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .333
6.1.
Adsorption of various types of heavy metals on fly ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 334
6.2.
Adsorption mechanism and kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335
6.3.
Adsorption isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
6.4.
Factors affecting adsorption of metal on fly ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
Removal of other inorganic components from wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .337
7.1.
Removal of phosphate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
7.2.
Removal of fluoride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
7.3.
Removal of boron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
Removal of organic compounds from wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
8.1.
Removal of phenolic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
* Tel.: 91 3842 233 797.

E-mail address: md_a2002@rediffmail.com
0360-1285/$ see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.pecs.2009.11.003
328
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327363
8.2.
Removal of pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
8.3.
Removal of other organic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340
Removal of dyes from wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340
9.1.
Azo dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340
9.2.
Thiazine dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340
9.3.
Xanthene dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342
9.4.
Arylmethane dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342
9.5.
Other dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342
Leaching of fly ash in water system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
Synthesis of zeolite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
11.1.
Application of zeolite synthesised from fly ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
Construction work/industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
Lightweight aggregate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
Road sub-base . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
Mine backfill . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
Cost estimation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
Barriers to utilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
Future research and prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
1. Introduction
Since wide scale coal ring for power generation began in the
1920s, many millions of tons of ash and related by-products have
been generated. The current annual production of coal ash worldwide is estimated around 600 million tones, with y ash constituting about 500 million tones at 7580% of the total ash produced
[1]. Thus, the amount of coal waste (y ash), released by factories
and thermal power plants has been increasing throughout the
world, and the disposal of the large amount of y ash has become
a serious environmental problem. The present day utilization of ash
on worldwide basis varied widely from a minimum of 3% to
a maximum of 57%, yet the world average only amounts to 16% of
the total ash [1]. A substantial amount of ash is still disposed of in
landlls and/or lagoons at a signicant cost to the utilizing
companies and thus to the consumers.
Coal is a dominant commercial fuel in India, where 565 mines
are operated by Coal India and other subsidiaries. In 2003,
production of hard coal was 358.4 Mt.; while utilization was 407.33
Mt. India is the sixth largest electricity generating and consuming
country in the world. Fly ash can be considered as the worlds fth
largest raw material resource [2]. An estimated 25% of y ash in
India is used for cement production, construction of roads and brick
manufacture [3]. The y ash utilization for these purposes is
expected to increase to nearly 32 Mt by 20092010. Currently, the
energy sector in India generates over 130 Mt of FA annually [4] and
this amount will increase as annual coal consumption increases by
2.2%. The large-scale storage of wet y ash in ponds takes up much
valuable agricultural land approximately (113 million m2), and may
result in severe environmental degradation in the near future,
which would be disastrous for India.
Fly ash particles are considered to be highly contaminating, due
to their enrichment in potentially toxic trace elements which
condense from the ue gas. Research on the potential applications
of these wastes has environmental relevance, in addition to
industrial interest. Most of the y ash which is produced is disposed
of as landll, a practice which is under examination for environmental concerns. Disposal of y ash will soon be too costly if not
forbidden. Considerable research is being conducted worldwide on
the use of waste materials in order to avert an increasing toxic
threat to the environment, or to streamline present waste disposal
techniques by making them more affordable. It follows that an

economically viable solution to this problem should include utilization of waste materials for new products rather than land
disposal.
Fly ash is generally grey in color, abrasive, mostly alkaline, and
refractory in nature. Pozzolans, which are siliceous or siliceous and
aluminous materials that together with water and calcium
hydroxide form cementitious products at ambient temperatures,
are also admixtures. Fly ash from pulverized coal combustion is
categorized as such a pozzolan. Fly ash also contains different
essential elements, including both macronutrients P, K, Ca, Mg and
micronutrients Zn, Fe, Cu, Mn, B, and Mo for plant growth. The geotechnical properties of y ash (e.g., specic gravity, permeability,
internal angular friction, and consolidation characteristics) make it
suitable for use in construction of roads and embankments, structural ll etc. The pozzolanic properties of the ash, including its lime
binding capacity makes it useful for the manufacture of cement,
building materials concrete and concrete-admixed products. The
chemical composition of y ash like high percentage of silica (60
65%), alumina (2530%), magnetite, Fe2O3 (615%) enables its use
for the synthesis of zeolite, alum, and precipitated silica. The other
important physicochemical characteristics of y ash, such as bulk
density, particle size, porosity, water holding capacity, and surface
area makes it suitable for use as an adsorbent.
From the perspective of power generation, y ash is a waste
material, while from a coal utilization perspective, y ash is
a resource yet to be fully utilized; producers of thermal electricity
are thus looking for ways to exploit y ash. The cement industry
might use it as a raw material for the production of concrete. Coal
y ash discharged from power plants can also be utilized as a byproduct, and its use in recycling materials for agriculture and
engineering is also being studied [5,6]. The conversion of y ash
into zeolite has also been widely examined [7].
Another interesting possibility might be use as a low-cost
adsorbent for gas and water treatment. Several investigations are
reported in the literature on the utilization of y ash for adsorption
of individual pollutants in an aqueous solution or ue gas. The
results are encouraging for the removal of heavy metals and
organics from industrial wastewater. This paper will review the
various applications of y ash, including low-cost adsorbents for
ue gas cleaning, wastewater treatment for removal of toxic ions
Nomenclature
A
B
Ce
Cs
Ct
k1
k2
ks
ki
qe
qt
DG0
DH0
K
Kd
Kf
m
1/n
q
R
S
DS0
t1/2
V
Vb
Vm
x/m
RedlichPeterson constant
RedlichPeterson constant
equilibrium concentration of the solution
surface concentration
solution concentration
pseudo-rst order rate constant
pseudo-second order rate constant
mass transfer co-efcient
rate parameter of intraparticle diffusion control stage
amount of adsorbate adsorbed at equilibrium (mg/g)
amount of adsorbate adsorbed at any time t (mg/g)
standard Gibbs free energy of adsorption (kJ/mol)
standard enthalpy change of adsorption (kJ/mol)
Langmuir equilibrium constant
distribution co-efcient
Freundlich constant
mass of the adsorbent
adsorption intensity
heat of adsorption
universal gas constant
specic surface area
standard entropy change of adsorption (JK1 mol1)
half-life period
eluted volume (ml)
volume of efuent at break point (ml)
Langmuir monolayer adsorption capacity
amount adsorbed per unit of the adsorbent
heterogeneity factor
Abbreviations
AASHTO American association of state highway and transport
ofcials
ABS
acrylonitrile butadiene styrene
ACC
autoclaved cellular concrete
ACCG
activated carbon-commercial grade
ACLG
activated carbon laboratory grade
Acid Orange 7 p-(2-hydroxy-1 naphthylazo)benzene sulfonic
acid
AEA
air entraining admixture
AMD
acid mine drainage
ASR
alkalisilica reaction
ASTM
American society for testing of materials
BDTDA benzyldimethyl tetradecylammonium
BFA
bagasse y ash
BG
Brilliant green
CANMET Canada centre for mineral and energy technology
CC
char-carbon
CCP
coal combustion products
CCB
coal combustion by-products
CEC
cation exchange capacity
CFA
coal y ash
CFS
chemical xation and solidication
and organic matters, synthesis of zeolite, mine backll, light weight

aggregate, road sub-base and construction/cement applications.
2. Properties of coal y ash
Characterisation of y ash in terms of composition, mineralogy,
surface chemistry and reactivity is of fundamental importance in
the development of various applications of y ash.
CPC
CR
DDD
DDE
DEF
DNP
DTA
EDTA
EPA
FA
FAZ-Y
FGD
FTIR
GGBFS
HDTMA
HeCB
HVFA
HSFA
IFA
LCA
LOI
MB
MSWI
MV
NMR
NPC
OG
OPC
PPC
RB
RBB
RCC
RHFA
RPC
RY
SDS
SSA
SEM
SMZ-Y
TCB
TCLP
TEA
TEM
TOC
TPABr
USEPA
UHPC
TNT
UHPC
WC
XRD
XRF
ZFA
329
cityl pyridinium chloride

Congo red
2,2-bis (4chloro-phenyl)-1,1,-dichloro ethane
2,2-bis (4chloro-phenyl)-1,1,-dichloro ethane
delayed ettringite formation
di-ntrophenol
differential thermal analysis
ethylene diamine tetraacetic acid
Environmental protection agency
y ash
y ash based zeolite
ue gas desulphurization
Fourier Transform infrared spectroscopy
ground granulated blast furnace slag
hexadecyl tetramethyl ammonium
2,21,3,31,4,5,6-heptachlorobiphenyl
high-volume y ash
high-sulphate y ash
impregnated y ash
life cycle assessments
loss on ignition
methylene blue
Municipal solid waste incinerator bottom ash
methyl violet
nuclear magnetic resonance
normal Portland cement
Orange-G
ordinary Portland cement
Pozzolana Portland cement
rhodamine B
Remazol brillant blue
reinforced concrete construction
rice husk y ash
reactive powder concrete
rifacion yellow HED
sodium dodecyl sulphate
sewage sludge ash
scanning electron microscope
surface modied y ash based zeolite
2,3,4-trichloro biphenyl
Toxicity Characteristic Leaching Procedure
tetramethyl ammonium
transmission electron microscope
total organic carbon
tetraporpyl ammonium bromide
United States environmental protection agency
ultra high-performance concrete
tri-nitro toluene
ultra high-performance concrete
wood charcoal
X-ray diffraction
X-ray uorescence
zeloite y ash
2.1. Physical properties

Fly ash consists of ne, powdery particles predominantly
spherical in shape, either solid or hollow, and mostly glassy
(amorphous) in nature. The carbonaceous material in the y ash is
composed of angular particles. The particle size distribution of most
bituminous coal y ash is generally similar to that of silt (less than
a 0.075 mm or No. 200 sieve). Although sub-bituminous coal y ash
330
is also silt-sized, it is generally slightly coarser than bituminous coal

y ash. The specic gravity of y ash usually ranges from 2.1 to 3.0,
while its specic surface area may vary from 170 to 1000 m2/kg [8
11]. The colour of y ash can vary from tan to gray to black,
depending on the amount of unburned carbon in the ash.
2.2. Chemical properties
The chemical properties of y ash are inuenced to a great extent
by the properties of the coal being burned and the techniques used for
handling and storage. There are basically four types, or ranks, of coal,
each vary in heating value, chemical composition, ash content, and
geological origin. The four types (ranks) of coal are anthracite, bituminous, sub-bituminous, and lignite. In addition to being handled in
a dry, conditioned, or wet form, y ash is also sometimes classied
according to the type of coal from which the ash was derived.
The principal components of bituminous coal y ash are silica,
alumina, iron oxide, and calcium, with varying amounts of carbon,
as measured by the loss on ignition (LOI). Lignite and sub-bituminous coal y ash is characterized by higher concentrations of
calcium and magnesium oxide and reduced percentages of silica
and iron oxide, as well as lower carbon content, compared with
bituminous coal y ash. Very little anthracite coal is burned in
utility boilers, so there are only small amounts of anthracite coal y
ash. Table 1 compares the normal range of the chemical constituents of bituminous coal y ash with those of lignite coal y ash and
sub-bituminous coal y ash. From the table, it is evident that lignite
and sub-bituminous coal y ash has a higher calcium oxide content
and lower loss of ignition than y ash from bituminous coals.
Lignite and sub-bituminous coal y ash may have a higher
concentration of sulphate compounds than bituminous coal y ash.
According to the American Society for Testing Materials (ASTM
C618) [12], the ash containing more than 70 wt% SiO2 Al2O3 Fe2O3 and being low in lime are dened as class F, while
those with a SiO2 Al2O3 Fe2O3 content between 50 and 70 wt%
and high in lime are dened as class C. Briey, the high-calcium
Class C y ash is normally produced from the burning of low-rank
coals (lignites or sub-bituminous coals) and have cementitious
properties (self-hardening when reacted with water). On the other
hand, the low-calcium Class F y ash is commonly produced from
the burning of higher-rank coals (bituminous coals or anthracites)
that are pozzolanic in nature (hardening when reacted with
Ca(OH)2 and water). The chief difference between Class F and Class
C y ash is in the amount of calcium and the silica, alumina, and
iron content in the ash. In Class F y ash, total calcium typically
ranges from 1 to 12%, mostly in the form of calcium hydroxide,
calcium sulphate, and glassy components, in combination with
silica and alumina. In contrast, Class C y ash may have reported
calcium oxide contents as high as 3040%. Another difference
between Class F and Class C is that the amount of alkalis (combined
sodium and potassium), and sulphates (SO4), are generally higher
in the Class C y ash than in the Class F y ash.
Table 1
Normal range of chemical composition for y ash produced from different coal
types.
Component (wt.%)
Bituminous
Sub-bituminous
Lignite
SiO2
Al2O3
Fe2O3
CaO
MgO
SO3
Na2O
K2O
LOI
2060
535
1040
112
05
04
04
03
015
4060
2030
410
530
16
02
02
04
03
1545
1025
415
1540
310
010
06
04
05
The mineralogical composition of y ash, which depends on the

geological factors related to the formation and deposition of coal,
its combustion conditions, can be established by X-ray diffraction
(XRD) analysis. The dominant mineral phases are quartz, kaolinite,
ilite, and sideraete. The less predominant minerals in the unreacted
coals include calcite, pyrite and hematite. Quartz and mullite are
the major crystalline constituents of low-calcium ash, whereas
high-calcium y ash consists of quartz, C3A, CS and C4AS.
The several distinct end uses of y ash differ considerably
among themselves in the stringency of the properties required in
the y ash for its successful utilization. The success of y ash in
structural ll applications rests primarily on the ability of the
material to be compacted to a reasonably strong layer of low unit
weight. This is primarily a function of particle size distribution, and
to some extent of the content of spherical particles. The chemical
characteristics of y ash are secondary, although the post
compaction cementation provided by some high-calcium y ash is
likely to prove benecial.
With highway bases chemical considerations come into play,
although not in an important way. Stabilization of some base
courses (and stabilized sub grades) may rest on lime y ash
chemical reactions, i.e. the classical pozzolanic reaction, with
lime. Low-calcium y ash may be entirely satisfactory or even
preferred, especially where sufcient time is available for these
slow reactions to take place. The only real chemical requirement is
that y ash has a sufcient content of glass that eventually will
react with added lime. Some road base applications of y ash
depend on the physical effects of y ash incorporation rather than
its reaction with lime.
The cement and concrete end-use areas are by far the most
demanding of the y ash in terms of adherence to strict criteria and
requirements. However, the requirements differ considerably
depending on the specic end use involved.
Fly ash for use as a raw material in cement manufacture is sold
and used primarily on the basis of its chemical composition, as
expressed in the usual oxide convention. Such factors as glass
content, the type of crystalline matter present, size distribution, etc.,
are relatively immaterial. Even high carbon content, which may be
limiting in most other end uses, may actually be benecial in cement
raw material use, since it provides a denite (although modest)
proportion of the fuel needed. Uniformity and chemical consistency
from day to day and week to week is the prime necessity.
Fly ash, as a blended cement component shares some of the
requirements for both raw material and direct concrete admixture
use. Since such y ash eventually is incorporated in concrete, its
chemical and physical characteristics must be suitable for that
purpose. However, since little or no adjustment can be provided at
the concrete mixing stage, y ash for use in blended cements must
be of consistent and uniform chemical and physical characteristics,
the consistency and predictability being as important as the
numerical values of the various parameters involved. Since the
blended cement manufacturer has little control over the concurrent
use of chemical admixtures or of mixing and curing conditions, the
y ash used should be relatively insensitive to such variations.
Especially to be considered here are rheological effects, strength
development characteristics, and possibilities for developing
eforescence. The color of the ash and its effect on the color of the
nal concrete to be produced by the blended cement may also be of
importance.
3. Properties of biomass ash
The use of biomass as fuel generates large amount of residual
ash which causes serious environmental problems. Biomass ash
does not contain toxic metals like in the case of coal ash. The ash
forming constituents in biomass fuels are quite diverse depending

on the type of biomass, type of soil and harvesting [13]. In general,
the major ash forming inorganic elements in biomass fuels are Ca,
K, Na, Si and P and some of these act as important nutrients for the
biomass [14]. However, some biomass fuels have high silicon
content (e.g. rice husk) while some have high alkali metal content
(wood). While the elemental composition of the ash is determined by the inorganic constituents in the parent biomass, the
crystallinity and mineralogy depends on the combustion technique used.
Typically, y ash from neat biomass combustion has more alkali
(Na and K) and less alumina (Al2O3) than coal y ash [13,15]. As
a class, biomass fuels exhibit more variation in both composition
and amount of inorganic material than is typical of coal. Therefore,
biomass y ash varies more than coal y ash, which depends on the
varieties of origin from woody to herbaceous and other resources
[14,16]; furthermore, even for the same type of biomass, the
properties of its y ash depends also on some growth and
production factors including weather, season, storage and
geographic origins [16,17].
Compared to coal y ash where signicant research has already
taken place and high utilisation gures are already reported in
several countries [16,18], commercial utilisation of biomass ash is
not widely reported. However, several research efforts are
underway for applications such as adsorbent, raw material for
ceramics, cement and concrete additive, material recovery, etc.
based on its characteristics. The composition, surface area, and
presence of unburnt material play an important role in determining
the application.
Many kinds of biomass y ash have similar pozzolanic properties as coal y ash, such as those from rice husk, wood, wheat straw
and sugar cane straw [1921] among which have been added in
concrete as mineral admixtures, improving the performance of
concrete.
Bagasse y ash has been examined as an adsorbent as well as an
additive in cement and concrete [1921]. However, its high carbon
content can cause a hindrance in its application for concrete. Rice
husk with its high silica content has been used as an insulator,
adsorbent, cement and concrete additive and as a substitute for
silica [22]. Studies on ash from arecanut shell, cashewnut shell and
groundnut shell ash are limited [21].
4. Fly ash utilization

There are many reasons to increase the amount of y ash being
re-utilized. A few of these reasons are given below.
Firstly, disposal costs are minimized; secondly, less area is
reserved for disposal, thus enabling other uses of the land and
decreasing disposal permitting requirements; thirdly, there may be
nancial returns from the sale of the by-product or at least an offset
of the processing and disposal costs; and fourthly, the by-products
can replace some scarce or expensive natural resources.
Utilization of coal combustion by-products, namely y ash, can
be in the form of an alternative to another industrial resource,
process, or application. These processes and applications include,
but are not limited to, addition to cement and concrete products,
structural ll and cover material, roadway and pavement utilization, addition to construction materials as a light weight aggregate,
inltration barrier and underground void lling, and soil, water and
environmental improvement. The following is a brief description of
each of the previously mentioned alternative uses of y ash and
associated research that has been conducted and how it relates to
each alternative use. In this section, the application of y ash has
been discussed.
331
5. Adsorbents for cleaning of ue gas

5.1. Sulphur compounds
Effort has been made to reduce SOx emissions by installing
equipment for ue gas desulphurization (FGD). The wet-type
limestone scrubbing processes is widely used because of its high
DeSOx efciency and easy operation. However, these processes
have drawbacks, such as high water consumption and the need for
wastewater treatment [6]. Dry-type FGD does not require wastewater treatment; however, it requires a large amount of absorbent
compared to wet-type FGD. This may be due to the fact that
a higher molar ratio of calcium to-sulphur is required to obtain
a high DeSOx efciency. The reactions are represented below.
NO D 1=2 O2 / NO2
(1)
SO2 D NO2 / SO3 D NO
(2)
CaOH2 D SO3 / CaSO4 D H2 O
(3)
As shown in the above chemical formulas, the sulfur dioxides in

the ue gas are xed as gypsum. On the other hand, they are xed
as sulte in other conventional dry processes such as limestone
injection and active manganese. Some of the spent absorbent discharged from the desulfurization process can be used as the raw
material for the absorbent pellets. In addition, this spent absorbent
is reused as a solidication agent for sludge and as a deodorant for
refrigerators, pet litter and so on [23]. The process ow is explained
as follows: the system is composed of an absorber body, an
absorbent feeder and a drawout facility, and an absorbent
manufacturing facility. The absorbents in a xed process are fed
into an absorber and drawn out of its lower part. Both absorption
and removal in sulfur dioxide are conducted during the time when
the absorbents move down from the upper part to the lower part of
the absorber. Flue gas containing sulfur dioxide is introduced to the
absorber to make contact with the absorbents, and then the treated
gas is discharged from a stack to the atmosphere [23]. A simplied
plan view is shown in Fig. 1.
Activated carbon was used to oxidize reduced sulphur
compounds; however, it is too costly for large-scale environmental
remediation applications. Coal y ash is a cheap absorbent for
dry-type FGD. Fly ash recycling in the ue gas desulphurization
process has shown promising results. Fly ash treated with calcium
hydroxide has been tested as a reactive adsorbent for SO2 removal
[24]. A mixture of y ash and calcium hydroxide for
Fig. 1. Schematic plant view of ue gas desulfurization using coal ash [23].
332
desulphurization was also studied by Davini [25,26]. It was found

that Ca(OH)2-y ash mixtures were a low-cost SO2 control option.
Davini [27] also tested a process using activated carbon derived
from y ash for SO2 and NOx adsorption from industrial ue gas;
this mixture exhibited similar characteristics to typical activated
carbon for ue gases.
The FGD process using coal ash has been commercialized, and
some industrial plants have achieved DeSOx efciencies of over
90%, such as the Ebetsu power station (50,000 Nm3/h) and the
Tomtoh Atsuma power station (644,000 Nm3/h) under a high molar
ratio of calcium to sulfur (1.01.2) [23]. During operation, there is
no need for wastewater treatment or gas reheating, and so this
process is considered to be an ideal choice for controlling the
emission of sulfur dioxide and an environmentally friendly method
for reuse of coal ash. Since the introduction of FGD in the late 1960s,
global market demand for FGD has been steady at between 5000
and 10,000 MW per year, and mainly wet-type limestone FGD units
have been installed [28]. As described in this part, wet limestone
FGD requires a wastewater treatment facility. Furthermore, it emits
carbon dioxide (greenhouse gas) into the atmosphere as follows.
CaCO3 slurryDSO2 D 1=2 O2 / CaSO4 slurry D CO2
(4)
Dry-type FGD using y ash is one of the processes that provide

a solution to the above-mentioned problems, but this FGD has not
yet spread worldwide.
5.2. Adsorption of NOx
Fly ash has also been proposed as adsorbents for NOx removal
from ue gases [29]. The properties of y ash particularly with
respect to NOx adsorption were closely examined for carbon
content and specic surface area. It was found that unburned
carbon remaining in the y ash particles contribute the main
surface area to y ash, and the carbon can be activated to further
improve the adsorption performance of the y ash. Experimental
results on activating coarser y ash particles showed that adsorption capacity can be increased through controlled gasication of the
unburned carbon. So, this carbon present in y ash can be
a precursor of activated carbons since it has gone through devolatilization during combustion in the power station furnace, and it,
requires only a process of activation [30]. The adsorption of NOx
using activated chars recovered from y ash was reported [31].
Carbon-rich fractions from a gasier were adsorbed one-third of
the NOx compared with a commercial carbon. Recently, activated
carbon from unburned carbon in coal y ash has also been used for
removal of NO [32]. It was found that mineral matter must be
removed efciently from unburnt carbon of y ash before activation, to obtain a more suitable activated carbon for environmental
applications in the gas phase.
5.3. Removal of mercury
Mercury has long been known as a potential hazard to-health
and environmental hazard; it is identied as one of the 189 toxic air
pollutants by the Clean Air Act Amendments of 1990. Because
mercury accumulates in the biosystem it is of particular concern; it
is very difcult to monitor and capture, and is high in the public
awareness.
To cope with the mercury emission problem, efforts have been
made to remove various types of mercury from the ue gas of
utility boilers. However, due to technical and economic limitations,
no process has been commercially utilized beyond pilot scale tests.
Among the current technologies being evaluated, activated carbon
injection is the process most promising for removing mercury from
ue gas, due to its high removal efciency. In this process, activated

carbon powder is injected into the ue gas stream and collected,
after adsorption, with a particulate matter control device. However,
the high cost of activated carbon hinders large-scale applications in
utility boilers [33]; therefore, it is desirable to nd an alternative
carbon.
Usually the unburned carbon content in y ash is in the range of
212%. However, with the introduction of the 1990 Clean Air Act
Amendments, caps have been established on the emission of
nitrogen oxides (NOx). Many coal-red utilities have begun to
retrot with low NOx burners to meet the emission requirements.
As a result of such transition, the carbon content of y ash increases
signicantly, up to 20% in some cases, due to the low oxygen and/or
low temperature combustion conditions required by those low NOx
combustion units. Since the unburned carbon separated from y
ash is a by-product, any practical application of such material
would be economically and environmentally advantageous to the
overall y ash beneciation process. Researchers at The Pennsylvania State University have developed a method to economically
separate unburned coal from y ash [34]. Preliminary study shows
that some unburned carbon from y ash has certain capabilities for
adsorbing elemental mercury. Such ndings triggered the idea of
using y ash carbon as a low-cost adsorbent in removing elemental
mercury from gas phases, such as utility ue gas, to replace costly
activated carbons.
The retention of hazardous elements by y ash produced in
combustion plants has been extensively studied in recent years. In
the case of mercury it has been observed that some y ash may
capture this element which would otherwise be emitted into the
atmosphere. Although the role of inorganic components of y ash
in this capture is still unclear, considerable attention has been paid
to the capture of mercury by unburned y ash carbons [3542].
A relationship has been reported between Hg content and the
percentage of carbon in y ash derived from the combustion of
bituminous coals [37] and coal blends containing anthracites
[42,43]. The role that the different types of unburned carbons play
in mercury capture in y ash has also been a matter of interest for
some studies associating types of particles with the amount of Hg,
captured [35,42,43]. The concentration of unburned carbons and
their respective ability to capture Hg have also been related to their
textural properties [37,4345], given that the BET surface area
successively increased from inertinite, isotropic coke (isotropic y
ash carbons) to anisotropic coke (anisotropic y ash carbons) [37].
The exact nature of Hgy ash interactions is still unknown and
the variables affecting the mercury adsorption need to be identied. In view of the signicant variations in the properties of y ash
obtained from different coals [43,4648], and to better understand
the properties of the materials inuencing the capture of Hg, LopezAnton et al. [49] have tried to establish a relationship between Hg0
and HgCl2 retention and the characteristics of y ash samples taken
from the combustion of feed coal blends of different characteristics.
The relationship between the types of particles, the BET (Bruner
Emmett Taylor) surface area and the quantities of mercury retained
was studied. It can be seen that the y ash exhibit different
retention capacities depending on the species in gas phase (Hg0 or
HgCl2). A comparison of the results obtained demonstrates that Hg0
is retained in y ash in a greater proportion than HgCl2. When the
raw y ash samples are compared with the fractions enriched in
unburned carbons it can be observed that retention capacity
increases slightly as the unburned carbon content (LOI) increased.
The mercury values recorded were compared to the content of each
type of organic component and total inorganic matter present in
the y ash. Because mercury retention depends on the mode of
occurrence of this element in gas phase the evaluation was based
on each individual mercury species. When the retention of Hg0 was
compared to the amount of each type of unburned carbons in the

y ash, no correlations were found. However, a general tendency
could be observed with the anisotropic, fused and porous structures (which are mainly network structures in all cases). The y ash
samples that have a greater surface area retain a higher quantity of
HgCl2, but this tendency shows several exceptions in the case of Hg.
The adsorption of mercury on carbon can be explained by the
physical and chemical interactions which occur between the
carbon surface and mercury. According to the theory proposed by
Dubini [50] the carbon surface contains some adsorption centers,
called primary sites. When a molecule of the adsorbate adsorbs on
a primary site, the adsorbed molecule can then act as a secondary
center for the adsorption of more molecules. The enhancement of
mercury adsorption after oxidizing unburned carbon at 400 C in
air shows that oxygen-containing functional groups may have an
important role, which is also suggested by Hall et al. [51]. Masaki
et al. [52] utilized synthetic y ash, consisting of calcium chloride
with 5% activated carbon, which showed very high efciency of
over 99% for mercury removal at 120 C. When the calcium chloride
content was more than 0.5% in the synthetic y ash with 5% activated carbon, mercury vapor was completely removed. However,
the most efcient removal was obtained when the activated carbon
content ranged from 5 to 7% in synthetic y ash with 1% calcium
chloride. The removal of mercury was affected by temperature, if
the activated carbon content was very small. It was assumed that
the complex chemical action with activated carbon and calcium
chloride was most signicant for metallic mercury removal by
actual y ash.
Table 2
Summary of adsorption of metals on y ash.
Metals Adsorbent
Adsorption
Temperature ( C) References
capacity (mg/g)
Zn2
Coal y ash
Fe impregnated y ash
Al impregnated y ash
Coal y ash
Coal y ash(I)
Coal y ash(II)
Bagasse y ash
Bagasse y ash
Fly ash
Fly ash
Fly ash
Fly ash
Rice husk ash
Bagasse y ash
Fly ash
Rice husk ash
Fly ash
6.513.3
7.515.5
7.015.4
0.252.8
0.251.19
0.071.30
2.342.54
13.21
4.64
0.27
0.0680.75
3.4
5.88
7.03
11.11
14.30
7.84
3060
3060
3060
20
20
20
3050
30
23
25
055
[81]
Fly ash
Fly ash-washed
Fly ash-acid
Fly ash
Fly ash zeolite
Fly ash
Fly ash (I)
Fly ash (II)
Bagasse y ash
Fly ash
Coal y ash
Rice husk ash
Afsin-Elbistan y ash
Seyitomer y ash
Bagasse y ash
Fly ash
Fly ash
198.2
195.2
180.4
1.68.0
95.6
0.670.83
0.080.29
0.00770.22
1.242.0
0.05
18.98
3.04
0.29
0.21
6.19
207.3
1.38
25
25
25
20
20
20
20
3050
25
25
[79]
Fly ash
Fly ash-washed
Fly ash-acid
Fly ash
Bagasse y ash
Fly ash
Fly ash
Treated rice husk ash
444.7
483.4
437.0
753
285566
18.8
18.0
12.61
25
25
25
32
3050
Fly ash
Fly ash wollastonite
Fly ash
Fly ash (I)
Fly ash (II)
Fly ash
Fly ash-washed
Fly ash-acid
Fly ash
Bagasse y ash
Fly ash
Fly ash
Coal y ash
Fly ash
CFA
CFA-600
CFANAOH
1.39
1.18
1.78.1
0.341.35
0.091.25
207.3
205.8
198.5
0.630.81
2.262.36
0.76
7.5
20.92
7.0
178.5249.1
126.4214.1
76.7137.1
30
30
20
20
25
25
25
25
3050
32
25
Fly ash
Fly ash(I)
Fly ash(II)
Bagasse y ash
Fly ash
Bagasse y ash
Fly ash
9.014.0
9.814.93
1015.75
0.400.98
0.061.16
1.121.70
3.9
6.48
0.03
3060
3060
3060
20
20
3050
[81]
Fly ash
52.6106.4
2040
[65]
Cd2
5.4. Adsorption of gaseous organics

Apart from the adsorption of NOx, SOx and mercury in ue gas,
y ash has also been used for adsorption of organic gas. The
adsorption of toluene vapours on y ash was investigated by Peloso
et al. [53]. It was found that y ash product obtained after particle
aggregation and thermal activation showed satisfactory adsorption
performance for toluene vapours [54]. The adsorption kinetics of
representative aromatic hydrocarbon and m-xylene, on y ash has
also been studied [55]. The results indicated that the kinetics of mxylene adsorption by y ash resembled kinetics reported for
penetration of absorbates into porous adsorbents. No increase in
adsorption rates was observed with increased temperature, and
rate constants decreased with increased vapour pressure. This
suggested that adsorption was diffusion-controlled.
Pb2
Cu
6. Removal of toxic metals from wastewater

Fly ash has potential application in wastewater treatment
because of its major chemical components, which are alumina,
silica, ferric oxide, calcium oxide, magnesium oxide and carbon,
and its physical properties such as porosity, particle size distribution and surface area. Moreover, the alkaline nature of y ash makes
it a good neutralising agent. Generally, in order to maximise metal
adsorption by hydrous oxides, it is necessary to adjust the pH of
wastewater using lime and sodium hydroxide [56,57].
Today, heavy metals are most serious pollutants, becoming
a severe public health problem. Heavy metal and metalloid removal
from aqueous solutions is commonly carried out by several
processes such as, chemical precipitation, solvent extraction, ion
exchange, reverse osmosis or adsorption etc. Among these
processes, the adsorption process may be a simple and effective
technique for the removal of heavy metals from wastewater.
333
Ni2
Cr3
[83]
[84]
[93]
[94]
[104]
[105]
[106]
[87]
[86]
[85]
[71]
[63]
[71]
[80]
[83]
[85]
[95]
[105]
[70]
[86]
[64]
[85]
[79]
[68]
30
3060
3060
3060
[79]
[92]
[87]
[75]
[73]
[68]
[80]
[84]
[79]
[69]
[93]
[100]
[87]
[70]
[75]
[74]
[84]
[95]
[87]
[85]
[67]
(continued on next page)
334
Table 2 (continued )
Metals Adsorbent
Adsorption
Temperature ( C) References
capacity (mg/g)
Cr6
Fly ash wollastonite

Fly ash China clay
Fly ash
Rice husk Ash
Fly ash
Fly ash(I)
Fly ash(II)
Bagasse y ash
2.92
0.31
23.86
25.64
1.38
1.82
1.67
0.55
0.82
4.254.35
3060
3060
3060
20
20
3050
[61]
Fly ash
Fly ash
Sulfo-calcic
Silico-aluminous ashes
Fly ash-C
Treated rice husk ash
Fly ash coal-char
Fly ash
Fly ash coal-char
2.82
11.0
12.5
13.4
5.0
3.2
0.630.73
6.72
3.789.2
7.727.8
0.0234.5
30
3060
3060
3060
30
30
521
30
25
20
25
[76]
[82]
Hg2
As3
As5
[62]
[82]
[85]
[85]
[97]
[87]
[87]
[77]
[73]
[109]
[107]
[109]
6.1. Adsorption of various types of heavy metals on y ash

Fly ash has been widely used as a low-cost adsorbent for the
removal of heavy metal. Table 2 summarizes the results of the
important metals investigated using y ash. Among these metal
ions, Ni, Cr, Pb, As, Cu, Cd and Hg are the most often investigated.
The use of y ash for removal of heavy metals was reported as early
as 1975. Gangoli et al. [58] reported the utilization of y ash for the
removal heavy metals from industrial wastewaters.
Removal of chromium ions, including Cr(VI) and Cr(III) using y
ash has been investigated by several researchers [59,60]. The effects
of chromium concentrations, y ash dosage, contact time, and pH
on the removal of chromium were reported. A homogeneous
mixture of y ash and wollastonite (1:1) was also reported to
remove Cr(VI) from aqueous solutions by adsorption [61]. Bhattacharya et al. [62,63] studied the removal of Cr(VI) and Zn (II) from
aqueous solution using y ash. Turkish y ash was also used for the
removal of Cr(VI) and Cd(II) from an aqueous solution on [64]. Fly
ash was found to have a higher adsorption capacity for Cd(II), as
compared to Cr(VI). The lime (crystalline CaO) content in the y ash
seemed to be a signicant factor inuencing the adsorption of
Cr(VI) and Cd(II). Fly ash obtained from the combustion of poultry
litter was also utilized as an adsorbent for the removal of Cr(III)
from aqueous solution [65]. Yadava et al. [66] investigated the
removal of cadmium by y ash by varying contact time, temperature and pH. The removal of Cd(II) has been found to be contact
time, concentration, temperature and pH dependent. The process
of removal follows rst order adsorption kinetics and the rate
controlling step is intraparticle transport into the pores of y ash
particles. The temperature dependence of Cd(II) adsorption on y
ash indicates the exothermic nature of adsorption. Alkaline
aqueous medium favors the removal of Cd(II) by y ash. The
increase in adsorption of Cd(II) with pH has been explained on the
basis of surface complex formation approach. Raw bagasse and coal
y ash have also been used as low-cost adsorbents for the removal
of chromium and nickel from aqueous solutions [67]. The extent of
adsorption at equilibrium was found to be dependent on the
physical and chemical characteristics of the adsorbent, adsorbate
and experimental system.
Fly ash was also utilized for the removal of copper from aqueous
solution. Removal efciency was found to be dependent on
concentration, pH and temperature [68]. The kinetics of adsorption
indicated the process to be diffusion controlled. Fly ash with

different quantities of carbon and minerals was also used for
removal of Cu(II) from an aqueous solution [69]. The carbon fraction
in y ash was important in the removal of Cu(II). The specic
adsorption capacities of carbon ranged from 2.2 to 2.8 mg Cu/g
carbon, while the capacities for mineral were only about 0.63
0.81 mg Cu/g mineral. Fly ash can also be shaped into pellets and
used for the removal of copper and cadmium ions from aqueous
solutions [70]. The calculated adsorption capacities for copper and
cadmium were found to be 20.92 and 18.98 mg/g, respectively. It was
found that y ash shaped into pellets could be considered as
a potential adsorbent for the removal of copper and cadmium from
wastewaters. Equilibrium studies for the adsorption of zinc and
copper from aqueous solutions were carried out using sugar beet
pulp and y ash [71]. The removal characteristics of Pb(II) and Cu(II)
from aqueous solution by y ash were investigated by Alinnor [72].
The utilization of rice husk ash was investigated for the adsorption of
Pb(II) and Hg(II) from aqueous water [73]. The Bangham equation
can be used to express the mechanism for adsorption of Pb(II) and
Hg(II), by rice husk ash. Its adsorption capability and adsorption rate
are considerably higher and faster for Pb(II) than for Hg(II). The ner
the rice husk ash particles used, the higher the pH of the solution and
the lower the concentration of the supporting electrolyte, potassium
nitrate solution, the more Pb(II) and Hg(II) absorbed on rice husk ash.
Raw and modied coal y ash effectively adsorbs Cu(II) from
wastewater [74]. These adsorptions were endothermic in nature;
the values of activation energy (between 1.3 and 9.6 kJ mol1) were
consistent with an ion exchange adsorption mechanism. The
adsorptions of Cu(II) onto coal y ash (CFA), CFA-600, and CFA
NaOH followed pseudo-second order kinetics. Changing the nature
of CFA did not improve its ability to adsorb Cu(II).
The presence of organic pollutants signicantly affected the
removal of heavy metals from wastewater. Wang et al. [75] investigated the competitive adsorption of heavy metals and humic acid
using y ash as adsorbent. It is found that, for a single pollutant
system, y ash can achieve adsorption of lead ion at 18 mg/g,
copper ion at 7 mg/g and humic acid at 36 mg/g, respectively. For
co-adsorption, complexation of heavy metals and humic acid plays
an important role. The presence of humic acid in water will provide
additional binding sites for heavy metals, thus promoting metal
adsorption on y ash. For PbHA and CuHA systems, Pb(II) and
Cu(II) adsorption can increase to 37 and 28 mg/g, respectively. The
heavy metal ions present in the system will compete with the
adsorption of humic acid on y ash, thus resulting in a decrease in
humic acid adsorption.
Fly ash was also found to be effective for the removal of mercury.
The adsorption capacity of coal y ash for mercury was comparable
to that of activated powdered charcoal [76]. The effectiveness of y
ash in adsorbing mercury from wastewater has been studied [77].
Selective adsorption of various metal ions (Na, K, Mg, Ca, Cu, Cd,
Mn, Hg, Cr, Pb, and Fe) by y ash was also reported [78]. Lead ions
were found to be selectively adsorbed at a mean value of 19 meq of
Pb(II) per 100 g of y ash. This selective adsorption could be due to
the formation of crystalline ettringite mineral after the hydration of
the y ash. Coal y ash has also been used for the removal of toxic
heavy metals, i.e. Cu(II), Pb(II) and Cd(II) from water [79]. The
breakthrough volumes of the heavy metal solutions have been
measured by dynamic column experiments in order to determine
the saturation capacities of the adsorbents. The adsorption
sequence is Cu > Pb > Cd in accordance with the order of insolubility of the corresponding metal hydroxides. Similar results on the
adsorption of Cd and Cu by y ash were also reported [80]. The
presence of high ionic strength or appreciable quantities of calcium
and chloride ions does not have a signicant effect on the
adsorption of these metals by y ash.
Banerjee et al. [60,61], studied the adsorption of various toxic

metal ions, Ni(II) and Zn(II), Cr(II) and Hg(II)], on y ash and Al and Fe
impregnated y ash. The impregnated y ash showed much higher
adsorption capacity for all the ions, as compared to that of untreated
y ash. The adsorption capacity of FA, AlFA, and FeFA for Cr(VI)
was found to be 1.379, 1.820, and 1.667 mg/g and that of Hg(II) was
11.00,12.50, and 13.40 mg/g. Bayat investigated the removal of Zn(II)
and Cd(II) [83], Ni(II) and Cu(II) [84], using lignite-based y ash and
activated carbon, and found that y ash was effective as activated
carbon. The percent adsorption of Zn(II) and Cd(II) increased with an
increase in concentration of Zn(II) and Cd(II), dosage of y ash and
temperature; maximum adsorption occurred in the pH range of 7.0
7.5. The effectiveness of y ash as an adsorbent improved with
increased calcium content (CaO). Fly ash was found to have a higher
adsorption capacity for Cd(II), compared to Cr(VI). Bagasse y ash
and rice husk ash were also utilized for the removal of Ni(II),Cd(II)
and Zn(II) from an aqueous solution [85,86].
Fly ash and y ash/lime mixture were investigated for the
removal of Cu, Ni, Zn, Cd and Pb [87,88]. The extent of removal was
achieved in the order of Pb(II) > Cu(II) > Ni(II) > Zn(II) > Cd(II).
Formation of calcium silicate hydrates (CSH) was assumed to be
responsible for increasing removal, and for decreasing desorption.
Two uidized-bed-sourced y ashes with different chemical
compositions, silico-aluminous y ash and sulfo-calcic y ash, were
tested to remove Pb(II), Cu(II), Cr(III), Ni(II), Zn(II), Cr(VI) [89] and
Hg(II) [90] from aqueous solutions. The percentage of adsorbed ions
was greater when they were in contact with silico-aluminous y
ash than sulfo-calcic y ash, except in the case of the ion Ni(II).
Mercury is bound to the ash surface due to several chemical reactions between mercury and various oxides (silicon, aluminium and
calcium silicate), on the surface of the ash.
Gupta and Terres [91] measured the changes in toxicity and
heavy metals in a municipal wastewater treatment plant efuent
by treatment with y ash. After the treatment with y ash, the
efuent showed a signicant reduction in toxicity, Cu, Pb and
PO43 and NO
3 contents. Fly ash removed Cu and Pb from the
efuent; the removal of these toxic heavy metals resulted in
a reduction of toxicity. The Gupta research group conducted a series
of investigations on the adsorption of heavy metals, using bagasse
y ash as adsorbents. They used bagasse y ash from sugar
industries for the removal of lead [92], copper and zinc [93,94],
cadmium, nickel [95] and chromium [96,97] from aqueous solutions. Copper and zinc are adsorbed by the developed adsorbent up
to 9095% in batch and column experiments. The batch test showed
90% removal for Cd and Ni, in about 60 and 80 min, respectively.
The removal of Zn is 100% at low concentrations, whereas removal
is 6065% at higher concentrations. The uptake decreases with
increased temperature, indicating that the process is exothermic in
nature. Lead and chromium are also adsorbed by the developed
adsorbent up to 9698%. The removal of these two metal ions (up to
9596%), was achieved by column experiments at a ow rate of
0.5 mL/min. The adsorption capacities of sewage sludge ash (SSA),
with y ash for copper ions were compared [98]. The estimated
maximum capacity of copper adsorbed by SSA was 3.24.1 mg/g
close to that of y ash. The adsorption isotherm of SSA for copper
ions generally followed the Langmuir model and depends on
particle size, loading, pH etc. The primary mechanisms of copper
removal by SSA included electrostatic attraction, surface complex
formation, and cation exchange. The precipitation of copper
hydroxide occurred only when the dosage of SSA and the equilibrium pH of wastewater were at a high level (30/40 g/l and greater
than 6.2, respectively).The feasibility of using y ash for the
removal of Cu(II) and Pb(II) from wastewater was investigated
[99,100]. The cation exchange capacity and specic surface area of
y ash increased with increased carbon content. The adsorption of
335
metal ions onto the surface of y ash was found to be proportional

to the carbon contents. This is because the amounts of adsorption
or ion exchange sites on carbon soot are higher than on mineral
surface. This is consistent with cation exchange capacity and
specic surface area. Consequently, carbon residual in the y ash
play a more important role than mineral matter in the removal of
metals by the y ash.
Fly ash was found to be good adsorbent for removal of zinc from
aqueous solutions [101]. Gashi et al. [102] reported that y ash
showed good adsorptive properties for removal of lead, zinc,
cadmium and copper from efuents in the battery and fertilizer
industries. Removal efciencies were greater than 70%. Adsorption
studies carried out to estimate heavy metal removal, using y ash
on wastewater at Varnasi, India, showed that removal was in the
following order: Pb > Zn > Cu > Cr > Cd > Co > Ni > Mn [103].
Adsorption of Cd (I), Ni(II), Cd(II), Pb(II), Zn(II) and Ag(I) on y ash
was investigated and found that the process was spontaneous and
endothermic [104]. A process for the treatment of industrial
wastewater containing heavy metals, using y ash adsorption and
cement xation of the metal-laden adsorbent, was investigated by
Huang research group [104106]. Results showed that y ash could
be an effective metal adsorbent, at least for Zn(II) and Cd(II) in
dilute industrial wastewaters. A 10% metal-laden y ash was tested
for leaching and it exhibited metal concentrations lower than the
drinking water standards.
Fly ash was also effective for the removal of arsenic from
aqueous solution. Fly ash, obtained from coal power stations, was
examined for removal of As (V) from water [107]. Kinetic and
equilibrium experiments were performed to evaluate As(V)
removal efciency by lignite-based y ash. Maple wood ash
without any chemical treatment was utilized to remediate As(III)
and As(V) from contaminated aqueous streams in low concentrations [108]. Static tests removed 80% arsenic, while the arsenic
concentration was reduced from 500 to <5 ppb, in dynamic column
experiments. The efciency of removal of As(V) and As(III) on charcarbon (CC), derived from y ash is compared with those of
commercially activated carbon [109].
It was reported that coal y ash is a good adsorbent for both
radionuclides of 137Cs and 90Sr [110]. Adsorption of radiocesium is
maximum around neutral region, whereas radiostrontium
adsorption increases with pH, especially above pH 8. Retention of
cesium sharply drops with ionic strength, whereas the adsorption
of strontium increases sharply and steadily at low and moderate
concentrations of inert electrolyte, respectively. Suggested mechanism of retention of radionuclide by y ash is specic adsorption
of Cs (I), and irreversible ion exchange uptake of Sr(II).
6.2. Adsorption mechanism and kinetics
For a solid liquid adsorption process, the solute transfer is
usually characterized by either external mass transfer (boundary
layer diffusion) or intraparticle diffusion or both. The adsorption
dynamics can be described by the following three consecutive
steps:
transport of solute from bulk solution through liquid lm to
adsorbent exterior surface;
solute diffusion into pore of adsorbent except for a small
quantity of sorption on external surface; parallel to this is
intraparticle transport mechanism of surface diffusion; and
adsorption of solute on interior surfaces of the pores and
capillary spaces of adsorbent.
The last step is an equilibrium reaction. Of the three steps, the
third step is rapid and negligible. The overall rate of adsorption will
336
be controlled by the slowest step that would be either lm diffusion

or pore diffusion controlled.
Various kinetic models have been suggested for adsorption,
including the Lagergren pseudo-rst order kinetics, the pseudosecond order kinetics, external diffusion model, and intraparticle
diffusion model, which are expressed in Eqs. (5)(8) as listed
below:
logqe qt logqe
empirical model used to describe adsorption in aqueous systems,

was also used to explain the observed phenomena of adsorption of
metal on y ash materials. The Freundlich isotherm is shown in the
following equation.
x
1=n
Kf Ce
m
(12)
The linear form of the equation can be written as:
k1
t
2:303
(5)
t
1
1
t
qt
k2 q2e qe
(6)
dCt
ks SCt Cs
dt
(7)

qt ki t 1=2
(8)
where k1, k2, ks and ki are the pseudo-rst order, pseudo-second

order rate constant, mass transfer coefcient, and rate parameter of
the intraparticle diffusion control stage, respectively, qe the amount
of solute adsorbed (mg/g) at equilibrium and qt the amount of
solute on the surface of the adsorbent (mg/g) at any time t, Cs and Ct
are surface and solution concentration, and S is the specic surface
area. Adsorption kinetics of heavy metals on y ash was investigated by several researchers. Most investigations reported that
adsorption of metal usually follows the rst order kinetics
[68,81,82], and that adsorption is pore diffusion controlled
[68,81,82,95,97]. Kelleher et al. [65] investigated adsorption of
Cr(III) on y ash, and kinetic studies suggested that overall rate of
adsorption was pseudo-second order.
x
1=n
log logKf logCe
m
where, Kf is the measure of sorption capacity, 1/n is sorption

intensity, and other parameters have been dened as in Eq. (13).
The RedlichPeterson model was also used to describe the
adsorption phenomenon. The RedlichPeterson equation has three
parameters, A, B and b. Parameter b ranges between 0 and 1.The
equation is represented below:
Ce
B 1
Ceb
x=m
A A
The Langmuir, Freundlich, RedlichPeterson, DubininKaganer

Radushkevich (DKR), Tempkin, and Sips isotherms were generally
used to describe observed adsorption phenomena of various metal
ions on y ash. The Langmuir isotherm applies to adsorption on
completely homogenous surfaces with negligible interaction
between adsorbed molecules. For a single solute, it is given by
x
Vm KCe
m
1 KCe
(9)
However, the linear form of the equation can be written as
Ce
1
Ce
x=m
KVm Vm
(10)
Where Ce is the equilibrium concentration of the solution, x/m is

the amount adsorbed per unit mass of adsorbent, m is the mass of
the adsorbent, Vm is the monolayer capacity, and K is an equilibrium
constant that is related to the heat of adsorption by equation:
q
K Ko exp
RT
(11)
where, q is the heat of adsorption. Langmuir model can describe

most adsorption phenomena of heavy metals on y ash
[76,77,83,84,91]. In most cases, Vm and K increase with temperature, suggesting that adsorption capacity and intensity of adsorption are enhanced a higher temperature. A linear plot from Eq. (10)
can be drawn for a particular metal adsorption, and the values, Vm
and K for isotherms of the metal under study can be obtained, by
using least squares method. The Freundlich model, which is an
(14)
This isotherm describes adsorption on heterogeneous surfaces,

as it contains the heterogeneity factor b. It can reduce to Langmuir
equation as b approaches one. Using Eq. (14), the parameters A, B,
and b were determined by curve tting.
The DKR equation can be represented as
ln Qe ln Qm b32
(15)
where, Qe is the amount adsorbed (mol/gm), Qm (mol/gm) is the

DKR monolayer capacity, b (mol2/J2) is a constant related to the
adsorption energy, and e is the Polanyi potential, which is related to
the equilibrium concentration through the expression:
3 RTln1=C
6.3. Adsorption isotherms
(13)
(16)
where T is the temperature and C is the equilibrium concentration

of the adsobate in solution. When lnQe was plotted against e2,
a straight line will be obtained. The value of b is related to the
adsorption energy, E, through the following relationship:
E 1=2b
1=2
(17)
Tempkin and Pyzhev considered the effects of some indirect

adsorbate/adsorbate interactions on adsorption isotherms and
suggested that because of these interactions the heat of adsorption
of all the molecules in the layer would decrease linearly with
coverage. The Tempkin isotherm has been used in the following
form:
qe RT=blnACe
(18)
Eq. (18) can be expressed in its linear form as:
qe RT=blnA RT=blnCe
(19)
B RT=b
(20)
A plot of qe versus ln Ce enables the determination of the

constants A and B. The constant B is related to the heat of adsorption [111].
Sips model suggests that the equilibrium data follow Freundlich
curve at lower solute concentration and follows Langmuir pattern
at higher solute concentration. The equation can be represented as
follows [112]:
Q Ks Ce b=1 as Ce b
(21)
337
where Ks (L/g) and as (L/mg) are Sips isotherm constants and b is

the exponent which lies between 1 and 0.
strongly adsorb or precipitate phosphates in many agricultural,

industrial and environmental applications.
6.4. Factors affecting adsorption of metal on y ash
7.1. Removal of phosphate
The adsorption of heavy metals on y ash is dependent on both

the initial concentration of heavy metals and contact time. It was
reported that the initial concentration of heavy metal has a strong
effect on the adsorption capacity of the y ash. The adsorption
capacity of y ash depends on the surface activities, such as, specic
surface area available for solute surface interaction, which is
accessible to the solute. The adsorption afnity of y ash for heavy
metal depends on the equilibrium between competitive adsorption
from all the cations, ionic size, stability of bonds between heavy
metals and y ash. The other important factor for the adsorption of
heavy metal on y ash is pH. In a certain pH range, most metal
adsorption increased with increased pH up to a certain value, and
then decreases with further increase in pH.
It is apparent that by increasing the adsorbent dose the
adsorption efciency increases, but adsorption density, the amount
adsorbed per unit mass, decreases. It is readily understood that the
number of available adsorption sites increased with increased
adsorption dose and resulted in increased removal efciency. The
decrease in adsorption density with increased adsorbent dose is
mainly due to unsaturation of adsorption sites through adsorption
reaction. Another reason may be because of the particle interaction,
such as aggregation, resulted from high adsorbent concentration.
Such aggregation would lead to decrease in total surface area of
adsorbent and an increase in diffusional path length [78]. Particle
interaction may also desorb some of adsorbate that is only loosely
and reversibly bound to carbon surface.
Thermodynamic parameters such as standard free energy
change (DG0), standard enthalpy change (DH0) and standard
entropy change (DS0), are calculated using the following equation.
Kuziemska rst reported an investigation using water extract of

brown coal y ash as coagulant for precipitation of phosphate in
1980. It was found that phosphate precipitation occurs immediately after introduction of coagulant, and after a short and intensive
mixing because of very high total alkalinity of extract [114].
Coal y ash was paid great attention as a potential material for
removal of phosphate, since it is easily available and cost effective
[115120]. Ugurlu and Salman [116] found that a Turkish y ash is
an efcient adsorbent for removal of phosphate due to high
concentration of calcite (33.83%). The inuence of temperature,
phosphate concentration, and y ash dosage on phosphate removal
was investigated. Tsitouridou and Georgiou [120] compared three
y ash with different calcium contents, and indicated that phosphate removal involved an adsorption and/or precipitation process.
Vordonis et al. [121] determined that uptake of orthophosphate by
four calcium-rich (1032%) Greek y ash exceeded the amount
predicted by monolayer coverage, suggesting either multilayer
adsorption or precipitation. Interaction of inorganic orthophosphate at water/solid interface was investigated.
Cheung and Venkitachalam [122] investigated the removal of
phosphate by y ash with high- and low-calcium contents and
concluded that phosphate removal was primarily due to the
precipitation of phosphate with Ca2 ions in solution. The removal
of phosphate by a medium calcium y ash (with CaO content of
11.57%) predominantly took place by precipitation mechanism, ion
exchange and weak physical interactions between the surface of
adsorbent and the metallic salts of phosphate [123]. Grubb et al.
[124] carried out batch equilibration experiments using low
calcium, acidic y ash for phosphate immobilization on the order of
10075% for 50 and 100 mg P/L solutions, respectively. For the
amorphous and crystalline phases studied, the immobilization of
phosphate in the y ash is attributed to the formation of insoluble
aluminum and iron phosphates at low to medium values of pH. The
removal of phosphate ion from aqueous solution was compared
with y ash, slag and ordinary Portland cement (OPC) and related
cement blends [125]. The rate and efciency of PO3
4 removal were
found to increase in the order: y ash, slag, OPC, apparently
mimicking the order of increasing percent CaO in the adsorbents.
Blending OPC with y ash or slag evidently resulted in diminished
PO3
4 removal efciency. Recently, Chen et al. [126] investigated the
removal of phosphate on different y ash. The sorption maxima of
phosphate (Qm) ranged from 5.51 to 42.55 mg/g. The Qm value
showed a signicantly positive correlation with total Ca content
(r 0.9836) and total Fe content (r 0.8049), but negative correlation with total Si and total Al content. Fractionation of Phosphorus
adsorbed by y ash revealed that loosely bound Phosphorus fraction and/or Ca Mg-P fraction were the dominant form of immobilized phosphate. Higher removal of phosphate occurred at
alkaline conditions for high-calcium y ash, at neutral pH levels for
medium calcium y ash, while low-calcium y ash immobilized
little phosphate at all pH values. This behavior was explained by the
reaction of phosphate with Ca and Fe related components. It was
concluded that P immobilization by y ash was governed by Ca
ingredient (especially CaO and CaSO4) and Fe ingredient (especially
Fe2O3d). The selection of a y ash with a high phosphate sorption
capacity is of utmost importance to obtain a sustained phosphate
removal in the long term in practice.
Acid modied y ash was effective in the removal of phosphate
from contaminated antibiotic wastewater. Adsorption, chemical
precipitation, and increase of BET were main mechanisms of
DG0
ln Kc
RT
DS0
R
DH0
RT
(22)
where, Kc is equilibrium constant that is resulted from the ratio of

equilibrium concentrations of metal ion on adsorbent and in the
solution, respectively. Linear property of ln Kc against 1/T was
proved in a number of studies on adsorption of heavy metal by y
ash materials [79,98]. DG0 or DS0 and DH0 are calculated from a plot
of ln Kc versus 1/T. A negative value of DG0 indicates the process to
be feasible and spontaneous nature of adsorption. A positive DH0
suggests the endothermic nature of adsorption, and DS0 is used to
describe randomness at the solidsolution interface during
adsorption.
Fly ash can be regenerated after the adsorption, using suitable
reagents. Batabyal et al. [113] regenerated the used saturated y ash
with 2% aqueous H2O2 solution. The regenerated y ash was dried,
cooled and used for further adsorption. The adsorption rate and
equilibrium time were same as the fresh y ash particles.
7. Removal of other inorganic components from wastewater
Apart from heavy metals in wastewater, some other inorganic
contaminants, such as phosphorous, uoride, and boron also exists
in waters and dangerous for human health. Phosphorous loading to
surface and groundwater from concentrated agricultural activities,
including soil fertilization, feed lots, diaries, and pig and poultry
farms is causing water quality problems in rivers, and lakes.
Because y ash is enriched with oxides of aluminum, iron, calcium,
and silica, y ash emerges as a potential candidate to treat phosphate-laden efuents since aluminum, iron and calcium are
338
removal of phosphate with modied y ash. The addition of y ash

to water produces insoluble or low solubility salt when combined
with phosphate. Solid phase phosphate compounds are separated
from water by sedimentation or classical ltration. But some y ash
particles may remain in the water and cause turbidity. Membrane
process is being used for various water and wastewater treatment
applications. Crossow microltration was effective in a number of
processes, including removal of colloidal organic and inorganic
solids, and various anions, and cations from aqueous streams with
the aid of surfactants, and macromolecules [127,128]. Removal of
phosphate ions from water using y ash in a crossow microltration membrane unit was examined [129].
7.2. Removal of uoride

Fluoride in water is essential for protection against dental caries,
and weakening of the bones, but higher levels can have an adverse
effect on health. The presence of excessive uorides in drinking
water is a matter of serious concern. The uoride toxicity indicates
that it cause weight loss, dental skeletal changes, indicators of
carcinogenesis, hypocalcemia (low blood calcium), hyperkalemia
(excess blood potassium) which will affect spine, cerebral impairment, and damage of soft tissues. Excess uoride consumption also
leads to cancer, osteoporosis, neurological, cerbrovascular effects,
and other physical ailments. Besides natural geological enrichment
of uoride in ground waters, there can also be formidable contributions from industries. High uoride containing wastewater is
generated by coal power plants, semiconductor manufacturing,
glass and ceramic production, electroplating, rubber and fertilizer
manufacturing. Fluoride concentration in industrial efuent is
generally higher than in natural waters, ranging from tens to
thousands of mg/L.
Wastewaters from phosphate fertilizer plants may contain up to
2% of uoride. Increased levels of uoride can also be present in
efuents from uorine industry, glass etching and in ground water
around aluminum smelters. The problem of high uoride concentration in ground water resource was an important health-related
geo-environmental issue. Examples include the state of Rajasthan,
India, where nearly 3 million people are reported to consume
excess uoride containing water, and upper regions of Ghana,
where 23% of wells have uoride concentrations above WHO recommended maximum guideline limit of 1.5 mg/L. In the Gdansk
region, high uoride levels (1.903.00 mg/L) were detected in
Malbork drinking water. There is a need for deuoridation of
industrial wastewaters, because of excessive amounts of uoride
may cause adverse health effects to humans and animals. Various
methods have been used to remove uoride from wastewaters.
These methods were divided into two groups: (a) precipitation
methods based on addition of chemicals to water and (b) adsorption methods in which uoride is removed by adsorption or ion
exchange reactions on some suitable substrate, capable of regeneration and reuse [130]. Several investigations were reported for
the removal of uoride from waters by using y ash. Chaturvedi
et al. [131] examined y ash for removal of uoride from water and
wastewaters at different concentrations, times, temperatures and
pH of the solution. Removal of uoride is favourable at low
concentration, high temperature and acidic pH. Nemade et al. [132]
carried out batch adsorption studies to determine removal efciency of uoride by y ash. Retention of uoride ion in dynamic
experiments on columns packed with y ash was studied in
aqueous solutions [133]. At lowest F concentration, F level in the
efuent initially increased and then gradually decreased down to
0 mg/L after 120 h. With higher F concentrations in the feed
solutions, F concentration in the efuent steadily decreased
reaching 0 mg/L after 120168 h. Coal y ash is an effective

adsorbent for F ions, especially at high concentrations in water.
7.3. Removal of boron
Boron occurs naturally in environment, and it is commonly
found in oceans. It is present as boric acid and borate ions in
aqueous solution. Boric acid and boron salts have extensive
industrial use in the manufacture of glass and porcelain; in wire
drawing; production of leather, carpets, cosmetics and photographic chemicals; for reproong fabrics; and weatherproong
wood. Very few investigations were reported on boron adsorption
using y ash. Hollis et al. [134] examined the effect of ash particle
size, pH, and Ca(OH)2 on dissolution and adsorption of boron by y
ash in aqueous media. A small amount of born was adsorbed by y
ash at pH 7. This was attributed to a ligand exchange mechanism.
Adsorption of boron increased with increased pH, up to 12, which
could not be explained by co-precipitation with CaCO3. Adsorption
of boron from aqueous solution using y ash was investigated in
batch and column reactors [135]. The Thomas and YoonNelson
models were applied to experimental data to predict breakthrough
curves, and to determine characteristics parameters of the column
useful for process design.
8. Removal of organic compounds from wastewater
8.1. Removal of phenolic compounds
Phenols are important organic pollutants discharged into environment causing unpleasant taste, and odour of drinking water.
Major sources of phenol pollution in aquatic environment are
wastewaters from paint, pesticide, coal conversion, polymeric resin,
petroleum, and petrochemicals industries. The chlorination of
natural waters for disinfection produces chlorinated phenols. There
are several methods reported for the removal of pollutants from
efuents. Fly ash has a good adsorption potential for phenolic
compounds. Table 3 presents a summary of adsorption capacity of
various organic compounds on y ash.
Fly ash has good adsorption potential for phenolic compounds.
Khanna and Malhotra [136] rst examined the potential of y ash
for the removal of phenol. They reported kinetics and mechanism
of phenol removal on y ash and provided useful data in the design
of phenoly ash adsorption systems. Adsorption of phenol, and
cresol, and their mixtures from aqueous solutions on activated
carbon and y ash were compared [137]. The effects of contact time
and initial solute concentration have been studied and isotherm
parameters were evaluated. The Freundlich isotherm was more
suitable for all the systems investigated. Removal of phenol
depends markedly on temperature and pH value of treatment
solution [138]. Adsorption isotherms for phenol, 3-chlorophenol,
and 2,4-dichlorophenol from water onto Texas Municipal Power
Agency (TMPA) y ash were determined [139]. The y ash adsorbed
67, 20, and 22 mg/g for phenol, chlorophenol, and 2,4-dichlorophenol, respectively, for the highest water phase concentrations.
The afnity of phenolic compounds for y ash is above the expected
amount corresponding to a monolayer coverage considering that
the surface area of y ash is only 1.87 m2/g. However, molecules
with strong functional groups align themselves vertically on the
surface; moreover, these adsorbed molecules can interact with
other molecules, making the next adsorption layer energetically
and statistically more favorable. They explained that the three
phenolic compounds, having a very strong functional group as well
as strong molecular interaction, display this type of behavior. The
isotherms examined were unfavourable (BET Type III) or cooperative (Curve S), indicating that adsorption becomes progressively

Table 3
Comparison of organic pollutant adsorption on y ash.
Organic compounds
Adsorbent
Capacity (mg/g)
References
Phenol
FA
Sugar y ash
FA-C
Wood FA
Coal-FA
FA-C
Fly ash
FA
Coal FA
FA
FA-C
Fly ash
Wood FA
FA
FA
Sugar y ash
Wood FA
FA
Bagasse y ash
Coal FA
Wood FA
Wood FA
Fly ash
Sugar FA
Sugar FA
Bagasse FA
Bagasse FA
FA
FA
FA
67
0.470.66
0.26
5.4
0.81.0
98.7
98.7
22
1.51.7
20
118.6
118.6
143.8
5.806.44
6.528.06
0.761.15
134.9
7.809.68
8.3
85.496.4
34.5
52.5
1.39
(7.57.7) 103
(6.56.7) 103
(2.42.5) 103
(2.02.1) 103
1.541.65
0.35
0.15
[139]
[143]
[148]
[142]
[147]
[141]
Ortho-chloro phenol
2,4-Dichloro phenol
3-Chloro phenol
Para-chloro phenol
2-Nitro phenol
3-Nitro phenol
4-Nitro phenol
Para-nitro phenol
Cresol
m-Cresol
p-Cresol
2,4 Dimethyl phenol
DDD
DDE
Lindane
Malathion
Carbofuran
TCB
HeCB
[147]
[142]
[139]
[141]
[151]
[143]
[142]
[151]
[143]
[142]
[143]
[146]
[134]
[113]
[160]
[161]
[162]
[164]
easier as more solutes are taken up. Phenols have a strong hydroxyl
functional group which interacts with the adsorbent surfaces,
resulting in vertical alignment of the molecule on the surface.
Moreover, additional adsorption is motivated and consequently
strengthened by the interaction between the adsorbed molecules.
This phenomenon is known to contribute signicantly to the
cooperative nature of adsorption and hence an S type curve.
The potential of y ash as a substitute for activated carbon for
the removal of phenolic compounds from wastewater was examined [140,141]. The maximum phenol loading capacity of each
adsorbent was 27.9 mg/g for y ash and 108.0 mg/g for granular
activated carbon. Adsorption of phenolic compounds on a mixture
of bottom and y ash was reported [142]. The effect of molecular
weight and molecular conguration on adsorption of phenol (Ph),
m-cresol (m-Cr), p-cresol (p-Cr), 2-nitrophenol (2-NP) and
4-nitrophenol (4-NP) from aqueous solution was investigated. The
ultimate capacity of the adsorbent is considerably less than that
predicted from summing the single-component data; this was
attributed to increased competition for adsorption sites. Bagasse y
ash was converted into a low-cost adsorbent and used for removal
of phenolic compounds [143145]. The uptake increases when
larger quantities of adsorbent are used. The presence of an anionic
detergent Manoxol-IB reduces uptake of phenol and p-nitrophenol.
Adsorbent prepared from y ash was successfully used to remove
cresol from an aqueous solution in a batch reactor [146].
Kao et al. [147] utilized y ash for removal of 2-chlorophenol (2CP) and 2,4-dichlorophenol (2,4-DCP). More adsorption takes place
with y ash of higher carbon content and larger specic surface area.
Adsorption of chlorophenol is not inuenced by matrix in wastewater. Chlorophenols in wastewater were also removed efciently
through a y ash column. The breakthrough time was inversely
proportional to ow rates. The effectiveness of less expensive
adsorbents such as peat, y ash and bentonite in removing phenol
from wastewater was also examined [148]. Peat, y ash and bentonite
were found to adsorb 46.1%, 41.6%, and 42.5% phenol, respectively.
339
Sarkar et al. [149] investigated the adsorption of some priority

organic pollutants, viz., phenol (hydroxybenzene), o-hydroxyphenol
(1,2-dihydroxybenzene),
m-hydroxyphenol
(1,3-dihydroxybenzene), and 4-nitrophenol (1-hydroxy-4-nitrobenzene), on y
ash. The process was complex consisting of both surface adsorption
and pore diffusion. Activation parameter data for ultimate adsorption
and pore diffusion are also evaluated. The data indicate that external
transport mainly governs rate-limiting process.
Batch adsorption experiments were conducted to estimate the
potential of y ash (FA) for removal of phenols from aqueous
solution [150,151]. Polar substituted phenol, having less steric
hindrance is better adsorbed than others. Substituted phenol with
hindered group is less adsorbed than phenol (m-nitrophenol >
o-nitrophenol > phenol > m-cresol > o-cresol). This order is related
to electron-withdrawing properties of substituents of phenolic
compound. Therefore, electron withdrawal or deactivation of
benzene ring favors formation of electron-donoracceptor
complexes between these rings and basic groups on the surface of
y ash. The removal mechanism of phenol is explained due to
chemical coagulation with metallic oxides. Bagasse y ash (BFA),
rice husk y ash (RHFA) and activated carbon (AC) were also
investigated for adsorption of 2,4-dichlorophenol and tetrachlorocatechol [152,153].
The potential of rice husk and rice husk ash for phenol
adsorption from aqueous solution was examined [154]. Rice husk
ash is very effective than rice husk for phenol removal. Rice husk
ash (RHA) obtained from a rice mill in Kenya was used for removal
of some phenolic compounds in water [155]. Adsorption capacities
of 1.53 104, 8.07 105, and 1.63 106 mol/g were determined
for phenol, resorcinol and 2-chlorophenol, respectively. Coal y ash
was used successfully to remove 2,4-dimethyl phenol by adsorption
from aqueous solutions [113]. Both diffusional and kinetic resistances affect the rate of adsorption and their relative effects vary
with operating temperatures. The rate of adsorption is controlled
by both diffusional and kinetic resistances at higher temperature,
whereas at low temperature, rate of adsorption is dominated by
diffusion effect. Regeneration of used y ash with H2O2 indicates
that y ash may be a useful cheap industrial adsorbent for wastewater treatment. Srivastava et al. [156] studied the adsorption of
phenol on carbon rich bagasse y ash (BFA) and activated carboncommercial grade (ACC) and laboratory grade (ACL). The high
negative value of change in Gibbs free energy (DG0) indicates
feasible and spontaneous adsorption of phenol on BFA. The overall
adsorption process is controlled by intraparticle diffusion of
phenol. Activated carbon (AC), bagasse ash (BA) and wood charcoal
(WC) were also used as adsorbents for removal of phenol from
water [157]. The effect of nitrate ion and EDTA on adsorption of
phenol was insignicant. Chloride ion has considerable negative
effects on removal by BA. The estimation of diffusion coefcients
indicated that lm diffusion control adsorption of phenol.
Phenolic compounds from paper mill industry wastewaters were
removed by using y ash, raw sepiolite and heat-activated sepiolite
as adsorbent [158]. Intraparticle model shows the presence of two
separate stages in adsorption process, namely, external diffusion and
pore diffusion. Heat-activated sepiolite is more effective than raw
sepiolite and y ash. The efciency of adsorption decreases with
increased adsorption temperature for both y ash and untreated
sepiolite. Fly ash was successfully used to recover phenol from
industrial wastewater, by lagooning mixture of y ash and wastewater; phenol was reduced from 4500 mg/L to 280 mg/L [159].
8.2. Removal of pesticides
Among various organic and inorganic water pollutants, pesticides are very dangerous and harmful because of their toxic and
340
carcinogenic nature. Bagasse y ash was converted into an effective

adsorbent and used for removal of DDD [2,2-bis(4-chlorophenyl)1,1-dichloroethane] and DDE [2,2-bis(4-chlorophenyl)-1,1-dichloroethene] pesticides from wastewater [160]. The DDD and DDE are
removed up to 93%. The removal was achieved up to 9798% in
column experiments at a ow rate of 0.5 mL/min. Bagasse y ash
was also examined for removal of lindane and malathion from
wastewater [161]. At lower concentrations, adsorption is controlled
by lm diffusion; while at higher concentrations, it is controlled by
particle diffusion mechanisms. Adsorption of carbofuran on y ash
was studied by Kumari and Saxena [162]. The degree of adsorption
of carbofuran was determined in accordance with the partial molar
free energies and Kd values. Batch studies were carried out to
investigate the removal of organic acids by adsorption on y ash
impregnated with hydroxides of Al, Cd, Cu, Fe and Ni [163]. The
percentage removals of cinnamic acid, indole-3- acetic acid, betanaphthaleneacetic acid, beta-naphthoxyacetic acid, oxalic acid and
trichloroacetic acid from water were 75%, 63.63%, 100%, 95.25%,
85.71% and 78.26%, respectively. Adsorption kinetics of PCBs on y
ash was conducted in controlled batch systems [164]. TCB and HeCB
are removed up to 97%. Activation energies for the adsorption
process ranged between 5.6 and 49.1 kJ/mol. The rate at which TCB
and HeCB are adsorbed onto y ash showed a diffusion limitation.
The uptake rate of TCB and HeCB increases with increased initial
concentration and gradually tends to a constant value. Adsorption
of TCB and HeCB was decreased when interfering ions and other
PCB congeners were present. Overall, y ash is used for an efcient
removal of PCBs from aqueous solutions.
8.3. Removal of other organic compounds
Banerjee et al. [165] investigated the adsorption of o-xylene on
y ash. Uptake rate of o-xylene increases signicantly with
increased initial concentration, and gradually approaches a plateau.
A signicant correlation was observed between rate of adsorption
and inverse of the square of particle diameter. Adsorption of
o-xylene by y ash is an exothermic process and spontaneous at the
temperature investigated. Activation energies for adsorption
process ranged between 3.1 and 4.3 kcal/mol. Adsorption of
o-xylene onto y ash was controlled by diffusion process.
Fly ash was also used to remove TNT in both batch and column
systems; in column systems 90% removal of TNT was reported
[166]. Bhargava et al. [167] examined removal of a detergent in
a xed-bed continuous ow y ash column and developed a relationship for the design of such systems. Using 1000 mg/L of y ash
containing 23.27% carbon, 74% removal of ABS was obtained with
a 2-h contact time [168]. Jain et al. [169] showed that adsorption of
oxalic acid from aqueous solution by y ash has two linear
components each following Langmuir isotherm. Fly ash was also
used as adsorbent for the removal of alcohols, aldehydes, ketones
and aromatics [170]. Immobilization of organic pollutants is
feasible by adsorbing contaminants onto y ash. The residual
carbon content played a signicant role in adsorption process.
Percent reductions of aromatic compounds were much higher
compared to other functional groups such as alcohols, aldehydes
and ketones. Batch shaking was conducted to determine the
adsorption potential of y and volcanic ashes in removing organic
pollutants from oxidation pond efuents [171]. Factors affecting
organic pollutant removals, such as concentrations and sizes of y
and volcanic ashes, initial pond efuent organic concentrations,
washed and unwashed conditions of y and volcanic ashes, were
investigated. The TOC (total organic carbon) removal efciency
varied from 30 to 58%. The organic removal efciency increased
with increased ash concentrations, with decreased initial pond
efuent organic concentrations and sizes of ash.
9. Removal of dyes from wastewater

Dyes and pigments are discharged into wastewaters from
various industrial sources, mainly from dye manufacturing and
textile nishing industries. There are various methods available for
the treatment of dyes from wastewater. Among them, adsorption
process provides an attractive alternative for the treatment of
wastewaters, especially if the adsorbent is inexpensive and does
not require an additional pre-treatment before its application. Table
4 summarizes the adsorption capacity of various dyes onto y ash.
9.1. Azo dyes
The Azo dyes are largest and most important group of dyes. They
are characterized by the presence of one or more azo groups, which
form bridges between two or more aromatic rings. Various
researchers have examined the potential of y ash for removal of
azo dyes from wastewater.
The adsorption of Congo red from solution was carried out using
calcium-rich y ash with different contact times, concentrations,
temperatures, and pH [172]. Bagasse y ash (BFA) was also utilized
for the adsorption of Congo red (CR) from aqueous solution [173].
Adsorption of the CR on BFA was most favourable in comparison to
activated carbons. Potential of y ash as adsorbent for removal of
Chrysoidine R from aqueous solution was reported by Matheswaran and Karunanithi [174]. A series of experiments were
carried out in a batch adsorption technique to obtain the effect of
process variables on adsorption. An azo dye, Acid Orange 7 [p-(2hydroxy-1 naphthylazo) benzene sulfonic acid] was removed by
adsorption onto bottom ash [175]. To assess the practical utility of
adsorbents, a xed-bed column was designed, and necessary
parameters were calculated by applying a mass transfer kinetic
approach. Experiments were also performed for recovery of loaded
dye through chemical regeneration of spent columns.
Batch adsorption studies were carried out for sorption of C.I.
Reactive Black 5 onto high-lime y ash [176]. The adsorption
kinetics of C.I. Reactive Black 5 onto high-lime y ash was studied to
characterize of the surface complexation reaction. Adsorption
kinetic and equilibrium studies of Remazol Brillant Blue (RB),
Remazol Red 133 (RR) and Rifacion Yellow HED (RY) from aqueous
solutions on y ash (FA) were studied in a batch mode operation
[177]. Removal of reactive dyes from aqueous solutions using FA
was well described by external mass transfer and intraparticle
diffusion models. External mass transfer and intraparticle diffusion
had rate limiting affects on the removal process. This was attributed
to relatively simple macropore structure of FA particles. The
adsorption of reactive dyes (Remazol Red, Remazol Blue and Rifacion Yellow) from aqueous solutions using y ash as an adsorbent
was examined [178]. The adsorbent was characterized using several
methods such as SEM, XRD and FTIR. The FTIR suggested that dye
on y ash is probably indicating y ash/dye complexation. XRD
pattern of y ash consisted of mainly quartz, mullite with some
magnetite and calcite. Surface morphology of y ash and dye
loaded y ash were obtained with SEM. Adsorption of dye on y ash
was described using pseudo-rst order and pseudo-second order
kinetics.
9.2. Thiazine dyes
Thiazine dyes are suitable for the study of photo-sensitized
reactions in micellar media, because of their low ionization
potential caused by the presence of two hetero-atoms, namely
nitrogen and sulphur.
Fly ash has been employed as adsorbents for the removal of
a typical basic dye, methylene blue, from aqueous solution [179].
341
Table 4
Comparison of dye adsorption on y ash.
Dye
Methylene blue
Crystal violet
Rosaniline hydrochloride
Rhodamine B
Egacid orange II
Egacid red G
Egacid yellow G
Midlon black VL
Acid blue 29
Acid blue 9
Acid red 91
Acid red 91
Acid red 91
Congo red
Malachite green
Egacid orange II
Orange-G
Fly ash type

Coal FA
FA-F
FA-F
FA-HNO3
FA
FA-NaOH
FA-NaOH-sono
FA
FA-HNO3
FA
Carbon enriched FA
FA
Colombian FA
Thailand FA
Fly ash
Fly ash
Coal FA
Carbon-free FA
Carbon enriched FA
Fly ash
Coal FA
FA-F
Colombian FA
Thailand FA
Fly ash (CFA)
FA-F
FA-F
FA-F
FA-F
FA
FA
FA
Fly ash
FA
FA-C
Baggase y ash
Baggase y ash
Fly ash (CFA)
Bagasse y ash
Adsorption capacity (mol/g)

5
14.4 10
1.89 105
1.4 105
2.2 105
6.0 106
8.0 106
(1640) 106
1.4 105
2.4 105
2 106
1.2 104
2 105
>2 105
>1.6 106
2.20 105
2.01 105
9.76 105
1.0 106
1.0 104
9.13 105
1.35 105
1.15 105
8.0 106
2.5 107
1.15 105
2.36 104
1.40 104
5.20 105
3.3 105
3.25 106
5.43 106
2.34 106
1.46
7.26 106
4.47 105
1.70 105
4.67 104
3.05 104
4.15 105
Heat treatment and chemical treatment have also been applied to

the as-received y ash and red mud samples. Heat treatment
reduces adsorption capacity, whereas acid treatment by HNO3
induces a different effect on y ash. Nitric acid treatment results in
an increase in the adsorption capacity of y ash. The effect of
different methods for y ash treatment using conventional chemical, sonochemical and microwave method on methylene blue dye
adsorption in aqueous solution was investigated [180]. Chemical
treatment using HCl will increase adsorption capacity. The
adsorption capacity of HCl treated y ash varies. Microwave treatment is a fast and efcient method while producing sample with
highest adsorption capacity. The y ash treated by H2SO4 was used
as a low-cost adsorbent for the removal of a typical dye, methylene
blue, from aqueous solution [181]. An increase in specic surface
area and dye-adsorption capacity was observed after acid treatment. Fly ash samples modied by NaOH solution and sonochemical treatment were examined for a basic dye (methylene blue)
adsorption in aqueous solution [182]. Sonochemical treatment of
y ash can signicantly increase adsorption capacity depending on
the concentration of NaOH and treatment time.
The adsorption of toluidine blue (TB) onto y ash was studied
from aqueous solution, in presence of cationic surfactant cetyl
pyridinium chloride (CPC) and anionic surfactant sodium dodecyl
sulfate (SDS) [183]. Two-step adsorption isotherms are observed for
TB adsorption in aqueous solution. The equilibrium saturation
adsorption capacities of y ash for TB decreased in presence of CPC
as a result of competitive adsorption for same sites between same
Temperature ( C)
Adsorption isotherm
25
22
30
30
30
30
30
Langmuir
Langmuir
RedlichPeterson
RedlichPeterson
Langmuir and Freundlich
RedlichPeterson
RedlichPeterson
Langmuir
Langmuir
Kinetic model
References
[202]
[205]
[186]
[182]
[186]
Pseudo-second order
25
25
[189]
25
Freundlich
Langmuir
Langmuir
Lagergren rst order
25
22
25
25
Freundlich
Langmuir
Lagergren rst order
22
22
22
22
Langmuir
Langmuir
Langmuir
Langmuir
Freundlich
Freundlich
Freundlich
20
Freundlich
Freundlich
[179]
[190]
[204]
[186]
[177]
[204]
[205]
[189]
[205]
[203]
Pseudo-second order
[172]
[173]
[197]
[205]
[198]
charged dye and surfactant molecules. The adsorption of cationic

dye at low SDS concentration is enhanced by adsolubilization
phenomenon because of favorable interaction with negatively
charged adsorbed micelles. Above critical micelle concentration
free micelles are formed, TB is distributed between free and
adsorbed aggregates, and therefore global adsolubilization
decreases. An adsorption isotherm of SDS and CPC in aqueous
solution was constructed for interpreting adsorption results of TB in
presence of surfactants.
Fly ash, in both an untreated and an acidied form, were
examined with respect to their ability to remove colour and organic
materials [184]. The apparent predominant mechanism varies with
pH and chemical characteristics of the ash. These mechanisms
include carbon adsorption, calcium precipitation of tannins and
humics, sorption on y ash surface by silica, alumina, and/or iron
oxide and, in acidied situation, coagulation of coloured colloids in
efuent dissolved from y ash. Many of these materials can,
however, be removed by using a two-stage y ash sorption process.
Fly ash and treated y ash by physical and chemical methods was
employed as adsorbents for the removal of a typical basic dye,
methylene blue, from aqueous solution [185]. Raw y ash showed
adsorption capacity at 1.4 105 mol/g and that heat treatment
reduces adsorption capacity but acid treatment by HNO3 results in
an increase in adsorption capacity of y ash (2.4 105 mol/g).
Adsorption capacity of y ash is dominantly contributed by porous
unburned carbon in y ash, rather than y ash itself [186]. There is
a signicant linear correlation between carbon content and
342
adsorption capacity. Further investigation show that unburned

carbon exhibits much high adsorption capacity than mineral parts
of y ash [187]. Pseudo-second order kinetic model would be better
in describing kinetics of dye adsorption than rst order kinetics
[188].
The use of coal y ash for removal of dyes, methylene blue (MB)
from aqueous solution was investigated [189]. The adsorption of
MB increased slightly and linearly with increase in solution pH. The
adsorption behavior strongly depended on the characteristics of
individual y ashes. Bagasse y ash was also used for the removal of
methylene blue [190]. The percentage of dye removal was higher at
high adsorbent concentrations. The presence of anionic surfactant
will decrease methylene blue adsorption.
9.3. Xanthene dyes
Xanthene dyes are derived from xanthene. The potential of coal
y ash for the removal of Rhodamine B (RB) from aqueous solution
has been studied [189]. In the RB adsorption, the maximum
adsorption was observed between pH 2.8 and 4.5. The adsorption
behavior was strongly depended on the characteristics of the
individual y ash. Bagasse y ash was also utilized for the removal
of rhodamine B [190]. Rhodamine B is strongly adsorbed at pH 2.
The percentage of dye removal was higher at high adsorbent
concentrations. The presence of anionic surfactant does not affect
the uptake of rhodamine B signicantly. The effect of different
methods for y ash treatment using conventional chemical, sonochemical and microwave method on Rhodamine B dye adsorption
in aqueous solution was investigated [180]. Chemical treatment
with HCl will increase the adsorption capacity.
9.4. Arylmethane dyes
Arylmethane dyes are so called because they are derived from
methane, but in which some of the hydrogen atoms are replaced
with aryl rings. Since a synonym for aryl is phenyl, they may also
legitimately be called phenylmethane dyes. This class of dyes is
generally divided into two categories: diarylemethane and
triarylmethane.
Gupta et al. [191,192] investigated the ability of y ash and
mixture of y ash and coal to remove Omega Chrome Red ME from
aqueous solutions. The pronounced removal of chrome dye in
acidic range may be due to the association of dye anions with
positively charged surface of adsorbent. Bottom ash was examined
for the removal of toxic textile dye, malachite green [193]. Plausible
mechanism of on-going adsorption process and thermodynamic
parameters involved were obtained by carrying out kinetic
measurements. A xed-bed column was designed and necessary
parameters were calculated by applying mass transfer kinetic
approach. Bottom ash was also utilized as adsorbent for removal of
Brilliant Blue FCF and methyl violet [194,195]. Recovery of Brilliant
Blue FCF was made by eluting dilute NaOH of pH 11 through each
column.The adsorption of Auramine-O (AO) dye on bagasse y ash
(BFA) and activated carbon-commercial grade (ACC) and laboratory
grade (ACL) was investigated [196]. The adsorption process was
found to be controlled by both lm and pore diffusion with lm
diffusion at earlier stages followed by pore diffusion at later stages.
BFA, without any pre-treatment showed high surface area, pore
volume and pore size exhibiting its potential to be used as an
adsorbent for the removal of AO. Adsorption of various dyes,
namely, malachite green, Orange-G (OG), and Methyl Violet (MV)
was investigated extensively from aqueous solution by using
bagasse y ash (BFA) [197,198]. Adsorption of MV on BFA (with
a more negative Gibbs free energy value) is more favored among
the dyes studied.
The utilization of coal y ash for the removal of dye (Victoria

Blue) from aqueous solution was rst reported by Khare et al. [199].
Adsorption increased with dye concentration and that the
maximum removal was achieved at pH 8. Bagasse y ash was also
used for the adsorption of brilliant green (BG) [200]. Adsorption of
BG on bagasse y ash is favorably inuenced by an increase in
operation temperature. The potential of y ash for removal of
crystal violet dyes was reported [180]. The effect of different
methods for y ash treatment using conventional chemical, sonochemical and microwave method on dye adsorption in aqueous
solution was investigated.
Adsorbents from coal y ash were prepared by a solid-state
fusion method using NaOH [201]. Amorphous aluminosilicate
geopolymers is formed and assessed as potential adsorbents for
removal of crystal violet, from aqueous solution. Adsorption
capacity of synthesized adsorbents depend on preparation conditions such as NaOH: y ash ratio and fusion temperature with
optimal conditions being at 1.2:1 weight ratio of Na: y ash at 250
350 C. The synthesized materials exhibit much higher adsorption
capacity than y ash itself and natural zeolite. Fly ash derived
geopolymeric adsorbents show higher adsorption capacity for
crystal violet than methylene blue.
9.5. Other dyes
Ramakrishna and Viraraghavan [202204] investigated the
potential of y ash for removal of dyes from wastewater. The
removal of each dye was inversely proportional to the size of y ash
particle. Lime content in y ash inuenced the dye adsorption to
a signicant degree better adsorption was observed at lower
particle sizes because of increased external surface area available
for adsorption. Brown coal y ash was also examined as low-cost
adsorbents for removal of synthetic dyes from waters [205]. The
dye adsorption decreased in presence of organic solvents (methanol, acetone). The presence of oppositely charged surfactants
exhibited a pronounced effect on dye sorption low concentrations
of surfactant enhanced sorption, whereas high concentrations
solubilised dyes and kept them in solution. Inorganic salts exhibited only a minor effect on dye sorption. Gupta et al. [195] investigated the potential of bottom ash for removal of alizarin yellow and
fast green from wastewater. The percentages of removal of alizarin
yellow and fast green were 87.5, and 97.0, respectively. Coal y ash
was used as a heterogeneous catalyst in peroxidative decolorization
of aqueous solution of several reactive drimarene dyes using
hydrogen peroxide [206].
The efcacy of surface modication of y ash by quaternary
ammonium cations in the removal of dyes from aqueous solution is
demonstrated [207]. A series of organo-y ash materials were
synthesized by treating y ash with quaternary ammonium cations
such as tetraethylammonium, hexadecyltrimethylammonium, and
benzyldimethyltetradecylammonium (TEA, HDTMA, and BDTDA).
The adsorption was affected by structure and size of quaternary
ammonium cations and dyes. Adsorption of dyes was considerably
enhanced by surface modication. All above reports demonstrated
that y ash could be an effective adsorbent for removal of various
dyes from wastewater.
It is also evident from the literature that natural materials, waste
materials from industry and agriculture and bio-adsorbents are an
interesting alternative to replace activated carbon for the adsorption of dyes, metals and organic compounds from wastewater
[208239]. Crini [240] has recently reviewed the low-cost
non-conventional adsorbents utilized for removal of dyes from
wastewater. He demonstrated that non-conventional low-cost
adsorbents have potential as readily available, inexpensive and
effective adsorbents. These adsorbents possess several advantages
that make them excellent materials for environmental purposes,

such as high capacity and rate of adsorption, high selectivity for
different concentrations and also rapid kinetics. Some promising
results could be found in the case of clays, peat and chitosan-based
materials [229,241,242]. Ahmaruzzaman [243] recently reviewed
the adsorption of phenolic compounds on low-cost adsorbents.
Some promising results could be found in the case of fungal
biomass, bentonite, starch, petroleum coke, coal, residual coal,
residual coal treated with H3PO4, charred sawdust, cyclodextrin,
silica beads, and sludge materials. Table 5 reported the adsorption
capacities of phenol, dye, and metal on other adsorbents in order to
compare with y ash.
It is evident that y ash has a great potential in the environmental applications. Fly ash is an interesting alternative to replace
activated carbon or zeolites for adsorption in the water pollution
treatment. Despite the number of published laboratory data, y ash
adsorbent has not been applied at an industrial scale. There are
several issues and drawbacks concerned on the adsorption of
organic compounds that should be addressed:
(i) The applicability of y ash as low-cost adsorbents for wastewater treatment depends strongly on its origin. The
percentage of unburned carbon, SiO2, and Al2O3 content in the
y ash generally varies with regions and thus, adsorption
capacity.
(ii) The effectiveness of adsorption process depends on the
properties of the adsorbent and adsorbate. It also depends on
the environmental conditions and variables used for the
adsorption process such as pH, ionic strength, temperature,
Table 5
Comparison of adsorption on phenols, dyes and metals on various other adsorbents.
Organic
compounds
Adsorbent
Capacity
(mg/g)
References
Phenol
Coal
Residual coal
Residual coal treated with H3PO4
Rice husk
Coke breeze
Rice husk
Rice husk char
Petroleum coke
Lignite
Neutralized red mud
Sewage sludge
13.23
45.45
142.8
4.508
0.172
4.508
7.91
6.01
10.0
4.127
94.0
[215]
Waste news paper

Coal
Sewage sludge
Rice husk
Straw
Date pits
Hazelnut shell
Coir pith
Banana peel
Orange peel
390
250
114.94
19.83
19.82
17.3
8.82
120.43
20.2
18.6
[222]
[220]
[223]
[221]
Blast furnace slag

Lignin
Lignin
Acid washed-tea industry waste
Tea industry waste
Powered waste sludge
Sugar beet pulp
Lignin
Solid residue of olive mill products
Red mud
Blast furnace slag
Coffee Husk
Claried sludge
103.3
95
73
12
11
168
35.6
11.24
5.40
12.59
17.65
5.57
15.53
[226]
[227]
[225]
[233]
[234]
[235]
[236]
[228]
[237]
[224]
[225]
[238]
[63]
Dye
(Basic blue 9)
Metal (Zn2)
[208]
[209]
[210]
[218]
[217]
[219]
[216]
343
existence of competing organic or inorganic compounds in

solution, initial adsorbent concentration, contact time and
speed of rotation etc. The industrial efuents were found to
contain several pollutants simultaneously. However, little
attention has been paid to the adsorption of pollutants from
the mixtures [244]. The development of the adsorption
process requires further investigation in the direction of
testing y ash adsorbents with the real industrial efuents.
(iii) The competitive adsorption of organic compounds on y ash
was reported in few cases. However, there is scarce data
available for the adsorption of organic compounds in presence
of metals and other contaminants. Therefore, more research
should be conducted in this area.
(iv) There is a lack of data concerning the reproducibility of the
adsorption properties and the equilibrium data, commonly
known as the adsorption isotherms. The design and efcient
operation of the adsorption processes also requires equilibrium adsorption data for use in the kinetic and mass transfer
models. These models play an important role in predictive
modeling for analysis and design of adsorption systems.
Further work in this area is needed.
10. Leaching of y ash in water system
Utilization of y ash in water involves the potential leaching of
some elements into water. This creates a problem of secondary
environmental pollution. The surface layer of y ash particles,
probably of microns in thickness, contains a signicant amount of
readily leachable material deposited during cooling after combustion. Therefore, the charge on the surface of y ash particle and
formation of diffuse double layer plays a signicant role in leaching.
The elements present were divided into two groups based on their
concentration dependence of particle size. The elements Mn, Ba, V,
Co, Cr, Ni, Ln, Ga, Nd, As, Sb, Sn, Br, Zn, Se, Pb, Hg and S are usually
volatile to a signicant extent in combustion process. The volatility
for these elements is inversely proportional to particle size.
Elements, such as, Mg, Na, K, Mo, Ce, Rb, Cs and Nb possess
a smaller volatilized fraction during coal combustion [245]. The
volatility is directly proportional to particle size. The elements Si,
As, Fe, Ca, Sr, La, Sm, Eu, Tb, Py, Yb, Y, Se, Zr, Ta, Na, Th, Ag and Zn are
either not volatilized or may show minor trends related to
geochemistry of mineral matter. The volatility of trace elements
increased from larger to smaller particle size and establishes an
inverse relationship of volatility and particle size [246].
Studies have shown that only about 13% y ash material is
soluble in water with lignite y ash of higher proportion of water
soluble constituents [247]. The leaching of major elements from
CFA was extensively reviewed [11]. Analysis of water extracts
[248,249] showed that the principal cations in water extracts are
calcium and sodium, whereas anions are dominated by OH, CO3
with aqueous extracts of ash saturated with Ca(OH)2. The alkalinity
and acidity controlled extractability of elements, such as, As, B, Be,
Cd, Cr, Cu, F, Mo, Se, V and Zn. Aqueous extracts of an acidic y ash
contained concentrations of Cd, Co, Cu, Mn, Ni, Zn, As, B, Be, Cd, F,
Mo, Se and V [250,251]. Leachate waters have markedly different
compositions, depending on the surface of y ash, ue gas process
conditions design of combustion systems, and whether lime or lime
stone injection processes were implemented for desulfurization.
Total dissolved solid concentrations may vary from hundreds to
tens of thousands of milligram/liter. A small sample can show
marked differences in leachate water chemistry, depending on
reaction time and water/solid ratio in batch equilibrations or with
column length, and ow rate in a dynamic leaching test. The
mineral and glass phases constitute y ash material, are formed
over a wide range of temperatures in furnace. All these phases are
344
unstable. They dissolve and then precipitate as stable and less

soluble secondary phases. The primary phases, highly soluble in
water, dissolved very slowly as they are trapped in glass and crystalline alumina silicates. Secondary hydrous alumino silicate
products are very insoluble [252] and build up on rinds on surface
of primary phase. The dissolution of primary phase is slowed down
as mass transport of ions and water between phases becomes
diffusion controlled.
Many important aspects of leaching behaviour of y ash were
reported by a number of researchers [245,253255]. Leachability of
heavy metals from the coal y ash is relatively low and leaching
extent is dependent on the conditions of water system. Trace metal
concentration in the leachate depends on y ash weight/solution,
pH, concentration of elements, temperature, pressure, and time. In
water, rapid leaching of most of the trace metals (except Cu), takes
place from the surface of ash particles in lower pH range; all trace
elements lie within acceptable limits [255].
A complex mixture of organic compounds is also associated
with y ash particles. The organic compounds identied in y ash
extracts include known mutagens and carcinogens. There are
leaching procedures for the dissolution of the organic compounds
of FA in 3040% hydrogen peroxide, concentrated nitric acid under
microwave conditions, or benzene. However, this chemical treatment also leaches components associated with both organic and
inorganic compounds in FA. For example, some unstable minerals
from the chloride, sulfate, sulde, oxide, and carbonate classes may
be leached, destroyed, or altered during this procedure. Formations
of articial minerals and phases such as oxyhydroxides, calcium
oxalate, nitrates, and others are also possible. Hence, such minerals
are not available or actual in the FA residue for any future mineralogical study. On the other hand, portions of organics may remain
in the residue, because of the less soluble behavior or when the
solvent cannot contact with organics encapsulated in other inorganic matrixes (especially glass).
There are traces of polycyclic aromatic hydrocarbons present in
the coal y ash, typically up to 25 mg/kg. Due to the low solubility,
the leachate from coal y ash contains very low concentrations of
polycyclic aromatic hydrocarbons (PAHs).
Several authors have investigated the capacity of y ash to
improve the quality of leachates generated by coal refuse [256], by
oxidation of a sulphide-rich mining waste [257,258] and in passive
treatment of acid mine drainage [259]. These authors observed that
generation of acidic leachates was prevented and inorganic
contaminants signicantly reduced. Erol et al. [260] studied the
ability of y ash to remove Cu2 and Pb2 in aqueous solutions.
These authors observed that the contaminant removal capacity of
the y ash was directly proportional to the CaO content. Polat et al.
[261] investigated y ash for neutralization of highly acidic heavy
metal-laden oily waste sludge while Potgieter-Vermaak et al. [262]
compared y ash, limestone and y ash as pre-treatment agents for
acid mine drainage. The authors observed that y ash can be used
as a neutralization/xation agent. It is expected that y ash will add
alkalinity and increase the pH on contacting acid mine drainage
(AMD). This will result in precipitation of metal hydroxides, oxides
and oxy-hydroxides with consequent adsorption or co-precipitation of trace metals. Release of anions such as SO2
4 and cations like
Ca will result in precipitation of gypsum resulting in much cleaner
water. The alkalinity of y ash may not be as high as that of lime or
limestone but availability in large quantities offers a cost effective
method of neutralizing acid mine drainage.
The main components of y ash are anhydrous phases such as
aluminosilicates and salts such as sulphates, oxides and chlorides
formed at high temperatures in coal-red power generating
stations [11,263]. Some of these phases (alkali metal oxides,
sulphates, and chlorides) are highly unstable at room temperature
and pressure and in presence of water. When y ash contacts water

these phases will dissolve completely, more stable and less soluble
mineral phases will thereafter precipitate. Hence, the concentration
of some constituent species in the leachate will be controlled by the
solubility of the precipitating secondary mineral phases and
concentration of other species will be controlled by their availability to the leachate solutions and by their diffusive ux into
solution from the leaching of the primary phases with time [264
266]. If a mineral solubility control exists for a species, its
concentration in the process water on treatment of acid mine
drainage with y ash can readily be predicted with chemical
equilibria models [267]. Several authors [268,269] established that
conducting leaching tests on a particular waste material at least at
two different liquid/solid (L/S) ratios can differentiate between
these two classes of species. They pointed out that if a species
concentration does not double when the L/S ratio is halved, there
must be a solid phase control on its concentration in solution.
Determination of whether the concentration of an element in y
ash leachate is controlled by mineral solubility is a challenge. In
reactions involving acid mine drainage with y ash, the precipitates
formed are largely amorphous [263,270] and hence cannot be
detected by XRD. Dilution by the major phases of y ash such as
glass, mullite and quartz could also account for their non-detectability. Unlike equilibration of y ash with demineralized water, the
AMD contains high concentration of SO42, Ca, Mg, Al, K and Fe
which are also present in y ash and will leach out on interaction
with the AMD. In the neutralization reactions, direct doubling of
element or ion concentration similar to a reaction of y ash with
demineralized water may not be observed. A simple increase in
concentration when FA: AMD (Fly ash: AMD) ratio is doubled
maintained for the duration of the experiment may signify nonexistence of solubility control. A decrease in concentration when
the FA: AMD ratio is doubled may therefore signify existence of
solubility control for that element or ion.
Namely, materials bonded with bitumen and cement tend to
have signicantly lower leaching abilities for two reasons: rst, ash
particles are surrounded by a bitumen or cement layer preventing
water seepage, and second, bonded materials are mainly used for
upper base courses that are, compared with the lower base courses,
thinner. Considering the above mentioned, as well as the fact that
this material, when well compacted, has a very low permeability,
usually 107 m/s, there is no signicant inuence of hazardous
elements on the surrounding waters and soil due to leaching.
Therefore, it is suggested that following measures/steps should
be taken before y ash is used as adsorbent for wastewater treatment: (1) leaching behaviour test for water system; (2) forced
extraction of mobile substances from y ash; (3) immobilisation of
mobile metals and other elements; (4) destruction of persistent
organic pollutants.
11. Synthesis of zeolite
Zeolites are crystalline aluminiumsilicates, with group I or II
elements as counter ions. Their structure is made up of a framework of [SiO4]4 and [AlO4]5 tetrahedra linked to each other at the
corners by sharing their oxygens (Fig. 2) [7]. The tetrahedra make
up a three-dimensional network, with lots of voids and open
spaces. It is these voids that dene many special properties of
zeolites, such as adsorption of molecules in the huge internal
channels. The substitution of Si (IV) by Al (III) in the tetrahedral
accounts for a negative charge of the structure (Fig. 2) which may
give rise to high CEC (up to 5 meq g1) when the open spaces allow
the access of cations. Zeolites may be found in natural deposits,
generally associated with alkaline activation of glassy volcanic
rocks, or synthesized from a wide variety of high-Si and Al starting
345
Table 6
Zeolites and other neomorphic phases synthesized from y ash and Joint Committee
of Powder Diffraction Standard (JCPDS) codes for XRD identication.
Fig. 2. Idealized structure of zeolite framework of tetrahedral [SiO4]4- with a Si/Al

substitution ([AlO4]5-) yielding a negative charge, and consequently a cation exchange
capacity [7].
materials. As a consequence of the peculiar structural properties of

zeolites, they have a wide range of industrial applications [271]
mainly based on:
Ion exchange: exchange inherent Na/K/Ca2 for other cations
on the basis of ion selectivity.
Gas adsorption: selective absorption of specic gas molecules.
Water adsorption: reversible adsorption of water without any
desorption chemical or physical change in the zeoltie matrix.
A promising approach to improve the utilization of y ash is to
convert it into low-grade zeolites. The compositional similarity of
y ash to some volcanic material, precursor of natural zeolites, was
the main reason to experiment with the synthesis of zeolites from
this coal by-product. Zeolite was obtained by hydrothermal treatment of y ash [272]. This potential use of y ash has an important
background, given intensive research on zeolite growth in geological materials, such as, volcanic rocks, and clay minerals [273,274].
Due to the presence of high content of reactive phases, such as,
aluminosilciate glass, and high specic surface area of y ash, this is
a suitable starting material for zeolite synthesis. Fly ash has a high
Si/Al ratio, which allows the synthesis of low-Si zeolites with a high
ion exchange capacity, a high selectivity for polar molecules, and
a large pore volume [275]. Consequently, these minerals have
important industrial applications, mainly as adsorbents for
removal, such as, waste waters, radioactive wastes and gases, and as
replacement for phosphate in detergents [276].
Since the initial studies by Holler and Wirsching [275], many
patents and technical articles proposed different hydrothermal
activation methods for the synthesis of different zeolites from y
ash. All methodologies developed are based on the dissolution of
AlSi-bearing y ash phase with alkaline solutions (mainly NaOH
and KOH solutions) and subsequent precipitation of zeolitic material. Table 6 showed the types of zeolite synthesized from coal y
ash. The potential industrial application of these zeolitic materials
is varied. The zeolite X has a large pore size (7.3 ) and high CEC
(5 meq/g), which make it an interesting molecular sieve and highcation exchange material. The small pore size of hydroxy-sodalite
(2.3 ) accounts for low potential application for both molecular
sieving and ion exchange. The main limitation of the processes for
synthesizing zeolites from y ash is to speed up reaction, relatively
high temperatures (125200 C) applied to dissolve Si and Al from
y ash particles. Under these conditions, many of the high-CEC and
large pore zeolites (zeolites A and X) cannot synthesized. If
temperature is reduced, then synthesis yield is reduced considerably and a very long activation time is required.
The synthesis of zeolites from y ash is classied into direct and
non-direct synthesis. For direct synthesis [277285], y ash was
hydrothermally treated with an alkaline solution. At temperature,
Zeolitic product
Chemical formula
JCPDS
NaP1 zeolite
Nap zeolite
Phillipsite
K-chabazite
Zeolite F linde
Herschelite
Faujasite
Zeolite A
Zeolite X
Zeolite Y
Perlialit
Analcime
Hydroxy-sodalite
Hydroxy-cancrinite
Kalsilite
Tobermorite
Na6Al6Si10O32$12H2O
Na3.6Al3.6Si12.4O32$12H2O
K2Al2Si3O10$H2O
K2Al2SiO6$H2O
KAlSiO4.1$5H2O
Na2Al2Si1.68O7.44$1.8H2O
Na2Al2Si3.3O8.8$6.7H2O
NaAlSi1.1O4.2$2.25H2O
NaAlSi1.23O4.46$3.07H2O
NaAlSi2.43O6.86$4.46H2O
K9NaCaAl12Si24O72$15H2O
NaAlSi2O6$H2O
Na1.08Al2Si1.68O7.44$1.8H2O
Na14Al12Si13O51$6H2O
KalSiO4
Ca5(OH)2Si6O16$4H2O
39-0219
34-0524
30-0902
12-0194
25-0619
31-1271
12-0228
43-0142
39-0218
38-0239
38-0395
19-1180
31-1271
28-1036
33-0988
19-1364
(lower than 100 C), zeolites P, X and NaP1 were obtained with
24 M NaOH solution, while hydroxy sodalite and zeolite-Y were
obtained with 410 M NaOH solution. At temperature, (higher than
120 C), zeolite NaP1, hydroxy sodalite and analcime were
obtained with 410 M NaOH solution. For non-direct synthesis
[286,287], silica and alumina were extracted from y ash with hot
alkaline solution and this resulted in the mixture of silicate and
aluminate extracts. These extracts were used as the starting
material for faujasite synthesis at 6090 C and time period of two
ve days.
Fusion with sodium hydroxide prior to hydrothermal reaction
was applied by Shigemoto et al. [288290] to improve the
conversion of y ash into NaX Zeolite. Several studies
[277,292,293] examined the efciency of Na and K-Zeolite synthesis
after alkaline activation of y ash in closed systems for short activation periods (8100 h). The time of activation (from hours or days
to minutes) can be signicantly reduced for zeolite synthesis using
microwave-assisted hydrothermal process [281]. This alkaline
conversion of y ash is based on combination of different activation
solution/y ash ratios, with temperature, pressure, and reaction
time to obtain different types of zeolite. Sodium or potassium
hydroxide solutions with different molarity, at atmospheric and
water vapor pressures, from 80 to 200 C and 3 to 48 h have been
combined to synthesize up to 13 different zeolites from same y ash
[284]. The zeolite contents of resulting material varied widely (40
75%) depending mainly on activation solution/y ash ratio and
reaction time. This methodology was applied at a pilot plant scale
for the production of 2.7 tons of zeolitic material in 8 h in a singlebatch experiment [284].
To avoid the synthesis process with the generation of wastewater, Park et al. [293,294], developed a synthesis strategy based on
salt mixtures instead of aqueous solutions as reaction medium. This
interesting process has limitations, since, up till now, only low-CEC
zeolites are obtained to high temperature needed in the activation
process. Hollman et al. [287], developed a two-stage synthesis
procedure that enables the synthesis of >99% pure zeolite products
from high-Si solutions from a light alkaline attack of y ash. The
solid residue from this attack was converted into classic zeolitic
products by using conventional conversion method. This process
has advantages of producing pure zeolitic material, instead of blend
zeolite/residual y ash particles obtained from other strategies.
Moreover, high-pore volume zeolites, including zeolites X and A,
may be obtained in this process.
The lignite y ash and rice husk ash were also used as raw
materials for ZSM-5 zeolite synthesis [295]. Factors affecting the yield
346
of ZSM-5 zeolite synthesized from y ash, i.e., the SiO2/Al2O3 mole

ratio, the presence of tetrapropyl ammonium bromide (TPABr, the
structure-directing material for ZSM-5 zeolite synthesis), holding
temperature and time, and initial pressure were investigated. The
zeolite P was synthesized at SiO2/Al2O3 mole ratios of 2.8200
without TPABr. For the synthesis of ZSM-5 zeolite, sodium silicate
solution was added to adjust the SiO2/Al2O3 mole ratio in raw ash. The
yield of ZSM-5 zeolite was 59 wt.%, when following conditions were
used: SiO2/Al2O3 mole ratio, 40; the holding temperature, 210 C; the
holding time, 4 h and the initial pressure, 4 bar.
In most studies, y ash activation is usually carried out in
digestion bombs or autoclaves, varying activation agent (mainly
KOH and NaOH), temperature (100 and 200 C), conversion time
(348 h), solution concentration (0.5, 1, 2, 3 and 5 M), pressure (the
vapor pressure at the temperature selected), and solution/sample
ratio (120 ml/g). The zeolitic material is ltered and washed with
water, dried at room temperature and analyzed by XRD. The
determination of CEC value and comparison of pure zeolite is recommended for a semi-quantitative estimation of zeolite contents of
synthetic materials. Most studies showed that NaOH solutions have
higher conversion efciency than KOH solutions under same
temperature. Most zeolites reported in the Table 6 obtained from
specic y ash. Reaction time required for synthesis yield is
inversely proportional to aluminumsilicate glass content of y
ash. The conversion efciencies are dependent on non-reactive
phases (mainly hematite, magnetite, lime), and resistant
aluminumsilicate phases, such as mullite and quartz, and the grain
size distribution. Thus, for higher aluminumsilicate glass content,
shorter activation periods and lower solution/y ash rates are
needed to reach high yields of zeolite.
As previously stated, the time needed to obtain a high synthesis
yield is inversely proportional to the glass content. High-glass y
ash is zeolitized in short period (68 h), but longer reaction times
(2448 h) are required to obtain similar synthesis yields from highmullite or quartz y ash. The highest synthesis yields are obtained
in 1224 h using a high-activation solution/y ash ratio (1020 ml/
g) due to total dissolution of mullite, quartz, and the glassy matrix.
However, this process suffers from a number of disadvantages, such
as, high water consumption and need for high activation periods.
The use of lower activation solution/y ash ratio (2 ml/g) led, in
addition to less water consumption, to a drastic reduction in the
activation time. However, total dissolution of quartz and mullite is
not achieved. Both temperature and concentration of the activation

agent have a very important inuence on the types of zeolite
obtained. Thus, by increasing both parameters, low-CEC zeolites
such as hydroxy-cancrinite and hydroxy-sodalite are obtained.
Conversely, low temperature and concentration allows the
synthesis of high-CEC zeolites, such as, NaP1, A, or chabazite. Querol
et al. [7] reviewed the synthesis of zeolites from y ash. They
provided an overview on the methodologies for zeolite synthesis
from coal y ash, and a detailed description of conventional alkaline conversion processes, with special emphasis on the experimental conditions to obtain high cation exchange capacity (CEC)
zeolites.
A new process for converting coal y ash into an articial zeolite
is described [296]. The process is comprised of a high-temperature
operation and water removal during the operation. Suitable operational parameters of the process were investigated using a test
unit, and optimal conditions were found to be 2.53.5 mol/dm3 of
NaOH, and 0.881.10 dm3/kg of liquid/solid, sodium hydroxide
charge from 2.2 to 3.9 mol/kg-CFA. The zeolites obtained from
a pilot plant had a higher cation exchangeable capacity than test
unit and were comparable to zeolites prepared using a conventional method. A pilot plant, having a 0.6 m3 of vessel was tested.
The zeolite obtained from pilot plant is not inferior to conventional
method, in spite of small amount of NaOH charge. Recently, a new
zeolite production process, licensed by the KEM Corporation [297],
was developed. The zeolitization of coal ash on a semi-industrial
scale was conducted by Kikuchi [6]. A simplied process ow
diagram is shown in the Fig. 3.
11.1. Application of zeolite synthesised from y ash
Simultaneously with the development of synthesis methods,
intensive research has been carried out on the potential application
of the zeolites synthesized from y ash. The high Al (III)/Si (IV) ratio
of these zeolites accounts for the high CEC of some of them such as
NaP1, 4A, X, KM, F, chabazite, herschelite, and faujasite. Owing to
this high CEC (up to 5 meq g1 of some pure zeolites), these zeolites
have a high potential in water decontamination.
Zeolite synthesized from y ash can be utilized in the treatment
of wastewater. Zeolite synthesized from y ash has the ability of
immobilizing phosphate from wastewater [298,299]. Therefore,
simultaneous removal of ammonium and phosphate from aqueous
Fig. 3. Process ow of zeolitization plant (1.5 tons: hour) [6].
solution by zeolite synthesized from y ash (ZFA) is possible. The

existence of exchangeable Ca2 on zeolite surface is critical to
precipitate phosphate in aqueous solution [298,299]. Phosphate
immobilization capacity (PIC) of the synthesized zeolites and corresponding raw y ash was determined using an initial phosphate
concentration of 1000 mg/L [300]. Results showed that there was
a remarkable increase in PIC (from 1.2 to 7.6 times) following the
synthesis process. Although calcium and iron components were
mainly involved in phosphate immobilization, there was no
signicant change of Ca and Fe content following conversion of y
ash into zeolite. Increase in dissociated Fe2O3 and specic surface
area probably accounted for enhancement in PIC of synthesized
zeolites compared with corresponding y ash. The specic surface
area increased 26.089.4 times as a result of the conversion of y
ash to zeolite. The maximum removal of phosphate occurred within
different pH ranges for zeolites which were synthesized from high,
medium and low-calcium y ash and this behavior was explained
by reaction of phosphate with calcium and iron components.
To develop an effective technique to enhance removal efciency
of phosphate at low concentrations, ZFA was modied with acid
treatment and simultaneous removal of ammonium and phosphate
in a wide range of concentration was investigated [301]. Treatment
with more concentrated H2SO4 led to the deterioration of ZFA
structure and a decrease in the cation exchange capacity. Treatment
by 0.01 mol/L H2SO4 improved the removal efciency of phosphate
by ZFA at all initial phosphorus concentrations, while the treatment
by concentrated H2SO4 (>0.9 mol/L) resulted in a limited maximum
phosphate immobilization capacity (PIC). It was concluded that
through a previous mild acid treatment (e.g. 0.01 mol/L of H2SO4),
ZFA can be used in the simultaneous removal of NH
4 and phosphorus at low concentrations in simulating real efuent. In another
study, Na-ZFA (zeolite synthesized from y ash) was converted into
Ca-, Mg-, Al-, and Fe-ZFA by salt treatment and the simultaneous
removal of ammonium and phosphate by ZFA saturated with
different cations was investigated [302]. It was shown that Al3ZFA had the highest removal efciencies (8098%) for ammonium,
followed by Mg2 (4358%), Ca2 (4054%), Na (<20%), and Fe3
(<1%). Both alkaline pH values (in the cases of Na, Ca2, Mg2) and
acidic pH value (in the case of Fe3) inhibited the sequestration of
ammonium. At low initial phosphate concentrations, the efciency
of phosphate removal by Al3- and Fe3-ZFA approached 100%,
followed by Ca2(6085%), Na (<25%), and Mg2(<5%). The
difference in phosphate removal efciency was explained by the
adsorption mechanisms. It was concluded that ZFA could be used in
simultaneous removal of NH
4 and phosphate at low concentrations
with presaturation by an appropriate cation such as Al3 through
salt treatment.
Zeolite synthesized from y ash can also be utilized in the
removal of heavy metals from wastewater. Several authors have
reported the utilization of y ash synthesized zeolite for the
removal of heavy metals from wastewater. Table 7 summarizes the
results of the important metals investigated using zeolite-synthesized y ash.
Zeolite was synthesized from Class C y ash by molten-salt
method, and the product obtained, zeolite y ash (ZFA) was used as
an adsorbent for removal of arsenate from water [303]. ZFA showed
a higher adsorption capacity (5.1 mg/g) than activated carbon
(4.0 mg/g), silica gel (0.46 mg/g), zeolite NaY (1.4 mg/g), and zeolite
5A (4.1 mg/g). Relatively higher adsorption capacity of ZFA than
zeolite NaY and 5A was attributed to the low Si/Al ratio and the
mesoporous secondary pore structure of ZFA. It was observed that
the adsorption capacity of zeolites was generally lower than activated alumina (16.6 mg/g), which is ascribed to small pores in
zeolite frameworks. The adsorption capacity of ZFA was signicantly improved, after loaded by alumina via a wet-impregnation
347
Table 7
Summary of adsorption of metals on y ash based zeolite.
Metals
Adsorbent
Zn2
Cd2
Fly
Fly
Fly
Fly
Fly
Fly
Fly
Fly
Fly
Fly
Fly
Pb2
Cu2
Ni2
Cr3
Co2
Cs
ash
ash
ash
ash
ash
ash
ash
ash
ash
ash
ash
zeolite
zeolite
zeolite
zeolite
zeolite
zeolite
zeolite
zeolite
zeolite
zeolite
zeolite
Adsorption
capacity (mg/g)
4A
X
X
4A
X
4A
4A
4A
30.80
95.6
97.78
70.6
420.61
50.45
90.86
8.96
41.61
13.72
443.9
Temperature ( C)
20
20
25
References
[308]
[307]
[309]
[307]
[309]
[308]
[309]
[308]
[306]
method. The modied ZFA (ZFAAl50) with optimum alumina

loading showed an adsorption capacity of 34.5 mg/g, which was 2.1
times higher than activated alumina. The Toxicity Characteristic
Leaching Procedure (TCLP) leachability tests indicated that spent
ZFA and alumina-modied ZFA complied with the EPA regulations
for safe disposal. The removal of arsenic, from drinking water by
ltration through modied y ash bed is also reported [304]. The
effects of different parameters like pH and presence of other
constituents are described. The effectiveness of the modied y ash
bed for the control of arsenic was demonstrated by taking different
quantities of arsenic(III) and arsenic(V) salts. The utilization of
zeolites synthesized from y ash (FA), and related co-disposal
ltrates as low-cost adsorbent material, was investigated [305]. The
synthesized zeolite was explored to establish its ability to remove
Pb(II) and Hg(II) from aqueous solution. The synthesized zeolite
was effective in reducing the Pb(II) and Hg(II) concentrations by
95% and 30%, respectively.
Fly ash was converted to zeolites by hydrothermal treatment,
and used for the removal of metal ions, radiocesium [306], lead and
cadmium [307]. Maximum uptake capacity was 3.34 mmol Cs/g,
which was 23 times higher than those of synthetic zeolite P, and
natural mordenites. Adsorption capacity for lead and cadmium was
70.58 mg lead/g-zeolite and 95.6 mg cadmium/g-zeolite, respectively, when the initial concentration for both ions was 100 mg/L.
The removal performance and the selectivity sequence of mixed
metal ions (Co(II), Cr(III), Cu(II), Zn(II) and Ni(II)) in aqueous solution were investigated by adsorption process on pure and chamfered-edge zeolite 4A prepared from coal y ash (CFA), commercial
grade zeolite 4A and the residual products recycled from CFA [308].
The adsorption process is pH and concentration dependent. The
sorption rate and sorption capacity of metal ions could be signicantly improved by increasing pH value. The removal mechanism of
metal ions was by adsorption and ion exchange processes. The coal
y ash (CFA) was modied to zeolite X, and used as an effective
adsorbent for the removal of Cu(II), Cd(II), and Pb(II) [309]. External
mass transfer step seemed take part as a rate limiting step for
sorption of Pb(II) at low initial concentration, and high adsorbent
dose. The process was controlled more signicantly by intraparticle
diffusion step at high initial concentration, and low sorbent dose.
However, Cu(II) was found to be generally controlled by intraparticle diffusion step at all concentration range examined in this
work. The sorption of Cd(II), on the other hand was controlled by
both external mass transfer and intraparticle diffusion steps at all
range of initial concentration. Surface-modied zeolite material has
been developed from commercial zeolite, and y ash-based zeolite,
by treating it with surface modiers, such as, hexadecyltrimethylammonium
bromide
and
tetramethylammonium
bromide [310]. The adsorbent was evaluated for removal of arsenic
and chromate anions. High selectivity, faster kinetics and high
348
adsorption capacity ensure cost effectiveness of these materials

compared to other conventional materials for dearsenication.
Surface modied zeolite from y ash is being used for adsorption of phenol and o-chlorophenol from wastewater [311]. The
comparison of adsorption of phenol and o-chlorophenol on
commercial zeolite-Y, y ash based zeolite (FAZ-Y) and surface
modied y ash based zeolite (SMZ-Y) were studied. Adsorption of
phenol on SMZ-Y was 4.05 and 3.24 times higher than the FAZ-Y
and commercial zeolite-Y, respectively. For o-chlorophenol, the
efciency is higher by a factor of 2.29 and 1.8 for FAZ-Y and
commercial zeolite-Y, respectively. This may attributed to hydrophobicity imparted by surfactant molecules on the surface of y ash
zeolite, consequently leading to organic partitioning. The presence
of salts has a substantially detrimental effect on adsorption of
phenol and o-chlorophenol.
The potential of y ash based zeolites for adsorption of thiophene and benzothiophene from n-hexane solution was investigated [312]. The zeolites obtained were sodalite (SOD), gismondine
(GIS), and cancrinite (CAN). It was found that GIS with higher
specic surface area and average pore volume had superior
performance to other synthesized materials. Adsorption capacity of
developed zeolites was compared to those of commercial zeolites,
i.e. NaY, HUSY, beta, and ZSM-5 obtained via the conventional
synthesis methods. The results suggested a potential of zeolites
derived from coal y ash for removal of refractory sulfur
compounds, such as thiophene, benzothiophene etc.
Fly ash was modied by hydrothermal treatment with NaOH to
hydroxysodalite zeolite [313]. The cation exchange capacity of the
modied ash was signicantly increased over that of the raw y
ash. Modied y ash adsorbed a cationic dye (methylene blue) to
a much greater extent than an anionic dye (alizarin sulphonate).
Saturation adsorption revealed that capacity of y ash for methylene blue had increased 10-fold during modication when
compared to raw ash. Adsorption is thus ascribed to be a surface
effect rather than involving incorporation into the channels of
hydroxysodalite structure.
Thus, it is concluded that zeolite from y ash can not be applied
in high-value applications, but used for some of the low value
applications that utilize the good ion exchange capacity of such
zeolite (but this ion exchange is almost non selective and therefore
can not be used as catalysts).
12. Construction work/industry
Utilization of y ash appears to be technically feasible in the
cement industry. There are essentially three applications for y ash
in cement, including (1) replacement of cement in Portland cement
concrete (2) pozzolanic material in the production of pozzolanic
cements, and (3) set retardant ingredient with cement as
a replacement of gypsum.
Cement is the most cost and energy intensive component of
concrete. The unit cost of concrete is reduced by partial replacement of cement with y ash. The utilization of y ash is partly based
on economic grounds as pozzolana for partial replacement of
cement, and partly because of its benecial effects, such as, lower
water demand for similar workability, reduced bleeding, and lower
evolution of heat. It has been used particularly in mass concrete
applications and large volume placement to control expansion due
to heat of hydration and also helps in reducing cracking at early
ages. The major drawback of bre reinforced concrete is its low
workability. To overcome this shortcoming, a material is needed,
which can improve the workability without comprising strength.
The use of y ash in concrete enhances the workability of concrete
and being widely recommended as partial replacement of cement.
This also reduces the cost of construction. Fly ash concrete provides
much strong and stable protective cover to the steel against natural
weathering action.
Because of the presence of cementitious compounds of calcium
and a reactive glass, the high-calcium y ash is quite suitable in
Portland cement products. Several studies are being conducted to
better understand the complexities of alkali aggregate reactivity
and sulphate resistance with respect to y ash in concrete. The
availability of high-lime y ash containing compounds found in
cement has led to high-strength concretes produced by the addition of y ash and plasticizers. High-strength and high-performance concrete can also be made with Class F y ash. The ball
bearing effect produced by the spherical y ash particles has
resulted in better pumpability of concrete and easier nishing with
trowels and other tools. The utilization of y ash in concrete
produces less permeability because of the spherical particles, and
therefore improved packing, i.e. more dense paste and pozzolanic
reaction. In mass concrete,with high-percentage replacement of
cement with y ash, there is a lower heat of hydration compared to
straight Portland cement concrete, particularly when Class F y ash
is used. Class C y ash may not lower the heat of hydration.
Traditionally, with bituminous-type y ash, 1525% of the cement
was replaced. The advent of cementitious, high-lime y ash has
permitted normal replacements of 2540% and up to 75% for
parking lots, driveways, and streets. Nowadays, chemical admixtures are essential components of the concrete mixtures. Newly
developed admixtures allow lowering the water/cement ratio to
very low levels without loss of workability. By incorporation of
superplasticizers (SPs), the early strength development of y ash
concrete can be accelerated to achieve the desired performance.
Generally, the long term ultimate mechanical properties of y ash
concretes are higher than those of plain Portland cement concretes.
The setting and hardening rates of y ash concrete at early ages are
slower, especially under cold weather conditions. Extended
hydration period makes the material more sensitive to curing
conditions. These problems may be solved by using various
methods such as steam curing. There are few studies on the effect of
steam curing on high-volume Class C y ash concrete.
There has been much concern about sulphate resistance of
concrete containing high-lime y ash. It was reported that Saskatchewan lignite y ash concrete increases sulphate resistance
[314]. Research with other high-lime y ash has produced conicting results with respect to sulphate resistance. Dunstan [315]
has proposed a sulphate resistance factor, R, which is equal to CaO5/Fe2O3 oxide analysis percentages. When R is less than 1.5, y ash
should improve sulphate resistance.
Mehta [316319] has discussed the factors that contribute to
attack of sulphates on y ash concrete. As noted in his review paper
on this subject [316], the agents responsible for concrete expansion
and cracking are alumina-bearing hydrates, such as calcium monosulfo-aluminate and calcium aluminate hydrate, which are
attacked by the sulphate ion to form ettringite and calcium trisulfoaluminate. Acidic-type interactions between sulphate ions and
calcium hydroxide also lead to strength and mass loss.
Exhaustive research has been conducted on y ash admixture
concrete and its properties. Research showed that y ash used as an
additive to Portland cement has a number of positive effects on the
resulting concrete. A decrease in water demand, decreasing the
water:cement ratio. An improvement of the packing of particle size
decreases air entrainment in the concrete. Although research has
indicated that decreased air entrainment adversely affects initial
freeze than durability of the concrete, if y ash concrete is allowed
to cure fully, the effects are minimum and the concrete mix will
perform satisfactorily.
Fly ash increases resistance to corrosion, and ingress of corrosive
liquids by reacting with calcium hydroxide in cement into a stable,
cementitious compound of calcium silicate hydrate. The original

calcium hydroxide was soluble, whereas the calcium silicate
hydrate is less soluble in y ash concrete, thereby reducing the
possibility of leaching of calcium hydroxide from the concrete. In
addition to calcium silicate hydrate being less soluble, reaction
products tend to the lling of capillary voids in the concrete
mixture, thereby reducing permeability of the concrete. Zhang et al.
[320] studied the leachability of trace metal elements from y ash
concrete. They studied the effect of leaching conditions, and found
that none of the trace metals analyzed (As, Cd, Cr, Cu, Pb, Se and Zn)
in the leachates from y ash concrete exceeded the regulated
concentration levels specied in the toxicity characteristic leaching
procedure (TCLP) test.
High-volume y ash concrete has emerged as a construction
material in its own right. This type of concrete contains more than
50% of y ash by mass of total cementitious materials. Many
researchers have used high volume of Class C, and Class F y ash in
concrete. Ravina and Mehta [321] reported that by replacing 35
50% of cement with y ash, there was 57% reduction in water
requirement for the designated slump, and the rate and volume of
bleeding water was either higher or about same compared with the
control mixture. Malhotra and colleagues [322328] reported
extensively on high-volume y ash concrete. Concrete, containing
high volume of Class F y ash exhibited excellent mechanical
properties, good durability with regard to repeated freezing and
thawing, very low permeability to chloride ions [322324], and
showed no adverse expansion when reactive aggregates were
incorporated into concrete [324]. Results up to 275 days of testing
have indicated that high replacement levels of cement with y ash
were highly effective in inhibiting alkalisilica reaction [325].
Superplasticized high-volume y ash concrete, containing up to
60% of y ash of total cementitious materials had poor abrasion
resistance than concrete without y ash [326]. Air-entrained highvolume y ash concrete exhibited excellent characteristics
regardless of the type of y ash and cements [327].
Addition of y ash as an admixture increased early-age
compressive strength and long-term corrosion resistance characteristics of concrete [328]. Abrasion resistance of concrete made
with Class C y ash was better than both concrete without y ash
and concretes containing Class F y ash [329]. High volumes of
Class C and Class F y ash can be used to produce high-quality
pavements in concrete with excellent performance [330]. Blending
of Class C y ash with Class F y ash showed either comparable or
better results than either of the control mixture without y ash or
the unblended Class C y ash [331]. Hwang et al. [332] examined
the effects of ne aggregate replacement on the rheology,
compressive strength, and carbonation properties of y ash and
mortar. Test results showed that rheological constants increased
with higher replacement level of y ash and that, when water-tocement ratio was maintained, the strength development and
carbonation properties were improved. Siddique [333] reported
that Class F y ash can be suitably used up to 50% of cement
replacement in concrete for use in precast elements, and reinforced
cement concrete construction. The use of high volumes of Class F y
ash as a partial replacement of cement in concrete decreased its 28day compressive, splitting tensile and exural strengths, modulus
of elasticity, and abrasion resistance of the concrete.
Singh and Garg [334] studied the cementitious binder from y
ash. The development of binder takes place through the formation
of ettringite, CSH gel and C4AH13. The study suggested that the
binders are eminently suitable for partial replacement (up to 25% of
the cement in concrete) without any detrimental effect on the
strength. Fly ash can be used in the range from 45% to 70% in
formulating these binders along with other industrial wastes to
help in mitigating environmental pollution. Oner et al. [335]
349
conducted a study on strength development of concrete containing

y ash, and optimum usage of y ash in concrete. Bouzoubaa et al.
[336] showed that except for resistance of the concrete to the
deicing salt scaling, mechanical properties and durability of
concrete made with this blended cement were superior compared
to the ungrounded y ash and cement concrete. Antiohos et al.
[337] investigated the properties of a series of blended cements
prepared by mixing clinker with a y ash of high-sulphate content.
No gypsum was added in the mixtures, since it is believed that
sulphate ions necessary for prolongation of the setting process
(commonly provided by gypsum) could be provided by y ash
enriched in sulphates. All samples tested exhibited satisfactory
initial and nal setting times and decent compressive strength
values, when compared to the reference specimen containing only
gypsum and no y ash.
The utilization of y ash in the construction of concrete dams
was investigated [338]. The compressive strengths of dam concrete
with 50% of y ash in 90 days are higher than those with 30% of y
ash or without y ash. Fly ash may decrease the deformation of dam
concrete with 50% of y ash, and the shrinkage and expansive strain
was reduced signicantlyabout 33% and 40% less than the specimens without y ash, respectively. The low-lime y ash was used to
develop chloride-resistant concrete by improving its physical
resistance to the ingress of chlorides and binding capacity of these
ions in the cover zone [339].
Researchers have modied y ash to increase the setting properties of cement. Lupu et al. [340] investigated the use of chemcially
modied y ash to control the setting of cement. The chemical
treatment of Class C y ash with a 0.2 wt% of CaCO3 solution results
in dramatic increase in setting time, and superior stability during
the induction period for cement slurries. The performance of CaCO3
treatment appears to be a consequence of each y ash particle
being provided with necessary Ca prior to hydration without being
dependant on cement-y ash particle interactions. Thus, the setting
process is no longer dependent on the particle shape, packing and
dispersion of the y ash and cement. They modied the class C, I
and F y ash with water, HNO3 and aqueous CaCO3 [341]. It was
found that the setting properties of the cement/y ash mixture
enhanced by changing morphology and surface chemistry of y ash
particles. The treatment of C-FA with an aqueous CaCO3 solution
results in a dramatic improvement in the setting time and the
setting prole on C-class FA; in contrast, the treatment has no effect
on the set time for F-FA and reduces the set time and appears to
result in an even more nonideal induction setting curve as
compared to the untreated C/I-FA. The enhancement observed for
the treatment of C-FA with aqueous CaCO3 solution is not a consequence of the water solution, since simply washing with water (i.e.,
C-FAH2O) results in the extraction of Na and Ca with a concomitant
increase in surface area and a performance similar to untreated I-FA
and F-FA. The acid (HNO3) treatment of I-FA and F-FA results in the
formation of an inert ller-like material, while acid treatment of
C-FA results in a material with completely undesirable setting
properties. Antiohos et al. [342] activated y ash chemically by
adding industrially produced quicklime. The presence of quicklime
accelerated the reaction rate of high-calcium y ash, whereas in
case of lower-calcium y ash, quicklime had a positive impact only
during the very early stages of hydration, and thereafter acted
inhibitory with respect to its reactivity development. Addition of
chemical activators, such as, Na2SO4 or CaCl2 accelerates pozzolanic
reactions, and changes pozzlanic reaction mechanisms between y
ash and lime [343]. These results in decreased setting time, accelerated strength development, and increased strength of materials
containing y ash, especially with a high percentage of y ash.
Thus, chemical activation of reactivity of y ash is an effective
method to increase the use of y ash in concrete.
350
The typical use of y ash in Indian Pozzolana Portland cement

(PPC) is in the range of 1525%. Higher usage of y ash is restricted,
due to a decrease in the strength of cement, especially the early
strength. This is attributed to the low reactivity of y ash [344]. The
reactivity of y ash can be increased through mechanical activation.
The effect of mechanical activation depends on the type of activation
device. The higher reactivity of mechanically activated y ash has
been exploited in developing the process of making PPC containing
higher proportion of y ash [345347]. Mechanical activation of y
ash results into a signicant increase in the early strength of cement,
as compared to commercial cement. It was found that 5060% of
mechanically activated y ash can be used as replacement for clinker
with strength higher or comparable to commercial cement. Apart
from strength, the cement samples meet all other criteria, e.g.
consistency setting time, autoclave expansion, and steel corrosion
resistance of cement was similar to commercial cement.
The exact mechanisms of the strength development in PPC
containing mechanically activated y ash are not understood
completely. The observation based on isothermal conduction
calorimetric studies are quite revealing in this context. To assess the
role of mechanical activation, hydration of cement formulations
containing xed amount of clinker (50%), and different proportions
of raw and mechanically activated y ash was investigated. The
study revealed that mechanical activation of y ash has an indirect
bearing on the hydration of cement phases, namely, tri-calcium
silicate (C3S) and tri-calcium aluminate (C3A). This was reected by
change in the maximum hydration rate of the phases (Ri where
i C3S, C3A), and the time of maximum hydration rate (Ti, i C3S,
C3A). It was observed that compressive strength, after 3 days and 28
days of hydration, showed a high degree of correlation with calorimetric results. The overall effect of mechanical activation of y
ash on cement strength may result from the formation of compact
microstructure, because of increased lime reactivity, and its bearing
on the hydration of clinker phases. Further studies are required to
understand the exact mechanism of hydration, and strength
development in PPC prepared with mechanically activated y ash.
Recently, Roller compacted concrete (ROCC) application showed
that usage of y ash in ROCC production was a wide spread practice,
such as, roads, dams, and large oor construction [348350]. Fly
ash modied the properties of concrete in both fresh and hardened
state including workability, strength and shrinkage [351,352].
Furthermore, using y ash in concrete reduces bleeding [353], heat
of hydration [354], permeability and porosity of concrete [355,356].
It increases abrasion resistance of concrete [357], and reduces alkali
aggregate reaction [358]. Utilization of y ash in accordance with
its physical property and chemical composition is restricted by
different standards. For instance, the ASTM C-618 [359] restricts the
amount of SiO2 Al2O3 Fe2O3 (SAF) to 50% for high-calcium y
ash, and 70% for low-calcium y ash. It was shown that a nonstandard y ash can also be used in concrete. Atis [356,360] showed
that Aberthaw y ash did not conform to the relevant standard;
alhtough, it provided excellent strength. Zhang et al. [361] showed
that a non-standard y ash could also be used in concrete.
Reactive powder concrete (RPC) is a rather new cement-based
material developed through microstructural engineering. Conventional RPC is composed of cement and very ne powders, such as,
crushed quartz and silica fume. The basic principles for the development of RPC have been explained by the Richard and Cheyrezy
[262363]. Cement dosage of RPC is generally over 8001000 kg/m3.
A high amount of cement not only affects the production costs, but
also has negative effects on the heat of hydration and cause
shrinkage problems. Replacing cement with mineral admixtures
seems to be a feasible solution to these problems. Furthermore,
incorporation of mineral admixtures may positively affect the
durability of concrete. Kejin and Zhi [364] showed that maximum
heat of cement hydration in binary/ternary cement (y ash and/or

ground granulated blast furnace slag) concrete decreased with
supplementary replacement of cementitious material. Massidda
et al. [365] studied the effects of autoclaving under saturated vapor
at 180 C on the physical and mechanical properties of reactivepowder mortars reinforced with brass coated steel bers. Autoclave
curing yielded exural strength of 30 MPa and compressive
strength of 200 MPa. Shaheen and Shrive [366] investigated the
freezethaw resistance of RPC. RPC has excellent freezethaw
resistance with no sign of damage up to 600 cycles according to
ASTM C 666 test procedure. Rougeau and Borys [367] showed that
ultra high-performance concrete (UHPC) can be produced with
ultra ne particles other than silica fume, such as, y ash, limestone
microller or metakaolin. Lee et al. [368] found that RPC has a good
repair and retrot potentials on compressive and exural strength.
The effects of compressive and exural strength with RPC of 10-mm
thickness are about 200% and 150% more than normal strength
concrete. Recently, Yazici et al. [369] demonstarted that cement and
silica fume content of RPC decreased using y ash. The effect of
these mineral admixtures on compressive strength of RPC was
investigated under autoclave curing. A novel technology of
combined utilization of high volumes of both coal ashbottom ash
and y ash, for lightweight concrete production was developed at
The College of Judea and Samaria (Ariel, Israel) [370373].
As compared to typical y ash, with a mean particle diameter
ranging from 2030 micrometers, ultra ne y ash can be produced
with a mean particle diameter of 15 microns. The reduced particle
size means that the pozzolanic reaction, which is normally a slow
process, is accelerated. Further, the ner particles may more
completely react than the coarser particles of y ash. So, the
durability and strength benets that one observes with a typical y
ash at a late age (more than one year) can be attained at a much
earlier age (less than 90 days) and with a smaller dosage of an ultra
ne y ash.
Typically, ultra ne y ash is used at a replacement rate of 515%
of the cement weight. At these dosage levels, it has been demonstrated that ultra ne y ash contribute more to concrete strength
gain and permeability reduction than common AASHTO M 295
(ASTM C 618) y ash, and will perform comparable to highly
reactive pozzolans, such as silica fume. Concrete durability properties, such as resistance to alkali sulfate reaction, sulfate attack,
and corrosion are also enhanced by ultra ne y ash.
Both AASHTO M 295 (ASTM C 618) Class C and Class F y ash
have their own specic advantages when used as a cementitious
material in concrete. It may be ideal to have a y ash with a low to
moderate LOI and that can be used to prepare a concrete that is very
effective in resisting alkali sulfate reaction, sulfate attack, and at the
same time have high early strengths. One way to achieve that is to
blend Class C and Class F y ash. The exact ratio of the blend will
depend upon the specic y ash and their desired behavior in the
concrete.
HVFAC refers to concrete where y ash comprises more than
30% of the total cementitious materials. HVFAC has a lower cost and
is more durable than conventional concrete, and affords improved
resistance to alkali-sulafate reaction and sulfate attack. Several
successful eld applications have been completed. Adequate early
strengths and set times are obtained by using high range water
reducers to achieve a very low water/cement ratio.
In order to increase considerably the utilization of y ash, and to
have a signicant impact on the production of cement, it is
necessary to advocate the use of concrete that will incorporate
large amounts of y ash as replacement for cement. However, such
concrete will have to demonstrate performance comparable to that
of conventional Portland cement concrete, and must be cost
effective. In 1985, CANMET developed a concrete incorporating
large volume of y ash that has all the attributes of high-performance concrete i.e. excellent mechanical properties, low permeability, superior durability, and that is environmentally friendly.
McCarthy and Dhir [374] have demonstrated that y ash is
generally under-utilised, particularly in relation to its application as
a binder. However, the authors have attempted to show, through
a number of different methods, by which this can be extended, in
particular the use of coarser y ash, materials of high LOI, and that
which has been treated with moisture. These provide considerable
potential for substantial increases in y ash utilisation. Fly ash can
be used more effectively in concrete by simple adjustment of the
concrete constituent materials or through more rened concrete
mix proportioning techniques. It has also considered how
improvements can be obtained through combination with one or
more other binder materials, beyond normal Portland cement. It is
believed that these routes are of importance towards developments
in and achievement of high-performance concrete.
An attempt has been made to consider methods for the
continued use of y ash as a binder through post-production processing if changes in the production process modify its properties. It
is demonstrated that y ash has a role to play in the development of
high-performance concretes through the use of multi-binder
combinations. It is shown that in other construction applications
where cementitious binders are required, such as grouting and
masonry, y ash can be used and will give similar or improved
properties compared to neat Portland cement binders.
The composition and characteristics of y ash have tended to
dictate the way the material is used in concrete. For example, in
structural concrete y ash levels of 30% of the binder content are
common, because at higher levels early strength of concrete may be
reduced. Adjustment to the constituent materials, e.g. the cement
characteristics, use of chemical admixtures and the way the
materials are proportioned, are potentially simple routes to further
exploiting y ash.
Experience with y ash in structural concrete has generally seen
the material used at levels of around 30% of the binder. At this level,
it has been demonstrated that, in almost all respects, similar or
enhanced performance compared to that of Portland cement
concrete of equivalent 28 day strength is possible. Where higher
levels have been used, these have tended to be in special situations
where, for example, control of heat or properties other than
strength has been important. As y ash is slower reacting than
Portland cement, use at higher levels can have a detrimental effect
on early concrete strength, which with greater levels of a relatively
slower reacting material will tend to be reduced. This can
frequently be a critical parameter in relation to the management of
site operations and overall economy of construction. Overcoming
this potential restriction is a necessary requirement towards the
use of higher y ash contents in concrete for mainstream structural
applications. A possible means of achieving this lies in the combination of y ash with cement that exhibits high early strength
characteristics or is fast reacting. This can be with cements which
are chemically composed or ground to a greater neness to provide
high early strength. The advantage of combining y ash with these
materials is two-fold. The dilution of cement with slow reacting y
ash will reduce the rate of setting and promote the development of
a better hydrate structure, while these cements will boost the early
strength of y ash concrete, potentially allowing greater levels of
material to be used.
Given the importance of efciently using binders and the
increased availability and use of super plasticizing admixtures,
a possible route to minimising the increases in binder content
required with y ash is through reduced water contents and
inclusion of these admixtures to maintain workability. This
approach is attractive because it is more effectively using the
351
constituent materials, with the dispersing effects of the super

plasticizing admixture promoting the formation of a better hydrate
structure and less surplus water in the concrete mix.
The majority of mix proportioning techniques available for
concrete tends to give coverage to the particle size distribution or
grading of aggregate, but do not consider the size and shape of the
binder particles. The aim of producing concrete, in particular with
respect to durability, centres around minimisation of voidage as the
binder matrix develops. If this is controlled initially by simply
considering the physical properties of all of the solid constituents
and optimising their proportions to minimise voidage, then the
demands on the developing matrix will be reduced and the process
of producing a dense material should be more readily achieved.
Several properties of concrete are improved when air is
entrained. The inclusion of air as small, sub-millimeter air bubbles
(less than 250 mm) makes the concrete more resistant toward
damage from freezing and thawing and improves its workability
and cohesion [375377], without or only to a small degree affecting
the production costs [378,379]. On the other hand, too high air
content reduces the strength of the concrete [376,377]. Air
entrainment occurs during agitation of the concrete paste, and the
amount, which is approximately 56 vol%, is controlled by air
entraining admixtures (AEAs). These are typically aqueous
mixtures of ionic or non-ionic surfactants derived from either
natural sources (wood resins, tall oil) or based on synthetic
chemicals [378]. Today, modern AEAs are mostly anionic in character [379]. Vinsol resin extracted from pinewood is one of the most
effective AEAs among the natural surfactants. The active compound
is the sodium salt of abietic acid (AAS). The surfactants adsorb
strongly to the airwater/cement interface, having their non-polar
end toward the interior of the air bubble and their polar end in the
aqueous phase or adsorbed on the surface of the cement particle
[376]. This effect stabilizes the air bubbles, which in the case of
missing AEAs would coalescence into larger bubbles leaving the
concrete mixture. The required amount of air to prevent concrete
from freezethaw damages has been discussed by Nasvik et al.
[380], who argues that modern surfactants create smaller bubbles
with less spacing between each other in the concrete paste. With
this combination, less entrained air is needed to obtain a freeze
thaw resistance.
The utilization of y ash in concrete has been reported to affect
the required dosage of AEAs to entrain the proper amount of air in
the concrete mixture [381384]. Instead of stabilizing the air
water/cement interface, the AEAs are strongly adsorbed by some
fractions of the y ash, leading to a reduced amount of AEAs
stabilizing the entrained air [385,386]. An increased dosage of AEAs
may compensate for the adsorption loss, but normal variations in
ash properties give rise to large and unacceptable variations in
entrained air [385,387]. Helmuth [388] has summarized how
variations in several properties of y ash have been found, even in
ashes acquired from the same power plant. The unburned carbon,
and not the inorganic fraction (mineral matter) of the y ash,
appears to be responsible for the adsorption of AEAs [385387].
A large part of the carbon surface is non-polar compared with the
polar surface of the inorganic particles. This provide active
adsorption sites for the hydrophobic part of the surfactants, thus
the carbon competes with the air/water interface. Baltrus et al.
[389] investigated the impact on air entrainment from alkaline ions
such as Ca2 and Mg2, which are able to form insoluble products
with surfactants. A signicant decrease in surfactant adsorption of
a y ash was observed, after it had been washed with deionized
water to remove soluble ions. Furthermore, the ltrate containing
these ions was added to an AEA solution and it immediately turned
cloudy indicating that the surfactants precipitated. Similar behavior
was observed when a calcium containing y ash was added to an
352
AEA solution. However, in this case, the surfactants were simultaneously adsorbed by the y ash and the initially formed precipitate
did slowly dissolve again. The same effect is seen in concrete pastes
where the surfactants are adsorbed on the surface of cement
particles and therefore, hardly any precipitations of surfactants
occur. The polar ends of the surfactants are oriented toward the
particle making them still able to contribute to air entrainment.
Other compounds of y ash, which may inuence the air
entrainment in concrete, have been reported by Gebler and Klieger
[390]. Laboratory data indicated that increased SO3 or total alkalis
(as Na2O), content in y ash lead to reduced air loss or decreased
AEA requirements in freshly mixed concrete, respectively. The
latter observation is noted to be in agreement showing that less
AEAs were required in Portland-cement mortars with increased
alkalis [391]. Finally, higher neness of y ash has been argued to
lead to increased required dosage of AEAs [382], but has been
stated by others to be of minor importance [383].
Post-treatment methods have been applied to improve y ash
quality. Ozonation, thermal treatment and physical cleaning of
carbon have been found to improve the y ash performance for
concrete utilization. The capability of the residual carbon to adsorb
AEAs can be reduced by exposing y ash to an oxidizing environment, which increases the oxygen population on the surface. Gao
et al. [392] discussed how both wet and dry methods can be applied
to improve y ash quality, but they argued that wet methods give
rise to problems such as high drying costs and loss of pozzolanic
activity of the treated ashes. From the evaluation of laboratory data
and economic calculations based on ozone requirements, price of
ozone, y ash sales price, and disposal costs, Gao et al. [392] estimated that development of a commercial post-treatment process
based on ozone appears to be protable. The process can take place
at ambient temperature, while thermal treatment in air requires
more than 300 C, which is considered to be impractical by the
authors [392]. Nevertheless, thermal post-treatment of y ash has
successfully been implemented in at least one case [393], where y
ash with an average LOI on 12.5 wt% was treated in a uidized bed
combustor. The process was operated without additional fuel. The
LOI of the product was approximately 2.5 wt% and it performed
well in concrete. It is noted, that patents have been drawn by Hurt
et al. [394,395], which describes a method for improvement of y
ash quality by ozone treatment.
Separation processes can recover carbon from y ash, making
the mineral-rich fraction suitable as concrete additive. Several
studies have been published describing how carbon in y ash can
be reduced by physical cleaning [396406] and many patents have
been drawn. However, none of the studies compared the AEA
adsorptivity of the y ash before or after the cleaning process. The
recovered carbon product is often disposed in landlls [407].
Fly ash produced from pulverized coal combustion is used in
concrete as pozzolanic additive, but has in some cases been
reported to interact with air entraining admixtures (AEAs), which
are important to enhance air entrainment in concrete. The interaction between AEAs and y ash appears to be related to the
residual carbon present in y ash due to its capability to adsorb the
AEAs in the concrete mixture. Regulations for approval of y ash as
concrete additive are typically based on the carbon content determined by the LOI test. However, the wide installation of improved
combustion technologies in order to reduce NOx emissions has lead
to generation of y ashes containing residual carbon having
a higher adsorption capacity of AEAs (per unit mass of carbon).
Therefore, y ashes can show poor performance in concrete utilization even at LOI values within the established regulations. There
are still some unresolved issues within this eld, and Pederson et al.
[408] recommended the following potential subjects to be included
in further work.
Steps should be taken toward a better understanding of the

relationship between combustion conditions and y ash quality.
This could be benecial in future design of combustion technologies, where both low NOx emissions and high-y ash quality may be
achieved. The relative contribution of soot and char to poor y ash
quality is still an unresolved issue which need further investigation.
Methods to distinguish and separate soot from char need to be
further developed in order to verify if soot contributes to the poor
performance of some y ash in concrete. Moreover, work should
include optimization of combustion conditions in order to avoid
soot formation and destroy or passivate formed soot in the furnace.
The demand of renewable energy sources has increased the use of
biomass in the production of heat and electricity. Approval of y
ash from biomass combustion as concrete additive may give rise to
new problems with air entrainment in concrete, especially in
power plants where highly reducing combustion conditions are
implemented. Only few studies have focused on this eld and
additional experiments and case studies are necessary to uncover
whether there is a problem. Combustion of other alternative fuels
may also affect the y ash quality, e.g. y ash from coal/petroleum
coke co-ring has shown a low AEA adsorption capacity. It has been
shown that both the particle size and the surface chemistry of
carbon have impact on AEA adsorption. Detailed characterization of
available adsorption sites, controlled by carbon properties such as
porosity and surface complexes, can help in development of
diffusion models for the AEAs into carbon in the concrete mixtures.
A model can be used as a tool to quantitatively predict AEA
requirements, both initial and over time, to obtain the needed air
entrainment in y ash concrete mixtures. It may include other
interfering parameters such as formation of insoluble compounds,
particles, ionic strength, mixing procedure and handling.
The disposal of metal-laden y ash is a problem. Various
methods have been suggested for the safe disposal of metal-laden
y ash. Metal-laden y ash can be incorporated into the cementitious mixture to a great extent without the risks of unacceptable
delay of cement setting and excess heavy metals leachability from
solidied products. Further, the metal-laden adsorbent was
immobilized into cement for ultimate disposal and no signicant
leaching was observed from the stabilized products. The proposed
technology (utilization of industrial wastes for efuent treatment
and then ultimate disposal of adsorbents laden with pollutants in
cementitious materials by xation) provides a two-fold aim of
wastewater treatment and solid waste management. The coal y
ash, used as immobilization agents for heavy metal ions in aqueous
solution, were loaded to saturation with Pb(II), Cd(II) and Cu(II), and
solidied by cement-based CFS technology to hard concrete blocks
which should not pose any risk to the environment [409]. The
setting and hardening characteristics of mortars and the exural
and mechanical strengths of the solidied specimens were optimized with respect to the dosage of natural and metal-loaded solid
wastes. The xed metals essentially did not leach out into water
over extended periods. The matrix-disrupting effect of lead was
eliminated by adding NaAlO2, Ca3(PO4)2 or Ca3(PO4)2 CaCl2 at
optimal dosages so as to improve the setting, hardening and
mechanical properties of the nal concrete block. Weng et al. [105],
indicated that for an extended curing time, it is possible to prepare
mortars with metal-laden y ash that have strength comparable to
cement only. However, further evaluation of the properties, such as
strength, durability, sulphate resistance, wetting/drying and
freezing/thawing cycles, and volume change of the metal-laden y
ash mortar, on a long-term basis is necessary before a conclusive
recommendation can be made on the use of this mortar for
construction purposes. It is striking to note that none of the
leachates from ASTM and USEPA tests exhibits heavy metal
concentrations exceeding the drinking water standards. Thus, it
appears that the xation process can be environmentally safe.

Metal-laden y ash should be considered for use in secondary
construction materials.
13. Lightweight aggregate
Use of y ash as a by-product aggregate in the manufacture of
lightweight construction products presents itself as a logical utilization process for a number of reasons. The main advantage is the
economic saving to the manufacturer, associated with the reduced
freight costs of shipping of the nished product, as compared to the
non-light weight product when weight is a factor. The reduced cost
is especially noticeable when products such as bricks are considered. Fly ash bricks weigh, on average, one-third less than
conventional clay-red bricks [410], enabling a truck to carry more
bricks per load, thus reducing shipping costs and improving prot
margins. The second economic reason is an abundance of low-cost
y ash available to make the bricks, yielding an excellent product.
Even though pulverised y ash brick at rst instance may appear to
be costlier than conventional products, ultimate nancial benet
can be evaluated in terms of its increased physical and chemical
properties. Depending on the type of soil, y ash (2050%) is used
along with clay to produce clay bricks which are more porous (40
50%) than y ash bricks (20%). Though clay-y ash bricks have high
strength and absorb less water than y ash bricks.
Fly ash bricks manufacturing units can be set up nearby thermal
power stations, because the main raw materials y ash is generated
by thermal power stations in a large quantity. Fly ash supplied by
thermal power stations at free of cost, the entrepreneur has to bear
only transportations charges from thermal power stations to the y
ash bricks manufacturing unit. There is good demand for y ash
bricks. The awareness among the people is required and also same
time the government has to give some special incentives for these
types of activities. The technologies are eco friendly, reduces solid
waste and dust in the nature. The cost is reasonable compared to
that of hallow brick and clay brick.
In the brick making industry, there has been research into how
to reuse different waste products in order to manufacture better
quality bricks [411414]. Although y ash is commonly used in
cements, it has rarely been applied to bricks. Recently it has been
shown that y ash might improve the compressive strength of
bricks and make them more resistant to frost [415]. Cicek and
Tanriverdi [416] observed the positive effect of the addition of y
ash, sand and hydrated lime in the compressive strength of the
bricks. In the eld of Architectural Heritage, there is almost no
research about y ash addition in the manufacture of replacement
bricks for use in restoration work. An essential criterion in this case
is that the bricks must have the same physical and mechanical
parameters (colour, porosity, hydraulic properties, etc.) as the
original bricks used in the building being restored.
The porosity of the brick depends directly on the mineralogical
composition of the raw material and the ring temperature, but
generally, bricks red at high temperatures are more vitreous and
undergo the greatest changes in size and porosity [417]. It has found
that y ash bricks are as durable as clay bricks and in fact in certain
aggressive environments perform better than clay bricks. Fly ash
can be used in the range of 4070%. The other ingredients are lime,
gypsum (/cement), sand, and stone dust/chips. Minimum
compressive strength (28 days) of 70 kg/cm2 can easily be achieved
and this can go up to 250 kg/cm2 (in autoclaved type).
Several studies show that y ash brick is a far superior building
material than burnt clay brick. The use of y ash brick provides
a stronger, more durable construction that is better protected from
eforescence and salinity with meaningful savings in construction
costs. But the greater benet lies in controlling two major
353
ecological problems of y ash disposal and the reduction of cultivable land that is needed for the production of burnt clay brick. The
advantage of these bricks over burnt clay bricks are: Lower
requirement of mortar in construction, Plastering over brick can be
avoided, Controlled dimensions, edges, smooth and ne nish and
can be in different colours using pigments, cost effective, energyefcient and environment friendly (as avoids the use of fertile clay).
The technical quality of compositionally different groups of solid
bricks red between 800 and 1000 C was evaluated [418]. The
textures of the bricks with y ash were very similar to the textures
of those without it, except that the samples with the additive
contained spherical y ash particles with diameters ranging from
0.1 to 10 mm. These particles led to a reduction in the density of the
bricks and a substantial improvement in their durability, with less
decay being caused by salt crystallization in the pores. This is
because y ash causes a reduction in the number of micropores, the
pores that make porous materials most vulnerable to salt-induced
decay. Use of this additive could have practical implications as
a means of recycling and for achieving cost savings in brick
production.
Fly ash in wet state with low quality was also used as raw
material to replace clay to make red bricks [419]. The effect of y
ash with high replacing ratio of clay on ring parameters and
properties of bricks were investigated. The results indicate that the
plasticity index of mixture of y ash and clay decreased dramatically with increased replacing ratio of y ash. Additive can be
chosen to improve the plasticity index of mixture to meet plastic
extrusion used in most brick making factories. The sintering
temperature of bricks with high replacing ratio of y ash was about
1050 C, which is 50100 C higher than that of clay bricks. The
properties of red bricks were improved by using pulverized y
ash. The red bricks with high volume ratio of y ash were of high
compressive strength, low water absorption, no cracking due to
lime, no frost and high resistance to frost-melting.
In addition to brick products, y ash has been utilized in the
manufacture of lightweight roong products such as rigid roong
tiles. The roong tiles have the advantage of being both lighter than
clay products and providing a class A re-rating making them an
excellent replacement for cedar shake roong in high re danger
areas. The manufacture of sintered y ash light weight aggregates is
an appropriate step to utilize a large quantity of y ash. Many
countries like the UK, USA, Germany, Poland and Russia are
producing lightweight aggregates commercially under different
trade names, such as Terlite, Lytag, Waylite corsonalite, sinterlite,
etc. Being lighter in weight, sintered y ash lightweight aggregates
will reduce the dead weight and material handling cost for multistoreyed constructions.
14. Road sub-base
Utilization of y ash as a material in the construction of roadways and associated peripheral projects has been a signicant
outlet for y ash. Fly ash has been used in embankment soil
stabilization, subgrade base course material, as an aggregate ller,
a bituminous pavement additive and as a mineral ller for bituminous concrete. Fly ash used as a soil stabilizer along roadway
embankments has been a benecial practice for a number of
reasons. In areas where borrow or ll and cover material are scarce,
y ash may be in plentiful supply from nearby electric power
generation facilities. Ease of availability combined with positive
physical properties can make y ash soil stabilization cost effective.
Shear strength is an important characteristic for soil stabilization
y ash utilization and it generally equals or exceeds the strength of
soils typically used for embankments [420,421]. This strength is
partially due to some y ash having self-hardening or pozzolanic
354
properties, which is a characteristic more common to class C y ash

and ash from atmospheric uidized bed boilers.
Construction of road embankments using y ash, involves
encapsulation of y ash in earthen core or with RCC facing panels.
Since there is no seepage of rain water into the y ash core, leaching
of heavy metals is also prevented. When y ash is used in concrete,
it chemically reacts with cement and reduces any leaching effect.
Even when it is used in stabilisation work, a similar chemical
reaction takes place which binds y ash particles. Hence chances of
pollution due to use of y ash in road works are negligible.
Use of y ash in road works results in reduction in construction
cost by about 1020%. Fly ash is available free of cost at the power
plant and hence only transportation cost, laying and rolling cost are
there in case of y ash. Hence, when y ash is used as a ll material,
the economy achieved is directly related to transportation cost of
y ash. If the lead distance is less, considerable savings in
construction cost can be achieved.
Similarly, the use of y ash in pavement construction results in
signicant savings due to savings in cost of road aggregates. If
environmental degradation costs due to use of precious top soil and
aggregates from borrow areas quarry sources and loss of fertile
agricultural land due to ash deposition are considered, the actual
savings achieved will be much higher and y ash use will be
justied even for lead distances up to say 100 km.
15. Mine backll
Mine back lling has demonstrated to be an attractive option for
those plants located near the coal mine. Back lling of underground
mines is technically vulnerable and especially holds good potentials
for those areas where sand is scarce. Open cast mine lling can
again be considered as land reclamation.
Fly ash grout injection is currently being considered for use at
a closed underground mining Site. The injection process would
reduce acid mine drainage (AMD) through a two-fold approach, by
neutralizing AMD and by preventing contact between water and
pyritic materials.
Acid mine drainage occurs in areas that have previously been
mined for coal and contain pyritic materials in spoil piles or in mine
shafts, where the pyritic material is in contact with both water and
atmospheric inuences. The spoil piles and mine shafts contain
iron pyrite in the tailings that chemically react with oxygen, water
and Thiobacllus bacteria, resulting in acid mine drainage.
Fly ash mine void lling has been carried out in both controlled
circumstances and in actual eld applications. Mine void lling is
undertaken for numerous reasons, the rst being for the control of
AMD, where the groundwater table intersects the mining rubble.
The second reason for y ash grout injection compliments AMD
control by lling mine voids and providing support to areas where
standing coal pillars are crumbling and causing land subsidence on
the surface. The third use for y ash injection is mine re control.
Underground coal mining operations conducted many years ago
removed large volumes of coal, leaving only small pillars to maintain the structural stability of the surrounding land surface. Environmental weathering over time caused the pillars to crumble and
AMD to occur due to the exposure of the pyritic material,
surrounding the coal seams, to the groundwater and atmosphere.
Through the use of high pressure injection, even areas that have
partially collapsed can be lled with y ash grout material to
prevent further subsidence, while disposing of large quantities of
y ash at the same time. The procedures for conducting underground mine void lling with y ash for AMD control, subsidence
control and re abatement are identical [422]. Two methods can be
used, dry y ash injection or wet slurry injection. Dry y ash
injection consists of drilling 6 inch diameter boreholes into the
mine void and placing steel casing down to that level. The dry y
ash is then injected at relatively low pressure (1230 psi) into the
mine void. The dry y ash easily owed 65 feet in either direction
from the borehole along the shaft as it lled to the mine roof. The
ash had an angle of repose of only 8 degrees from the horizontal
exhibiting excellent ow characteristics. The eventual lling at the
roof covered 15 feet in either direction from the borehole and
provided an airtight seal for the mine shaft. Moisture from
surrounding strata eventually provided the y ash with the water
needed for hydration and the y ash hardened, exhibiting no signs
of shrinkage or settling.
Fly ash-water slurry injection is conducted in much the same
manner as dry ash injection with the exception of the use of higher
injection pressures (up to 100 psi) and a slightly larger 10 inch
borehole being drilled [422]. Experimental results determined that
an ideal water content equating to approximately 100 gallons per
ton of y ash (25% water by total mix weight), produces a slurry
that pumps easily and does not shrink upon drying.
Bulk quantities of coal y ash have been used to replace the
conventionally used sand for reclaiming underground mines.
During 19992000, the national Thermal Power Corporation
Limited (NTPC), India used about 60,000 ton of ash for backlling
underground mines of Singareni Colliery Company Limited,
Southern India, in collaboration with Central Mining Research
Institute, India[423]. The potential application of coal y ash in
reclaiming abandoned coal mine is of great practical signicance.
Research and Development are still on for commercial use of such
huge quantum of y ash as mine-lling material. Since about 80%
coal is produced from open cast mines, Coal India Ltd., is in crucial
stage of being able to handle this excessive overburden and planning for y ash back lling in the abandoned mines for eco-engineering development with viable plant life. On the contrary Coal
India Ltd., itself, is facing problem of disposal of the abundant
overburden wastes (w6000 million m3) as against their in situ
volume of the available open cast mine pits (4000 million m3) and
regaining the conguration of the landscape [424]. Since there are
various limitations and threats to environmental degradation,
effective scientic work is to be done before a rm decision is taken
for bulk use of y ash in reclaiming abandoned mines.
The technical feasibility of disposing coal combustion by-products in underground mines has been proven and the selection of
this disposal alternative will be decided based primarily on cost and
regulatory compliance issues. As such, additional research on the
technical issues of injecting coal combustion by-products or coal
combustion by-product slurries should only be needed in limited
special circumstances. On the other hand, more research into the
chemical aspect and the interaction of the coal combustion byproducts, mine water, local geology, and groundwater is needed to
assess the environmental impact of coal combustion by-product
mine injection. Also, many new coal combustion by-products are
being generated and are presenting challenges for surface disposal,
let alone for underground disposal. For example, many electric
utilities have installed FGD scrubbers to meet the requirements of
the 1990 Clean Air Act Amendments. These by-products are
different both physically and chemically from y ash and require
additional research. A pilot study of xated scrubber sludge injection into an abandoned underground mine was recently performed
by the Indianapolis Power and Light Company at their Petersburg
Station. No degradation of groundwater was found following the
injection at this project.
16. Cost estimation
Fly ash is available free of cost at the power plant and hence only
transportation cost, laying and rolling cost are there in case of y
ash. Waste baggase y ash is available for $2 ton1, and considering

the cost of transport, chemicals, electrical energy, etc., used in the
process, the nished product would cost approximately $15
ton1[94].
In order to evaluate the nancial implications of y ash utilization in road construction as an alternative, comparative costs of
conventional and y ash based road construction for a given
geometry are needed. Kumar and Patil [425] assumed that y ash is
available free of cost and in the form suitable for road construction.
The cost of y ash based road construction depends mainly on the
cost of various resources replaced by y ash and lead (transportation distance). The y ash transportation cost would have
some nite value depending upon the lead. The soil is locally
available in abundance whereas other materials like stone aggregate, stone chips, etc., are to be transported to the work site. The
loading/unloading cost of the conventional material and y ash is
also assumed to be the same. The construction cost of a given layer
of y ash based road formation is the sum of the two cost terms
representing (i) conventional layer cost construction minus cost of
resource savings due to y ash utilization and (ii) transportation
cost of y ash.
Based on cost data of different resources saved, the costs of y
ash based road construction with exible and rigid pavement for
different lead were calculated. It can be seen that the cost savings in
y ash based embankment road construction is nearly 31% which is
in close agreement with the range of 3040% savings cited by
construction agencies in India [426]. It is also found that the
maximum percentage savings in construction cost can be obtained
in GSB layer due to complete replacement of the materials by y
ash. It was found that the total road construction cost savings
percentage decreases with lead due to increase in the y ash
transportation cost. The effect of lead on construction cost savings
reveals that the investment on y ash based road construction
would be nancially attractive only for a lead less than 60 and
90 km for exible and rigid pavements, respectively.
Use of y ash in road works results in reduction in construction
cost by about 1020%. Typically cost of borrow soil varies from
about Rs.100200 per cubic metre. Fly ash is available free of cost at
the power plant and hence only transportation cost, laying and
rolling cost are there in case of y ash. Hence, when y ash is used
as a ll material, the economy achieved is directly related to
transportation cost of y ash. If the lead distance is less, considerable savings in construction cost can be achieved. Similarly, the use
of y ash in pavement construction results in signicant savings
due to savings in cost of road aggregates. If environmental degradation costs due to use of precious top soil and aggregates from
borrow areas quarry sources and loss of fertile agricultural land due
to ash deposition are considered, the actual savings achieved will
be much higher and y ash use will be justied even for lead
distances up to say 100 km.
17. Barriers to utilization
There are a number of technical, economic, institutional, and
legal barriers to the use of large quantities of coal y ash. Technical
and economic barriers are not mutually exclusive in that technological advancements usually result in economic feasibility. Principal technical barriers include issues related to coal y ash
production, specications and standards, materials characterization, product demonstration and commercialization, and userrelated factors. Economic barriers to increased use of coal y ash
can be key among all factors affecting by-product use. With proper
economic incentives, other barriers to increased use of coal y ash
can be overcome. For coal-burning electric utilities, the revenues
from the sale of coal y ash are often insignicant. The high cost of
355
transportation of low unit-value coal y ash and competition from

locally available natural materials pose two of the most important
economic barriers.
Among the institutional and legal barriers are the lack of
knowledge of potential ash uses, sporadic data on environmental
and health effects, compositional inconsistencies in the products,
belief that other raw materials are readily available, lack of State
guidelines, and viewpoint of the industry that Environmental
protection agency (EPA) regulations and procurement guidelines
are too complicated and rigid rather than being general guidelines
for use.
An American Society for Testing and Materials subcommittee
under the Committee E-50 on Environmental Assessment, on
which the U.S. Geological Survey (USGS) is represented, was
recently formed to address the question of standards and denitions of coal and coal combustion products (CCP)-related terms.
Subcommittee members evaluated the latest draft of the denitions document. Recommendations were submitted to the
committee for action in 2001. This draft calls for the change of coal
combustion products (CCPs) to coal combustion by-products (CCBs)
to iterate the ideal denition of a product, which is the principal
reason for a process. It is argued that coal is burned to produce
energy, not ash. Therefore, energy is the product of coal-burning
processes; anything else is a by-product. Concerned industry and
government representatives, scientists, and engineers have formed
a number of national and international organizations to address the
removal of barriers to use of coal y ash.
Fly ash transportation cost for reclamation of abundant mine
and road construction is a major constraint. Restriction of excavation of earth for lling low-lying areas and construction of
embankment within 200 km radius of thermal power plant is
essential. Further, there should be a mandatory condition in the
policy legislation to use y ash in place of soil for such applications.
Lack of awareness on the advantages of y ash based products
among end-users is limiting new initiatives and market potential.
There should be an integrated approach by the coordination of
technologists, architects and manufacturers for the production of
superior quality of y ash based products to meet the consumer
acceptability and increased marketability. In addition, in association with scientists, policy makers and y ash generators, awareness of the quality parameters and benecial effects of y ash based
building materials and its utility should be made clear to the
general public for mass consumption and effective utilisation of y
ash. There is a production of huge quantity of y ash followed by
emission of green house gases and intrude signicantly for global
warming. Also similar situations exist in many developed and
developing countries. Hence, to comply with environmental
requirement, serious efforts are to be made to tackle this alarming
situation of y ash management to reduce the adverse effect on
environment and ecology and future hypothesis by nding remedial measures for the social development. Cost benet analysis of
y ash versus conventional building materials are needed to be
thoroughly evaluated for the concrete recommendation for maximising the use of coal y ash.
Barriers to utilisation of coal y ash on land occur in marketing,
transport, and through the potential for leachates containing trace
elements from y ash. These are being overcome by various means
in the utilisation sectors. It is essential to follow best engineering
practices to ensure that there is no environmental risk.
18. Future research and prospects
Fly ash has a great potential in environmental applications and
interesting alternative to replace activated carbon or zeolites for
adsorption in the air or water pollution treatment. Adsorption
356
performance of y ash strongly depends on its origin and chemical

treatment used for activation. Up to date, no industrial scale
application has been realized. Economic barriers have to be overcome in terms of high value and high volume utilization for the
industrial applications of y ash. Generally, raw y ash has low
adsorption capacity. Modication of y ash would enhance the
adsorption capacity [179]. Fly ash contains aluminosilicates and
a potential source for the synthesis of zeolites. Zeolite has a variety
of applications as adsorbents and ion exchangers and exhibits
much higher capacity than the raw y ash. Some investigations
have been made in the hydrothermal conversion of y ash into
different types of zeolites using the extracted supernatant solution.
Few researchers have been succeeded in the conversion of the bulk
y ash into pure zeolite [7]. The presence of silico-aluminate phases
in y ash makes it a suitable raw material for the synthesis of
geopolymer. Fly ash can be used for the synthesis of geopolymers
[427,428], mullite and quartzcristobalitetridymite. The amorphous aluminosiliate nature of y ash makes it a possible raw
material for many industrial reactions, such as, the synthesis of
ultramarine blue. Repeated harvesting of foodstuffs depletes trace
elements in the soil. Although, the use of y ash as soil amendment
has been studied, the full scale application of this technology has
not been implemented. In future, farmers may use y ash rather
than lime to enrich their soil. The trace elements in y ash might be
used to replace trace elements in the soil, and to increase mineral
content in the soil. Therefore, more research should be conducted
in these areas.
Unburned carbon is an important component of y ash, whose
composition in y ash varies with combustion efciency. In y ash,
unburned carbon contents generally range between 2% and 12%.
The higher percentage of unburned carbon in y ash will lead to
efciency loss and poor marketability for cement production.
Unburned carbon is similar to the precursors for production of
premium carbon materials, such as, activated carbon. Activated
carbon made from unburned carbon of y ash has a signicant
potential of cost advantage over other activated carbon. Therefore,
separation of unburned carbon from y ash will be benecial to y
ash application, either for carbon recycling or mineral y ash
application in cement production and zeolite synthesis. However,
few investigations have been currently conducted in the utilization
of unburned carbon for production of activated carbon. More
efforts should be attempted in this area.
Autoclaved cellular concrete (ACC), is a light weight building
product with high insulating value, which can be manufactured
using 6075% y ash by weight. Fly ash, with carbon content up to
12% may be used, thereby, allowing the high volume use of ash from
sources that do not meet ready-mix concrete specications. Further
research in this area is needed.
Fly ash can be considered as a valuable resource and needs to be
studied, in order to facilitate the application of y ash to new and
innovative areas of economic interest. This review aimed to act as
a stepping-stone for the prospective researchers into the rewarding
eld of y ash.
19. Conclusion
This paper has attempted to cover a wide spectrum of information so that the reader can better understand y ash utilization.
Understanding coal formation and combustion processes provides
both a background and basis for the alternative uses of the resultant
y ash. This review has shown that, in most cases, reported work to
date in this area has been of laboratory scale, and further development work is needed.
Fly ash, although posing environmental pollution, it is an
important raw material for various applications. The utilization of
y ash in construction, removal of organic compounds, heavy

metals, dyes, and zeolite synthesis can help a great deal in the
reduction of environmental pollution. For maximum benet, new
technologies for the efcient utilization of y ash should be made
use. To improve removal efciencies and adsorption capacities,
chemical modications of y ash is needed. The unburned carbon
in y ash plays an important role for adsorption and converted to
activated carbon, which will enhance the adsorption capacity.
Separation of unburned carbon from the minerals can bring
benets for applications of unburned carbon and utilization of
mineral section for cement production and zeolite synthesis. There
should be a greater emphasis on the development of new technology for efcient utilization of y ash. Fly ash utilization programme must be extensively taken up covering various aspects at
different level to minimize the environmental pollution. The review
pointed out that the key issue of critical comparison between y
ash generated products and processes, and those derived from
more traditional routes has not been extensively tackled. More
analysis of long-term economic and environmental impacts,
possibly through employing life cycle assessments (LCAs) is
needed. There is a scarcity of information on the environmental
impact of y ash as an ingredient in the preparation of materials.
Acknowledgement
The author would like to thank the reviewers of this manuscript
for their valuable suggestions and comments.
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Progress in Energy and Combustion Science 36 (2010) 327363

Contents lists available at ScienceDirect

Progress in Energy and Combustion Science

A review on the utilization of y ash

* Tel.: 91 3842 233 797.

M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327363

techniques by making them more affordable. It follows that an

M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327363

and organic matters, synthesis of zeolite, mine backll, light weight

cityl pyridinium chloride

2.1. Physical properties

M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327363

is also silt-sized, it is generally slightly coarser than bituminous coal

The mineralogical composition of y ash, which depends on the

M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327363

forming constituents in biomass fuels are quite diverse depending

4. Fly ash utilization

5. Adsorbents for cleaning of ue gas

SO2 D NO2 / SO3 D NO

CaOH2 D SO3 / CaSO4 D H2 O

As shown in the above chemical formulas, the sulfur dioxides in

M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327363

desulphurization was also studied by Davini [25,26]. It was found

Dry-type FGD using y ash is one of the processes that provide

ue gas, due to its high removal efciency. In this process, activated

M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327363

compared to the amount of each type of unburned carbons in the

5.4. Adsorption of gaseous organics

6. Removal of toxic metals from wastewater

(continued on next page)

M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327363

Fly ash wollastonite

6.1. Adsorption of various types of heavy metals on y ash

indicated the process to be diffusion controlled. Fly ash with

M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327363

Banerjee et al. [60,61], studied the adsorption of various toxic

metal ions onto the surface of y ash was found to be proportional

M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327363

be controlled by the slowest step that would be either lm diffusion

empirical model used to describe adsorption in aqueous systems,

The linear form of the equation can be written as:

where k1, k2, ks and ki are the pseudo-rst order, pseudo-second

where, Kf is the measure of sorption capacity, 1/n is sorption

The Langmuir, Freundlich, RedlichPeterson, DubininKaganer

However, the linear form of the equation can be written as

Where Ce is the equilibrium concentration of the solution, x/m is

where, q is the heat of adsorption. Langmuir model can describe

This isotherm describes adsorption on heterogeneous surfaces,

where, Qe is the amount adsorbed (mol/gm), Qm (mol/gm) is the

where T is the temperature and C is the equilibrium concentration

Tempkin and Pyzhev considered the effects of some indirect

Eq. (18) can be expressed in its linear form as:

A plot of qe versus ln Ce enables the determination of the

M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327363

where Ks (L/g) and as (L/mg) are Sips isotherm constants and b is

strongly adsorb or precipitate phosphates in many agricultural,

6.4. Factors affecting adsorption of metal on y ash

7.1. Removal of phosphate

The adsorption of heavy metals on y ash is dependent on both

Kuziemska rst reported an investigation using water extract of

where, Kc is equilibrium constant that is resulted from the ratio of

M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327363