Progress in Energy and Combustion Science 36 (2010) 327–363

Contents lists available at ScienceDirect

Progress in Energy and Combustion Science

journal homepage: www.elsevier.com/locate/pecs

A review on the utilization of fly 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: Fly ash, generated during the combustion of coal for energy production, is an industrial by-product which
Received 8 August 2009 is recognized as an environmental pollutant. Because of the environmental problems presented by the fly
Accepted 10 November 2009 ash, considerable research has been undertaken on the subject worldwide. In this paper, the utilization of
Available online 28 December 2009
fly ash in construction, as a low-cost adsorbent for the removal of organic compounds, flue gas and
metals, light weight aggregate, mine back fill, road sub-base, and zeolite synthesis is discussed.
Keywords:
A considerable amount of research has been conducted using fly ash for adsorption of NOx, SOx, organic
Fly ash
compounds, and mercury in air, dyes and other organic compounds in waters. It is found that fly ash is
Adsorption
Wastewater a promising adsorbent for the removal of various pollutants. The adsorption capacity of fly ash may be
Heavy metals increased after chemical and physical activation. It was also found that fly ash has good potential for use
Dye in the construction industry. The conversion of fly ash into zeolites has many applications such as ion
Organics exchange, molecular sieves, and adsorbents. Converting fly ash into zeolites not only alleviates the
Zeolite disposal problem but also converts a waste material into a marketable commodity. Investigations also
Construction revealed that the unburned carbon component in fly ash plays an important role in its adsorption
capacity. Future research in these areas is also discussed.
Ó 2009 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
2. Properties of coal fly ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
2.1. Physical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
2.2. Chemical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
3. Properties of biomass ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
4. Fly ash utilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .331
5. 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
6. 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
7. 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
8. Removal of organic compounds from wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
8.1. Removal of phenolic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338

* Tel.: þ91 3842 233 797.

E-mail address: md_a2002@rediffmail.com

0360-1285/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.pecs.2009.11.003
328 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363

8.2. Removal of pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339

8.3. Removal of other organic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340
9. 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
10. Leaching of fly ash in water system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
11. Synthesis of zeolite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
11.1. Application of zeolite synthesised from fly ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
12. Construction work/industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
13. Lightweight aggregate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
14. Road sub-base . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
15. Mine backfill . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
16. Cost estimation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
17. Barriers to utilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
18. Future research and prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
19. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356

1. Introduction techniques by making them more affordable. It follows that an

economically viable solution to this problem should include utili-
Since wide scale coal firing for power generation began in the zation of waste materials for new products rather than land
1920s, many millions of tons of ash and related by-products have disposal.
been generated. The current annual production of coal ash world- Fly ash is generally grey in color, abrasive, mostly alkaline, and
wide is estimated around 600 million tones, with fly ash consti- refractory in nature. Pozzolans, which are siliceous or siliceous and
tuting about 500 million tones at 75–80% of the total ash produced aluminous materials that together with water and calcium
[1]. Thus, the amount of coal waste (fly ash), released by factories hydroxide form cementitious products at ambient temperatures,
and thermal power plants has been increasing throughout the are also admixtures. Fly ash from pulverized coal combustion is
world, and the disposal of the large amount of fly ash has become categorized as such a pozzolan. Fly ash also contains different
a serious environmental problem. The present day utilization of ash essential elements, including both macronutrients P, K, Ca, Mg and
on worldwide basis varied widely from a minimum of 3% to micronutrients Zn, Fe, Cu, Mn, B, and Mo for plant growth. The geo-
a maximum of 57%, yet the world average only amounts to 16% of technical properties of fly ash (e.g., specific gravity, permeability,
the total ash [1]. A substantial amount of ash is still disposed of in internal angular friction, and consolidation characteristics) make it
landfills and/or lagoons at a significant cost to the utilizing suitable for use in construction of roads and embankments, struc-
companies and thus to the consumers. tural fill etc. The pozzolanic properties of the ash, including its lime
Coal is a dominant commercial fuel in India, where 565 mines binding capacity makes it useful for the manufacture of cement,
are operated by Coal India and other subsidiaries. In 2003, building materials concrete and concrete-admixed products. The
production of hard coal was 358.4 Mt.; while utilization was 407.33 chemical composition of fly ash like high percentage of silica (60–
Mt. India is the sixth largest electricity generating and consuming 65%), alumina (25–30%), magnetite, Fe2O3 (6–15%) enables its use
country in the world. Fly ash can be considered as the world’s fifth for the synthesis of zeolite, alum, and precipitated silica. The other
largest raw material resource [2]. An estimated 25% of fly ash in important physicochemical characteristics of fly ash, such as bulk
India is used for cement production, construction of roads and brick density, particle size, porosity, water holding capacity, and surface
manufacture [3]. The fly ash utilization for these purposes is area makes it suitable for use as an adsorbent.
expected to increase to nearly 32 Mt by 2009–2010. Currently, the From the perspective of power generation, fly ash is a waste
energy sector in India generates over 130 Mt of FA annually [4] and material, while from a coal utilization perspective, fly ash is
this amount will increase as annual coal consumption increases by a resource yet to be fully utilized; producers of thermal electricity
2.2%. The large-scale storage of wet fly ash in ponds takes up much are thus looking for ways to exploit fly ash. The cement industry
valuable agricultural land approximately (113 million m2), and may might use it as a raw material for the production of concrete. Coal
result in severe environmental degradation in the near future, fly ash discharged from power plants can also be utilized as a by-
which would be disastrous for India. product, and its use in recycling materials for agriculture and
Fly ash particles are considered to be highly contaminating, due engineering is also being studied [5,6]. The conversion of fly ash
to their enrichment in potentially toxic trace elements which into zeolite has also been widely examined [7].
condense from the flue gas. Research on the potential applications Another interesting possibility might be use as a low-cost
of these wastes has environmental relevance, in addition to adsorbent for gas and water treatment. Several investigations are
industrial interest. Most of the fly ash which is produced is disposed reported in the literature on the utilization of fly ash for adsorption
of as landfill, a practice which is under examination for environ- of individual pollutants in an aqueous solution or flue gas. The
mental concerns. Disposal of fly ash will soon be too costly – if not results are encouraging for the removal of heavy metals and
forbidden. Considerable research is being conducted worldwide on organics from industrial wastewater. This paper will review the
the use of waste materials in order to avert an increasing toxic various applications of fly ash, including low-cost adsorbents for
threat to the environment, or to streamline present waste disposal flue gas cleaning, wastewater treatment for removal of toxic ions
 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363 329

Nomenclature CPC cityl pyridinium chloride

CR Congo red
A Redlich–Peterson constant DDD 2,2-bis (4chloro-phenyl)-1,1,-dichloro ethane
B Redlich–Peterson constant DDE 2,2-bis (4chloro-phenyl)-1,1,-dichloro ethane
Ce equilibrium concentration of the solution DEF delayed ettringite formation
Cs surface concentration DNP di-ntrophenol
Ct solution concentration DTA differential thermal analysis
k1 pseudo-first order rate constant EDTA ethylene diamine tetraacetic acid
k2 pseudo-second order rate constant EPA Environmental protection agency
ks mass transfer co-efficient FA fly ash
ki rate parameter of intraparticle diffusion control stage FAZ-Y fly ash based zeolite
qe amount of adsorbate adsorbed at equilibrium (mg/g) FGD flue gas desulphurization
qt amount of adsorbate adsorbed at any time t (mg/g) FTIR Fourier Transform infrared spectroscopy
DG0 standard Gibb’s free energy of adsorption (kJ/mol) GGBFS ground granulated blast furnace slag
DH0 standard enthalpy change of adsorption (kJ/mol) HDTMA hexadecyl tetramethyl ammonium
K Langmuir equilibrium constant HeCB 2,21,3,31,4,5,6-heptachlorobiphenyl
Kd distribution co-efficient HVFA high-volume fly ash
Kf Freundlich constant HSFA high-sulphate fly ash
m mass of the adsorbent IFA impregnated fly ash
1/n adsorption intensity LCA life cycle assessments
q heat of adsorption LOI loss on ignition
R universal gas constant MB methylene blue
S specific surface area MSWI Municipal solid waste incinerator bottom ash
DS0 standard entropy change of adsorption (JK1 mol1) MV methyl violet
t1/2 half-life period NMR nuclear magnetic resonance
V eluted volume (ml) NPC normal Portland cement
Vb volume of effluent at break point (ml) OG Orange-G
Vm Langmuir monolayer adsorption capacity OPC ordinary Portland cement
x/m amount adsorbed per unit of the adsorbent PPC Pozzolana Portland cement
b heterogeneity factor RB rhodamine B
RBB Remazol brillant blue
Abbreviations RCC reinforced concrete construction
AASHTO American association of state highway and transport RHFA rice husk fly ash
officials RPC reactive powder concrete
ABS acrylonitrile butadiene styrene RY rifacion yellow HED
ACC autoclaved cellular concrete SDS sodium dodecyl sulphate
ACCG activated carbon-commercial grade SSA sewage sludge ash
ACLG activated carbon laboratory grade SEM scanning electron microscope
Acid Orange 7 p-(2-hydroxy-1 naphthylazo)benzene sulfonic SMZ-Y surface modified fly ash based zeolite
acid TCB 2,3,4-trichloro biphenyl
AEA air entraining admixture TCLP Toxicity Characteristic Leaching Procedure
AMD acid mine drainage TEA tetramethyl ammonium
ASR alkali–silica reaction TEM transmission electron microscope
ASTM American society for testing of materials TOC total organic carbon
BDTDA benzyldimethyl tetradecylammonium TPABr tetraporpyl ammonium bromide
BFA bagasse fly ash USEPA United States environmental protection agency
BG Brilliant green UHPC ultra high-performance concrete
CANMET Canada centre for mineral and energy technology TNT tri-nitro toluene
CC char-carbon UHPC ultra high-performance concrete
CCP coal combustion products WC wood charcoal
CCB coal combustion by-products XRD X-ray diffraction
CEC cation exchange capacity XRF X-ray fluorescence
CFA coal fly ash ZFA zeloite fly ash
CFS chemical fixation and solidification

and organic matters, synthesis of zeolite, mine backfill, light weight
aggregate, road sub-base and construction/cement applications.
2. Properties of coal fly ash
Characterisation of fly ash in terms of composition, mineralogy,
surface chemistry and reactivity is of fundamental importance in
the development of various applications of fly ash.
2.1. Physical properties
Fly ash consists of fine, powdery particles predominantly
spherical in shape, either solid or hollow, and mostly glassy
(amorphous) in nature. The carbonaceous material in the fly ash is
composed of angular particles. The particle size distribution of most
bituminous coal fly ash is generally similar to that of silt (less than
a 0.075 mm or No. 200 sieve). Although sub-bituminous coal fly ash
330 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363

is also silt-sized, it is generally slightly coarser than bituminous coal The mineralogical composition of fly ash, which depends on the
fly ash. The specific gravity of fly ash usually ranges from 2.1 to 3.0, geological factors related to the formation and deposition of coal,
while its specific surface area may vary from 170 to 1000 m2/kg [8– its combustion conditions, can be established by X-ray diffraction
11]. The colour of fly ash can vary from tan to gray to black, (XRD) analysis. The dominant mineral phases are quartz, kaolinite,
depending on the amount of unburned carbon in the ash. 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
2.2. Chemical properties
high-calcium fly ash consists of quartz, C3A, CS and C4AS.
The several distinct end uses of fly ash differ considerably
The chemical properties of fly ash are influenced to a great extent
among themselves in the stringency of the properties required in
by the properties of the coal being burned and the techniques used for
the fly ash for its successful utilization. The success of fly ash in
handling and storage. There are basically four types, or ranks, of coal,
structural fill applications rests primarily on the ability of the
each vary in heating value, chemical composition, ash content, and
material to be compacted to a reasonably strong layer of low unit
geological origin. The four types (ranks) of coal are anthracite, bitu-
weight. This is primarily a function of particle size distribution, and
minous, sub-bituminous, and lignite. In addition to being handled in
to some extent of the content of spherical particles. The chemical
a dry, conditioned, or wet form, fly ash is also sometimes classified
characteristics of fly ash are secondary, although the post
according to the type of coal from which the ash was derived.
compaction cementation provided by some high-calcium fly ash is
The principal components of bituminous coal fly ash are silica,
likely to prove beneficial.
alumina, iron oxide, and calcium, with varying amounts of carbon,
With highway bases chemical considerations come into play,
as measured by the loss on ignition (LOI). Lignite and sub-bitumi-
although not in an important way. Stabilization of some base
nous coal fly ash is characterized by higher concentrations of
courses (and stabilized sub grades) may rest on lime fly ash
calcium and magnesium oxide and reduced percentages of silica
chemical reactions, i.e. the classical ‘‘pozzolanic’’ reaction, with
and iron oxide, as well as lower carbon content, compared with
lime. Low-calcium fly ash may be entirely satisfactory or even
bituminous coal fly ash. Very little anthracite coal is burned in
preferred, especially where sufficient time is available for these
utility boilers, so there are only small amounts of anthracite coal fly
slow reactions to take place. The only real chemical requirement is
ash. Table 1 compares the normal range of the chemical constitu-
that fly ash has a sufficient content of glass that eventually will
ents of bituminous coal fly ash with those of lignite coal fly ash and
react with added lime. Some road base applications of fly ash
sub-bituminous coal fly ash. From the table, it is evident that lignite
depend on the physical effects of fly ash incorporation rather than
and sub-bituminous coal fly ash has a higher calcium oxide content
its reaction with lime.
and lower loss of ignition than fly ash from bituminous coals.
The cement and concrete end-use areas are by far the most
Lignite and sub-bituminous coal fly ash may have a higher
demanding of the fly ash in terms of adherence to strict criteria and
concentration of sulphate compounds than bituminous coal fly ash.
requirements. However, the requirements differ considerably
According to the American Society for Testing Materials (ASTM
depending on the specific end use involved.
C618) [12], the ash containing more than 70 wt% SiO2 -
Fly ash for use as a raw material in cement manufacture is sold
þ Al2O3 þ Fe2O3 and being low in lime are defined as class F, while
and used primarily on the basis of its chemical composition, as
those with a SiO2 þ Al2O3 þ Fe2O3 content between 50 and 70 wt%
expressed in the usual oxide convention. Such factors as glass
and high in lime are defined as class C. Briefly, the high-calcium
content, the type of crystalline matter present, size distribution, etc.,
Class C fly ash is normally produced from the burning of low-rank
are relatively immaterial. Even high carbon content, which may be
coals (lignites or sub-bituminous coals) and have cementitious
limiting in most other end uses, may actually be beneficial in cement
properties (self-hardening when reacted with water). On the other
raw material use, since it provides a definite (although modest)
hand, the low-calcium Class F fly ash is commonly produced from
proportion of the fuel needed. Uniformity and chemical consistency
the burning of higher-rank coals (bituminous coals or anthracites)
from day to day and week to week is the prime necessity.
that are pozzolanic in nature (hardening when reacted with
Fly ash, as a blended cement component shares some of the
Ca(OH)2 and water). The chief difference between Class F and Class
requirements for both raw material and direct concrete admixture
C fly ash is in the amount of calcium and the silica, alumina, and
use. Since such fly ash eventually is incorporated in concrete, its
iron content in the ash. In Class F fly ash, total calcium typically
chemical and physical characteristics must be suitable for that
ranges from 1 to 12%, mostly in the form of calcium hydroxide,
purpose. However, since little or no adjustment can be provided at
calcium sulphate, and glassy components, in combination with
the concrete mixing stage, fly ash for use in blended cements must
silica and alumina. In contrast, Class C fly ash may have reported
be of consistent and uniform chemical and physical characteristics,
calcium oxide contents as high as 30–40%. Another difference
the consistency and predictability being as important as the
between Class F and Class C is that the amount of alkalis (combined
numerical values of the various parameters involved. Since the
sodium and potassium), and sulphates (SO4), are generally higher
blended cement manufacturer has little control over the concurrent
in the Class C fly ash than in the Class F fly ash.
use of chemical admixtures or of mixing and curing conditions, the
Table 1 fly ash used should be relatively insensitive to such variations.
Normal range of chemical composition for fly ash produced from different coal Especially to be considered here are rheological effects, strength
types.
development characteristics, and possibilities for developing
Component (wt.%) Bituminous Sub-bituminous Lignite efflorescence. The color of the ash and its effect on the color of the
SiO2 20–60 40–60 15–45 final concrete to be produced by the blended cement may also be of
Al2O3 5–35 20–30 10–25 importance.
Fe2O3 10–40 4–10 4–15
CaO 1–12 5–30 15–40
MgO 0–5 1–6 3–10 3. Properties of biomass ash
SO3 0–4 0–2 0–10
Na2O 0–4 0–2 0–6 The use of biomass as fuel generates large amount of residual
K2O 0–3 0–4 0–4 ash which causes serious environmental problems. Biomass ash
LOI 0–15 0–3 0–5
does not contain toxic metals like in the case of coal ash. The ash
 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363
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 deter-
mined by the inorganic constituents in the parent biomass, the
crystallinity and mineralogy depends on the combustion tech-
nique used.
Typically, fly ash from neat biomass combustion has more alkali
(Na and K) and less alumina (Al2O3) than coal fly 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 fly ash varies more than coal fly 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 fly ash depends also on some growth and
production factors including weather, season, storage and
geographic origins [16,17].
Compared to coal fly ash where significant research has already
taken place and high utilisation figures 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 fly ash have similar pozzolanic proper-
ties as coal fly ash, such as those from rice husk, wood, wheat straw
and sugar cane straw [19–21] among which have been added in
concrete as mineral admixtures, improving the performance of
concrete.
Bagasse fly ash has been examined as an adsorbent as well as an
additive in cement and concrete [19–21]. 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 fly 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
financial 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 fly 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 fill and cover material, roadway and pavement utiliza-
tion, addition to construction materials as a light weight aggregate,
infiltration barrier and underground void filling, and soil, water and
environmental improvement. The following is a brief description of
each of the previously mentioned alternative uses of fly ash and
associated research that has been conducted and how it relates to
each alternative use. In this section, the application of fly ash has
been discussed.
331
5. Adsorbents for cleaning of flue gas
5.1. Sulphur compounds
Effort has been made to reduce SOx emissions by installing
equipment for flue gas desulphurization (FGD). The wet-type
limestone scrubbing processes is widely used because of its high
DeSOx efficiency 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 waste-
water 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 efficiency. The reactions are represented below.
NO D 1=2 O2 / NO2 (1)
SO2 D NO2 / SO3 D NO (2)
CaðOHÞ2 D SO3 / CaSO4 D H2 O (3)
As shown in the above chemical formulas, the sulfur dioxides in
the flue gas are fixed as gypsum. On the other hand, they are fixed
as sulfite in other conventional dry processes such as limestone
injection and active manganese. Some of the spent absorbent dis-
charged from the desulfurization process can be used as the raw
material for the absorbent pellets. In addition, this spent absorbent
is reused as a solidification agent for sludge and as a deodorant for
refrigerators, pet litter and so on [23]. The process flow 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 fixed 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 simplified
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 fly ash is a cheap absorbent for
dry-type FGD. Fly ash recycling in the flue 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 fly ash and calcium hydroxide for
Fig. 1. Schematic plant view of flue gas desulfurization using coal ash [23].
332 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363
desulphurization was also studied by Davini [25,26]. It was found
that Ca(OH)2-fly ash mixtures were a low-cost SO2 control option.
Davini [27] also tested a process using activated carbon derived
from fly ash for SO2 and NOx adsorption from industrial flue gas;
this mixture exhibited similar characteristics to typical activated
carbon for flue gases.
The FGD process using coal ash has been commercialized, and
some industrial plants have achieved DeSOx efficiencies 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 (1.0–1.2) [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 ðslurryÞDSO2 D 1=2 O2 / CaSO4 ðslurryÞ D CO2 (4)
Dry-type FGD using fly 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 flue gases [29]. The properties of fly ash – particularly with
respect to NOx adsorption – were closely examined for carbon
content and specific surface area. It was found that unburned
carbon remaining in the fly ash particles contribute the main
surface area to fly ash, and the carbon can be activated to further
improve the adsorption performance of the fly ash. Experimental
results on activating coarser fly ash particles showed that adsorp-
tion capacity can be increased through controlled gasification of the
unburned carbon. So, this carbon present in fly ash can be
a precursor of activated carbons since it has gone through devola-
tilization 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 fly ash was reported [31].
Carbon-rich fractions from a gasifier were adsorbed one-third of
the NOx compared with a commercial carbon. Recently, activated
carbon from unburned carbon in coal fly ash has also been used for
removal of NO [32]. It was found that mineral matter must be
removed efficiently from unburnt carbon of fly ash before activa-
tion, 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 identified 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 difficult 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 flue 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
flue gas, due to its high removal efficiency. In this process, activated
carbon powder is injected into the flue 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 find an alternative
carbon.
Usually the unburned carbon content in fly ash is in the range of
2–12%. However, with the introduction of the 1990 Clean Air Act
Amendments, caps have been established on the emission of
nitrogen oxides (NOx). Many coal-fired utilities have begun to
retrofit with low NOx burners to meet the emission requirements.
As a result of such transition, the carbon content of fly ash increases
significantly, 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 fly
ash is a by-product, any practical application of such material
would be economically and environmentally advantageous to the
overall fly ash beneficiation process. Researchers at The Pennsyl-
vania State University have developed a method to economically
separate unburned coal from fly ash [34]. Preliminary study shows
that some unburned carbon from fly ash has certain capabilities for
adsorbing elemental mercury. Such findings triggered the idea of
using fly ash carbon as a low-cost adsorbent in removing elemental
mercury from gas phases, such as utility flue gas, to replace costly
activated carbons.
The retention of hazardous elements by fly ash produced in
combustion plants has been extensively studied in recent years. In
the case of mercury it has been observed that some fly ash may
capture this element which would otherwise be emitted into the
atmosphere. Although the role of inorganic components of fly ash
in this capture is still unclear, considerable attention has been paid
to the capture of mercury by unburned fly ash carbons [35–42].
A relationship has been reported between Hg content and the
percentage of carbon in fly 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 fly 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 [37,43–45], given that the BET surface area
successively increased from inertinite, isotropic coke (isotropic fly
ash carbons) to anisotropic coke (anisotropic fly ash carbons) [37].
The exact nature of Hg–fly ash interactions is still unknown and
the variables affecting the mercury adsorption need to be identi-
fied. In view of the significant variations in the properties of fly ash
obtained from different coals [43,46–48], and to better understand
the properties of the materials influencing the capture of Hg, López-
Antón et al. [49] have tried to establish a relationship between Hg0
and HgCl2 retention and the characteristics of fly 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 fly 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 fly ash in a greater proportion than HgCl2. When the
raw fly 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 fly 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
 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363 333

compared to the amount of each type of unburned carbons in the Table 2

fly ash, no correlations were found. However, a general tendency Summary of adsorption of metals on fly ash.

could be observed with the anisotropic, fused and porous struc- Metals Adsorbent Adsorption Temperature ( C) References
tures (which are mainly network structures in all cases). The fly ash capacity (mg/g)
samples that have a greater surface area retain a higher quantity of Zn2þ Coal fly ash 6.5–13.3 30–60 [81]
HgCl2, but this tendency shows several exceptions in the case of Hg. Fe impregnated fly ash 7.5–15.5 30–60
Al impregnated fly ash 7.0–15.4 30–60
The adsorption of mercury on carbon can be explained by the
Coal fly ash 0.25–2.8 20 [83]
physical and chemical interactions which occur between the Coal fly ash(I) 0.25–1.19 20 [84]
carbon surface and mercury. According to the theory proposed by Coal fly ash(II) 0.07–1.30 20
Dubini [50] the carbon surface contains some adsorption centers, Bagasse fly ash 2.34–2.54 30–50 [93]
called primary sites. When a molecule of the adsorbate adsorbs on Bagasse fly ash 13.21 30 [94]
Fly ash 4.64 23 [104]
a primary site, the adsorbed molecule can then act as a secondary Fly ash 0.27 25 [105]
center for the adsorption of more molecules. The enhancement of Fly ash 0.068–0.75 0–55 [106]
mercury adsorption after oxidizing unburned carbon at 400  C in Fly ash 3.4 – [87]
air shows that oxygen-containing functional groups may have an Rice husk ash 5.88 [86]
Bagasse fly ash 7.03 [85]
important role, which is also suggested by Hall et al. [51]. Masaki
Fly ash 11.11 [71]
et al. [52] utilized synthetic fly ash, consisting of calcium chloride Rice husk ash 14.30 [63]
with 5% activated carbon, which showed very high efficiency of Fly ash 7.84 [71]
over 99% for mercury removal at 120  C. When the calcium chloride Cd2þ Fly ash 198.2 25 [79]
content was more than 0.5% in the synthetic fly ash with 5% acti- Fly ash-washed 195.2 25
vated carbon, mercury vapor was completely removed. However, Fly ash-acid 180.4 25
the most efficient removal was obtained when the activated carbon Fly ash 1.6–8.0 – [80]
Fly ash zeolite 95.6 20
content ranged from 5 to 7% in synthetic fly ash with 1% calcium
Fly ash 0.67–0.83 20 [83]
chloride. The removal of mercury was affected by temperature, if Fly ash (I) 0.08–0.29 20 [85]
the activated carbon content was very small. It was assumed that Fly ash (II) 0.0077–0.22 20
the complex chemical action with activated carbon and calcium Bagasse fly ash 1.24–2.0 30–50 [95]
chloride was most significant for metallic mercury removal by Fly ash 0.05 25 [105]
Coal fly ash 18.98 25 [70]
actual fly ash. Rice husk ash 3.04 [86]
Afsin-Elbistan fly ash 0.29 [64]
Seyitomer fly ash 0.21
Bagasse fly ash 6.19 [85]
5.4. Adsorption of gaseous organics Fly ash 207.3 [79]
Fly ash 1.38 [68]
Apart from the adsorption of NOx, SOx and mercury in flue gas, Pb2þ Fly ash 444.7 25 [79]
fly ash has also been used for adsorption of organic gas. The Fly ash-washed 483.4 25
adsorption of toluene vapours on fly ash was investigated by Peloso Fly ash-acid 437.0 25
et al. [53]. It was found that fly ash product obtained after particle Fly ash 753 32
Bagasse fly ash 285–566 30–50 [92]
aggregation and thermal activation showed satisfactory adsorption Fly ash 18.8 [87]
performance for toluene vapours [54]. The adsorption kinetics of Fly ash 18.0 [75]
representative aromatic hydrocarbon and m-xylene, on fly ash has Treated rice husk ash 12.61 30 [73]
also been studied [55]. The results indicated that the kinetics of m- Cu 2þ
Fly ash 1.39 30 [68]
xylene adsorption by fly ash resembled kinetics reported for Fly ash þ wollastonite 1.18 30
penetration of absorbates into porous adsorbents. No increase in Fly ash 1.7–8.1 – [80]
adsorption rates was observed with increased temperature, and Fly ash (I) 0.34–1.35 20 [84]
Fly ash (II) 0.09–1.25 20
rate constants decreased with increased vapour pressure. This
Fly ash 207.3 25 [79]
suggested that adsorption was diffusion-controlled. Fly ash-washed 205.8 25
Fly ash-acid 198.5 25
Fly ash 0.63–0.81 25 [69]
Bagasse fly ash 2.26–2.36 30–50 [93]
6. Removal of toxic metals from wastewater Fly ash 0.76 32 [100]
Fly ash 7.5 – [87]
Coal fly ash 20.92 25 [70]
Fly ash has potential application in wastewater treatment
Fly ash 7.0 [75]
because of its major chemical components, which are alumina, CFA 178.5–249.1 30–60 [74]
silica, ferric oxide, calcium oxide, magnesium oxide and carbon, CFA-600 126.4–214.1 30–60
and its physical properties such as porosity, particle size distribu- CFA–NAOH 76.7–137.1 30–60
tion and surface area. Moreover, the alkaline nature of fly ash makes Ni2þ Fly ash 9.0–14.0 30–60 [81]
it a good neutralising agent. Generally, in order to maximise metal Fe impregnated fly ash 9.8–14.93 30–60
adsorption by hydrous oxides, it is necessary to adjust the pH of Al impregnated fly ash 10–15.75 30–60
Fly ash(I) 0.40–0.98 20 [84]
wastewater using lime and sodium hydroxide [56,57].
Fly ash(II) 0.06–1.16 20
Today, heavy metals are most serious pollutants, becoming Bagasse fly ash 1.12–1.70 30–50 [95]
a severe public health problem. Heavy metal and metalloid removal Fly ash 3.9 [87]
from aqueous solutions is commonly carried out by several Bagasse fly ash 6.48 [85]
processes such as, chemical precipitation, solvent extraction, ion Fly ash 0.03 [67]

exchange, reverse osmosis or adsorption etc. Among these Cr3þ Fly ash 52.6–106.4 20–40 [65]
processes, the adsorption process may be a simple and effective
(continued on next page)
technique for the removal of heavy metals from wastewater.
334 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363

Table 2 (continued ) indicated the process to be diffusion controlled. Fly ash with
Metals Adsorbent Adsorption Temperature ( C) References different quantities of carbon and minerals was also used for
capacity (mg/g) removal of Cu(II) from an aqueous solution [69]. The carbon fraction
Cr6þ Fly ash þ wollastonite 2.92 – [61] in fly ash was important in the removal of Cu(II). The specific
Fly ash þ China clay 0.31 – adsorption capacities of carbon ranged from 2.2 to 2.8 mg Cu/g
Fly ash 23.86 – [62] carbon, while the capacities for mineral were only about 0.63–
Rice husk Ash 25.64 –
0.81 mg Cu/g mineral. Fly ash can also be shaped into pellets and
Fly ash 1.38 30–60 [82]
Fe impregnated fly ash 1.82 30–60 used for the removal of copper and cadmium ions from aqueous
Al impregnated fly ash 1.67 30–60 solutions [70]. The calculated adsorption capacities for copper and
Fly ash(I) 0.55 20 [85] cadmium were found to be 20.92 and 18.98 mg/g, respectively. It was
Fly ash(II) 0.82 20 [85] found that fly ash shaped into pellets could be considered as
Bagasse fly ash 4.25–4.35 30–50 [97]
a potential adsorbent for the removal of copper and cadmium from
Hg2þ Fly ash 2.82 30 [76] wastewaters. Equilibrium studies for the adsorption of zinc and
Fly ash 11.0 30–60 [82]
copper from aqueous solutions were carried out using sugar beet
Fe impregnated fly ash 12.5 30–60
Al impregnated fly ash 13.4 30–60 pulp and fly ash [71]. The removal characteristics of Pb(II) and Cu(II)
Sulfo-calcic 5.0 30 [87] from aqueous solution by fly ash were investigated by Alinnor [72].
Silico-aluminous ashes 3.2 30 [87] The utilization of rice husk ash was investigated for the adsorption of
Fly ash-C 0.63–0.73 5–21 [77] Pb(II) and Hg(II) from aqueous water [73]. The Bangham equation
Treated rice husk ash 6.72 30 [73]
As3þ Fly ash coal-char 3.7–89.2 25 [109]
can be used to express the mechanism for adsorption of Pb(II) and
As5þ Fly ash 7.7–27.8 20 [107] Hg(II), by rice husk ash. Its adsorption capability and adsorption rate
Fly ash coal-char 0.02–34.5 25 [109] are considerably higher and faster for Pb(II) than for Hg(II). The finer
the rice husk ash particles used, the higher the pH of the solution and
the lower the concentration of the supporting electrolyte, potassium
6.1. Adsorption of various types of heavy metals on fly ash nitrate solution, the more Pb(II) and Hg(II) absorbed on rice husk ash.
Raw and modified coal fly ash effectively adsorbs Cu(II) from
Fly ash has been widely used as a low-cost adsorbent for the wastewater [74]. These adsorptions were endothermic in nature;
removal of heavy metal. Table 2 summarizes the results of the the values of activation energy (between 1.3 and 9.6 kJ mol1) were
important metals investigated using fly ash. Among these metal consistent with an ion exchange adsorption mechanism. The
ions, Ni, Cr, Pb, As, Cu, Cd and Hg are the most often investigated. adsorptions of Cu(II) onto coal fly ash (CFA), CFA-600, and CFA–
The use of fly ash for removal of heavy metals was reported as early NaOH followed pseudo-second order kinetics. Changing the nature
as 1975. Gangoli et al. [58] reported the utilization of fly ash for the of CFA did not improve its ability to adsorb Cu(II).
removal heavy metals from industrial wastewaters. The presence of organic pollutants significantly affected the
Removal of chromium ions, including Cr(VI) and Cr(III) using fly removal of heavy metals from wastewater. Wang et al. [75] inves-
ash has been investigated by several researchers [59,60]. The effects tigated the competitive adsorption of heavy metals and humic acid
of chromium concentrations, fly ash dosage, contact time, and pH using fly ash as adsorbent. It is found that, for a single pollutant
on the removal of chromium were reported. A homogeneous system, fly ash can achieve adsorption of lead ion at 18 mg/g,
mixture of fly ash and wollastonite (1:1) was also reported to copper ion at 7 mg/g and humic acid at 36 mg/g, respectively. For
remove Cr(VI) from aqueous solutions by adsorption [61]. Bhatta- co-adsorption, complexation of heavy metals and humic acid plays
charya et al. [62,63] studied the removal of Cr(VI) and Zn (II) from an important role. The presence of humic acid in water will provide
aqueous solution using fly ash. Turkish fly ash was also used for the additional binding sites for heavy metals, thus promoting metal
removal of Cr(VI) and Cd(II) from an aqueous solution on [64]. Fly adsorption on fly ash. For Pb–HA and Cu–HA systems, Pb(II) and
ash was found to have a higher adsorption capacity for Cd(II), as Cu(II) adsorption can increase to 37 and 28 mg/g, respectively. The
compared to Cr(VI). The lime (crystalline CaO) content in the fly ash heavy metal ions present in the system will compete with the
seemed to be a significant factor influencing the adsorption of adsorption of humic acid on fly ash, thus resulting in a decrease in
Cr(VI) and Cd(II). Fly ash obtained from the combustion of poultry humic acid adsorption.
litter was also utilized as an adsorbent for the removal of Cr(III) Fly ash was also found to be effective for the removal of mercury.
from aqueous solution [65]. Yadava et al. [66] investigated the The adsorption capacity of coal fly ash for mercury was comparable
removal of cadmium by fly ash by varying contact time, tempera- to that of activated powdered charcoal [76]. The effectiveness of fly
ture and pH. The removal of Cd(II) has been found to be contact ash in adsorbing mercury from wastewater has been studied [77].
time, concentration, temperature and pH dependent. The process Selective adsorption of various metal ions (Na, K, Mg, Ca, Cu, Cd,
of removal follows first order adsorption kinetics and the rate Mn, Hg, Cr, Pb, and Fe) by fly ash was also reported [78]. Lead ions
controlling step is intraparticle transport into the pores of fly ash were found to be selectively adsorbed at a mean value of 19 meq of
particles. The temperature dependence of Cd(II) adsorption on fly Pb(II) per 100 g of fly ash. This selective adsorption could be due to
ash indicates the exothermic nature of adsorption. Alkaline the formation of crystalline ettringite mineral after the hydration of
aqueous medium favors the removal of Cd(II) by fly ash. The the fly ash. Coal fly ash has also been used for the removal of toxic
increase in adsorption of Cd(II) with pH has been explained on the heavy metals, i.e. Cu(II), Pb(II) and Cd(II) from water [79]. The
basis of surface complex formation approach. Raw bagasse and coal breakthrough volumes of the heavy metal solutions have been
fly ash have also been used as low-cost adsorbents for the removal measured by dynamic column experiments in order to determine
of chromium and nickel from aqueous solutions [67]. The extent of the saturation capacities of the adsorbents. The adsorption
adsorption at equilibrium was found to be dependent on the sequence is Cu > Pb > Cd in accordance with the order of insolu-
physical and chemical characteristics of the adsorbent, adsorbate bility of the corresponding metal hydroxides. Similar results on the
and experimental system. adsorption of Cd and Cu by fly ash were also reported [80]. The
Fly ash was also utilized for the removal of copper from aqueous presence of high ionic strength or appreciable quantities of calcium
solution. Removal efficiency was found to be dependent on and chloride ions does not have a significant effect on the
concentration, pH and temperature [68]. The kinetics of adsorption adsorption of these metals by fly ash.
 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363
Banerjee et al. [60,61], studied the adsorption of various toxic
metal ions, Ni(II) and Zn(II), Cr(II) and Hg(II)], on fly ash and Al and Fe
impregnated fly ash. The impregnated fly ash showed much higher
adsorption capacity for all the ions, as compared to that of untreated
fly ash. The adsorption capacity of FA, Al–FA, and Fe–FA 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 fly ash and
activated carbon, and found that fly 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 fly ash and
temperature; maximum adsorption occurred in the pH range of 7.0–
7.5. The effectiveness of fly 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 fly 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 fly 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 fluidized-bed-sourced fly ashes with different chemical
compositions, silico-aluminous fly ash and sulfo-calcic fly 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 fly
ash than sulfo-calcic fly ash, except in the case of the ion Ni(II).
Mercury is bound to the ash surface due to several chemical reac-
tions 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 effluent
by treatment with fly ash. After the treatment with fly ash, the
effluent showed a significant reduction in toxicity, Cu, Pb and
PO43 and NO 3 contents. Fly ash removed Cu and Pb from the
effluent; 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
fly ash as adsorbents. They used bagasse fly ash from sugar
industries for the removal of lead [92], copper and zinc [93,94],
cadmium, nickel [95] and chromium [96,97] from aqueous solu-
tions. Copper and zinc are adsorbed by the developed adsorbent up
to 90–95% 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 60–65% 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 96–98%. The removal of these two metal ions (up to
95–96%), was achieved by column experiments at a flow rate of
0.5 mL/min. The adsorption capacities of sewage sludge ash (SSA),
with fly ash for copper ions were compared [98]. The estimated
maximum capacity of copper adsorbed by SSA was 3.2–4.1 mg/g
close to that of fly 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 equilib-
rium pH of wastewater were at a high level (30/40 g/l and greater
than 6.2, respectively).The feasibility of using fly ash for the
removal of Cu(II) and Pb(II) from wastewater was investigated
[99,100]. The cation exchange capacity and specific surface area of
fly ash increased with increased carbon content. The adsorption of
335
metal ions onto the surface of fly 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
specific surface area. Consequently, carbon residual in the fly ash
play a more important role than mineral matter in the removal of
metals by the fly ash.
Fly ash was found to be good adsorbent for removal of zinc from
aqueous solutions [101]. Gashi et al. [102] reported that fly ash
showed good adsorptive properties for removal of lead, zinc,
cadmium and copper from effluents in the battery and fertilizer
industries. Removal efficiencies were greater than 70%. Adsorption
studies carried out to estimate heavy metal removal, using fly 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 fly 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 fly ash adsorption and
cement fixation of the metal-laden adsorbent, was investigated by
Huang research group [104–106]. Results showed that fly ash could
be an effective metal adsorbent, at least for Zn(II) and Cd(II) in
dilute industrial wastewaters. A 10% metal-laden fly 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 efficiency by lignite-based fly ash. Maple wood ash
without any chemical treatment was utilized to remediate As(III)
and As(V) from contaminated aqueous streams in low concentra-
tions [108]. Static tests removed 80% arsenic, while the arsenic
concentration was reduced from 500 to <5 ppb, in dynamic column
experiments. The efficiency of removal of As(V) and As(III) on char-
carbon (CC), derived from fly ash is compared with those of
commercially activated carbon [109].
It was reported that coal fly 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 mech-
anism of retention of radionuclide by fly ash is specific 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 film 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 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363

be controlled by the slowest step that would be either film diffusion empirical model used to describe adsorption in aqueous systems,
or pore diffusion controlled. was also used to explain the observed phenomena of adsorption of
Various kinetic models have been suggested for adsorption, metal on fly ash materials. The Freundlich isotherm is shown in the
including the Lagergren pseudo-first order kinetics, the pseudo- following equation.
second order kinetics, external diffusion model, and intraparticle
diffusion model, which are expressed in Eqs. (5)–(8) as listed
x 1=n
¼ Kf Ce (12)
below: m
The linear form of the equation can be written as:
k1
logðqe  qt Þ ¼ logqe  t (5) x
2:303 1=n
log ¼ logKf þ logCe (13)
m
t 1 1 where, Kf is the measure of sorption capacity, 1/n is sorption
¼ þ t (6)
qt k2 q2e qe intensity, and other parameters have been defined as in Eq. (13).
The Redlich–Peterson model was also used to describe the
dCt adsorption phenomenon. The Redlich–Peterson equation has three
¼ ks SðCt  Cs Þ (7) parameters, A, B and b. Parameter b ranges between 0 and 1.The
dt
equation is represented below:
 
qt ¼ ki t 1=2 (8) Ce B 1
¼ þ Ceb (14)
x=m A A
where k1, k2, ks and ki are the pseudo-first order, pseudo-second
order rate constant, mass transfer coefficient, and rate parameter of This isotherm describes adsorption on heterogeneous surfaces,
the intraparticle diffusion control stage, respectively, qe the amount as it contains the heterogeneity factor b. It can reduce to Langmuir
of solute adsorbed (mg/g) at equilibrium and qt the amount of equation as b approaches one. Using Eq. (14), the parameters A, B,
solute on the surface of the adsorbent (mg/g) at any time t, Cs and Ct and b were determined by curve fitting.
are surface and solution concentration, and S is the specific surface The DKR equation can be represented as
area. Adsorption kinetics of heavy metals on fly ash was investi-
gated by several researchers. Most investigations reported that ln Qe ¼ ln Qm  b32 (15)
adsorption of metal usually follows the first order kinetics
where, Qe is the amount adsorbed (mol/gm), Qm (mol/gm) is the
[68,81,82], and that adsorption is pore diffusion controlled
DKR monolayer capacity, b (mol2/J2) is a constant related to the
[68,81,82,95,97]. Kelleher et al. [65] investigated adsorption of
adsorption energy, and e is the Polanyi potential, which is related to
Cr(III) on fly ash, and kinetic studies suggested that overall rate of
the equilibrium concentration through the expression:
adsorption was pseudo-second order.
3 ¼ RTlnð1=CÞ (16)
6.3. Adsorption isotherms where T is the temperature and C is the equilibrium concentration
of the adsobate in solution. When lnQe was plotted against e2,
The Langmuir, Freundlich, Redlich–Peterson, Dubinin–Kaganer– a straight line will be obtained. The value of b is related to the
Radushkevich (DKR), Tempkin, and Sips isotherms were generally adsorption energy, E, through the following relationship:
used to describe observed adsorption phenomena of various metal
ions on fly ash. The Langmuir isotherm applies to adsorption on 1=2
E ¼ 1=ð2bÞ (17)
completely homogenous surfaces with negligible interaction
between adsorbed molecules. For a single solute, it is given by Tempkin and Pyzhev considered the effects of some indirect
adsorbate/adsorbate interactions on adsorption isotherms and
x Vm KCe suggested that because of these interactions the heat of adsorption
¼ (9)
m 1 þ KCe of all the molecules in the layer would decrease linearly with
coverage. The Tempkin isotherm has been used in the following
However, the linear form of the equation can be written as
form:
Ce 1 Ce
¼ þ (10) qe ¼ RT=bðlnACe Þ (18)
x=m KVm Vm
Eq. (18) can be expressed in its linear form as:
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 qe ¼ RT=blnA þ RT=blnCe (19)
the adsorbent, Vm is the monolayer capacity, and K is an equilibrium
constant that is related to the heat of adsorption by equation:
B ¼ RT=b (20)
q
K ¼ Ko exp (11)
RT 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 adsorp-
where, q is the heat of adsorption. Langmuir model can describe
tion [111].
most adsorption phenomena of heavy metals on fly ash
Sips model suggests that the equilibrium data follow Freundlich
[76,77,83,84,91]. In most cases, Vm and K increase with tempera-
curve at lower solute concentration and follows Langmuir pattern
ture, suggesting that adsorption capacity and intensity of adsorp-
at higher solute concentration. The equation can be represented as
tion are enhanced a higher temperature. A linear plot from Eq. (10)
follows [112]:
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 Q ¼ ðKs Ce Þb=½1 þ ðas Ce Þb (21)
 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363
where Ks (L/g) and as (L/mg) are Sips isotherm constants and b is
the exponent which lies between 1 and 0.
6.4. Factors affecting adsorption of metal on fly ash
The adsorption of heavy metals on fly 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 fly ash. The adsorption
capacity of fly ash depends on the surface activities, such as, specific
surface area available for solute surface interaction, which is
accessible to the solute. The adsorption affinity of fly ash for heavy
metal depends on the equilibrium between competitive adsorption
from all the cations, ionic size, stability of bonds between heavy
metals and fly ash. The other important factor for the adsorption of
heavy metal on fly 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 efficiency 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 efficiency. 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.
DG0 DS0 DH0
ln Kc ¼  ¼  (22)
RT R RT
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 fly
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 solid–solution interface during
adsorption.
Fly ash can be regenerated after the adsorption, using suitable
reagents. Batabyal et al. [113] regenerated the used saturated fly ash
with 2% aqueous H2O2 solution. The regenerated fly ash was dried,
cooled and used for further adsorption. The adsorption rate and
equilibrium time were same as the fresh fly ash particles.
7. Removal of other inorganic components from wastewater
Apart from heavy metals in wastewater, some other inorganic
contaminants, such as phosphorous, fluoride, 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 fly ash is enriched with oxides of aluminum, iron, calcium,
and silica, fly ash emerges as a potential candidate to treat phos-
phate-laden effluents since aluminum, iron and calcium are
337
strongly adsorb or precipitate phosphates in many agricultural,
industrial and environmental applications.
7.1. Removal of phosphate
Kuziemska first reported an investigation using water extract of
brown coal fly ash as coagulant for precipitation of phosphate in
1980. It was found that phosphate precipitation occurs immedi-
ately after introduction of coagulant, and after a short and intensive
mixing because of very high total alkalinity of extract [114].
Coal fly ash was paid great attention as a potential material for
removal of phosphate, since it is easily available and cost effective
[115–120]. Ugurlu and Salman [116] found that a Turkish fly ash is
an efficient adsorbent for removal of phosphate due to high
concentration of calcite (33.83%). The influence of temperature,
phosphate concentration, and fly ash dosage on phosphate removal
was investigated. Tsitouridou and Georgiou [120] compared three
fly ash with different calcium contents, and indicated that phos-
phate removal involved an adsorption and/or precipitation process.
Vordonis et al. [121] determined that uptake of orthophosphate by
four calcium-rich (10–32%) Greek fly ash exceeded the amount
predicted by monolayer coverage, suggesting either multilayer
adsorption or precipitation. Interaction of inorganic orthophos-
phate at water/solid interface was investigated.
Cheung and Venkitachalam [122] investigated the removal of
phosphate by fly ash with high- and low-calcium contents and
concluded that phosphate removal was primarily due to the
precipitation of phosphate with Ca2þ ions in solution. The removal
of phosphate by a medium calcium fly 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 fly ash for phosphate immobilization on the order of
100–75% for 50 and 100 mg P/L solutions, respectively. For the
amorphous and crystalline phases studied, the immobilization of
phosphate in the fly 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 fly ash, slag and ordinary Portland cement (OPC) and related
cement blends [125]. The rate and efficiency of PO3 4 removal were
found to increase in the order: fly ash, slag, OPC, apparently
mimicking the order of increasing percent CaO in the adsorbents.
Blending OPC with fly ash or slag evidently resulted in diminished
PO34 removal efficiency. Recently, Chen et al. [126] investigated the
removal of phosphate on different fly ash. The sorption maxima of
phosphate (Qm) ranged from 5.51 to 42.55 mg/g. The Qm value
showed a significantly positive correlation with total Ca content
(r ¼ 0.9836) and total Fe content (r ¼ 0.8049), but negative corre-
lation with total Si and total Al content. Fractionation of Phosphorus
adsorbed by fly ash revealed that loosely bound Phosphorus frac-
tion and/or Ca þ Mg-P fraction were the dominant form of immo-
bilized phosphate. Higher removal of phosphate occurred at
alkaline conditions for high-calcium fly ash, at neutral pH levels for
medium calcium fly ash, while low-calcium fly 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 fly ash was governed by Ca
ingredient (especially CaO and CaSO4) and Fe ingredient (especially
Fe2O3d). The selection of a fly ash with a high phosphate sorption
capacity is of utmost importance to obtain a sustained phosphate
removal in the long term in practice.
Acid modified fly ash was effective in the removal of phosphate
from contaminated antibiotic wastewater. Adsorption, chemical
precipitation, and increase of BET were main mechanisms of
338 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363
removal of phosphate with modified fly ash. The addition of fly 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 filtration. But some fly ash
particles may remain in the water and cause turbidity. Membrane
process is being used for various water and wastewater treatment
applications. Crossflow microfiltration 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 fly ash in a crossflow micro-
filtration membrane unit was examined [129].
7.2. Removal of fluoride
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 fluorides in drinking
water is a matter of serious concern. The fluoride 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 impair-
ment, and damage of soft tissues. Excess fluoride consumption also
leads to cancer, osteoporosis, neurological, cerbrovascular effects,
and other physical ailments. Besides natural geological enrichment
of fluoride in ground waters, there can also be formidable contri-
butions from industries. High fluoride containing wastewater is
generated by coal power plants, semiconductor manufacturing,
glass and ceramic production, electroplating, rubber and fertilizer
manufacturing. Fluoride concentration in industrial effluent 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 fluoride. Increased levels of fluoride can also be present in
effluents from fluorine industry, glass etching and in ground water
around aluminum smelters. The problem of high fluoride concen-
tration 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 fluoride containing water, and upper regions of Ghana,
where 23% of wells have fluoride concentrations above WHO rec-
ommended maximum guideline limit of 1.5 mg/L. In the Gdansk
region, high fluoride levels (1.90–3.00 mg/L) were detected in
Malbork drinking water. There is a need for defluoridation of
industrial wastewaters, because of excessive amounts of fluoride
may cause adverse health effects to humans and animals. Various
methods have been used to remove fluoride from wastewaters.
These methods were divided into two groups: (a) precipitation
methods based on addition of chemicals to water and (b) adsorp-
tion methods in which fluoride is removed by adsorption or ion
exchange reactions on some suitable substrate, capable of regen-
eration and reuse [130]. Several investigations were reported for
the removal of fluoride from waters by using fly ash. Chaturvedi
et al. [131] examined fly ash for removal of fluoride from water and
wastewaters at different concentrations, times, temperatures and
pH of the solution. Removal of fluoride is favourable at low
concentration, high temperature and acidic pH. Nemade et al. [132]
carried out batch adsorption studies to determine removal effi-
ciency of fluoride by fly ash. Retention of fluoride ion in dynamic
experiments on columns packed with fly ash was studied in
aqueous solutions [133]. At lowest F concentration, F level in the
effluent 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 effluent steadily decreased
reaching 0 mg/L after 120–168 h. Coal fly 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 photo-
graphic chemicals; for fireproofing fabrics; and weatherproofing
wood. Very few investigations were reported on boron adsorption
using fly ash. Hollis et al. [134] examined the effect of ash particle
size, pH, and Ca(OH)2 on dissolution and adsorption of boron by fly
ash in aqueous media. A small amount of born was adsorbed by fly
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 fly ash was investigated in
batch and column reactors [135]. The Thomas and Yoon–Nelson
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 envi-
ronment 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
effluents. Fly ash has a good adsorption potential for phenolic
compounds. Table 3 presents a summary of adsorption capacity of
various organic compounds on fly ash.
Fly ash has good adsorption potential for phenolic compounds.
Khanna and Malhotra [136] first examined the potential of fly ash
for the removal of phenol. They reported kinetics and mechanism
of phenol removal on fly ash and provided useful data in the design
of phenol–fly ash adsorption systems. Adsorption of phenol, and
cresol, and their mixtures from aqueous solutions on activated
carbon and fly 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) fly ash were determined [139]. The fly ash adsorbed
67, 20, and 22 mg/g for phenol, chlorophenol, and 2,4-dichlor-
ophenol, respectively, for the highest water phase concentrations.
The affinity of phenolic compounds for fly ash is above the expected
amount corresponding to a monolayer coverage considering that
the surface area of fly 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 coopera-
tive (Curve S), indicating that adsorption becomes progressively
 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363 339

Table 3 Sarkar et al. [149] investigated the adsorption of some priority

Comparison of organic pollutant adsorption on fly ash. organic pollutants, viz., phenol (hydroxybenzene), o-hydroxyphenol
Organic compounds Adsorbent Capacity (mg/g) References (1,2-dihydroxybenzene), m-hydroxyphenol (1,3-dihydrox-
Phenol FA 67 [139] ybenzene), and 4-nitrophenol (1-hydroxy-4-nitrobenzene), on fly
Sugar fly ash 0.47–0.66 [143] ash. The process was complex consisting of both surface adsorption
FA-C 0.26 [148] and pore diffusion. Activation parameter data for ultimate adsorption
Wood FA 5.4 [142]
and pore diffusion are also evaluated. The data indicate that external
Ortho-chloro phenol Coal-FA 0.8–1.0 [147]
FA-C 98.7 [141] transport mainly governs rate-limiting process.
Fly ash 98.7 Batch adsorption experiments were conducted to estimate the
2,4-Dichloro phenol FA 22 [147] potential of fly ash (FA) for removal of phenols from aqueous
Coal FA 1.5–1.7 [142] solution [150,151]. Polar substituted phenol, having less steric
3-Chloro phenol FA 20 [139]
Para-chloro phenol FA-C 118.6 [141]
hindrance is better adsorbed than others. Substituted phenol with
Fly ash 118.6 hindered group is less adsorbed than phenol (m-nitrophenol >
2-Nitro phenol Wood FA 143.8 [151] o-nitrophenol > phenol > m-cresol > o-cresol). This order is related
FA 5.80–6.44 [143] to electron-withdrawing properties of substituents of phenolic
3-Nitro phenol FA 6.52–8.06 [142]
compound. Therefore, electron withdrawal or deactivation of
4-Nitro phenol Sugar fly ash 0.76–1.15 [151]
Wood FA 134.9 [143] benzene ring favors formation of electron-donor–acceptor
FA 7.80–9.68 [142] complexes between these rings and basic groups on the surface of
Para-nitro phenol Bagasse fly ash 8.3 [143] fly ash. The removal mechanism of phenol is explained due to
Cresol Coal FA 85.4–96.4 [146] chemical coagulation with metallic oxides. Bagasse fly ash (BFA),
m-Cresol Wood FA 34.5 [134]
p-Cresol Wood FA 52.5
rice husk fly ash (RHFA) and activated carbon (AC) were also
2,4 Dimethyl phenol Fly ash 1.39 [113] investigated for adsorption of 2,4-dichlorophenol and tetra-
DDD Sugar FA (7.5–7.7)  103 [160] chlorocatechol [152,153].
DDE Sugar FA (6.5–6.7)  103 The potential of rice husk and rice husk ash for phenol
Lindane Bagasse FA (2.4–2.5)  103 [161]
adsorption from aqueous solution was examined [154]. Rice husk
Malathion Bagasse FA (2.0–2.1)  103
Carbofuran FA 1.54–1.65 [162] ash is very effective than rice husk for phenol removal. Rice husk
TCB FA 0.35 [164] ash (RHA) obtained from a rice mill in Kenya was used for removal
HeCB FA 0.15 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 fly ash
easier as more solutes are taken up. Phenols have a strong hydroxyl was used successfully to remove 2,4-dimethyl phenol by adsorption
functional group which interacts with the adsorbent surfaces, from aqueous solutions [113]. Both diffusional and kinetic resis-
resulting in vertical alignment of the molecule on the surface. tances affect the rate of adsorption and their relative effects vary
Moreover, additional adsorption is motivated and consequently with operating temperatures. The rate of adsorption is controlled
strengthened by the interaction between the adsorbed molecules. by both diffusional and kinetic resistances at higher temperature,
This phenomenon is known to contribute significantly to the whereas at low temperature, rate of adsorption is dominated by
cooperative nature of adsorption and hence an S type curve. diffusion effect. Regeneration of used fly ash with H2O2 indicates
The potential of fly ash as a substitute for activated carbon for that fly ash may be a useful cheap industrial adsorbent for waste-
the removal of phenolic compounds from wastewater was exam- water treatment. Srivastava et al. [156] studied the adsorption of
ined [140,141]. The maximum phenol loading capacity of each phenol on carbon rich bagasse fly ash (BFA) and activated carbon-
adsorbent was 27.9 mg/g for fly ash and 108.0 mg/g for granular commercial grade (ACC) and laboratory grade (ACL). The high
activated carbon. Adsorption of phenolic compounds on a mixture negative value of change in Gibbs free energy (DG0) indicates
of bottom and fly ash was reported [142]. The effect of molecular feasible and spontaneous adsorption of phenol on BFA. The overall
weight and molecular configuration on adsorption of phenol (Ph), adsorption process is controlled by intraparticle diffusion of
m-cresol (m-Cr), p-cresol (p-Cr), 2-nitrophenol (2-NP) and phenol. Activated carbon (AC), bagasse ash (BA) and wood charcoal
4-nitrophenol (4-NP) from aqueous solution was investigated. The (WC) were also used as adsorbents for removal of phenol from
ultimate capacity of the adsorbent is considerably less than that water [157]. The effect of nitrate ion and EDTA on adsorption of
predicted from summing the single-component data; this was phenol was insignificant. Chloride ion has considerable negative
attributed to increased competition for adsorption sites. Bagasse fly effects on removal by BA. The estimation of diffusion coefficients
ash was converted into a low-cost adsorbent and used for removal indicated that film diffusion control adsorption of phenol.
of phenolic compounds [143–145]. The uptake increases when Phenolic compounds from paper mill industry wastewaters were
larger quantities of adsorbent are used. The presence of an anionic removed by using fly ash, raw sepiolite and heat-activated sepiolite
detergent Manoxol-IB reduces uptake of phenol and p-nitrophenol. as adsorbent [158]. Intraparticle model shows the presence of two
Adsorbent prepared from fly ash was successfully used to remove separate stages in adsorption process, namely, external diffusion and
cresol from an aqueous solution in a batch reactor [146]. pore diffusion. Heat-activated sepiolite is more effective than raw
Kao et al. [147] utilized fly ash for removal of 2-chlorophenol (2- sepiolite and fly ash. The efficiency of adsorption decreases with
CP) and 2,4-dichlorophenol (2,4-DCP). More adsorption takes place increased adsorption temperature for both fly ash and untreated
with fly ash of higher carbon content and larger specific surface area. sepiolite. Fly ash was successfully used to recover phenol from
Adsorption of chlorophenol is not influenced by matrix in waste- industrial wastewater, by lagooning mixture of fly ash and waste-
water. Chlorophenols in wastewater were also removed efficiently water; phenol was reduced from 4500 mg/L to 280 mg/L [159].
through a fly ash column. The breakthrough time was inversely
proportional to flow rates. The effectiveness of less expensive 8.2. Removal of pesticides
adsorbents such as peat, fly ash and bentonite in removing phenol
from wastewater was also examined [148]. Peat, fly ash and bentonite Among various organic and inorganic water pollutants, pesti-
were found to adsorb 46.1%, 41.6%, and 42.5% phenol, respectively. cides are very dangerous and harmful because of their toxic and
340 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363
carcinogenic nature. Bagasse fly 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-dichlor-
oethene] pesticides from wastewater [160]. The DDD and DDE are
removed up to 93%. The removal was achieved up to 97–98% in
column experiments at a flow rate of 0.5 mL/min. Bagasse fly ash
was also examined for removal of lindane and malathion from
wastewater [161]. At lower concentrations, adsorption is controlled
by film diffusion; while at higher concentrations, it is controlled by
particle diffusion mechanisms. Adsorption of carbofuran on fly 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 fly ash
impregnated with hydroxides of Al, Cd, Cu, Fe and Ni [163]. The
percentage removals of cinnamic acid, indole-3- acetic acid, beta-
naphthaleneacetic 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 fly
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 fly 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, fly ash is used for an efficient
removal of PCBs from aqueous solutions.
8.3. Removal of other organic compounds
Banerjee et al. [165] investigated the adsorption of o-xylene on
fly ash. Uptake rate of o-xylene increases significantly with
increased initial concentration, and gradually approaches a plateau.
A significant correlation was observed between rate of adsorption
and inverse of the square of particle diameter. Adsorption of
o-xylene by fly 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 fly 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 fixed-bed continuous flow fly ash column and developed a rela-
tionship for the design of such systems. Using 1000 mg/L of fly 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 fly 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 fly ash. The residual
carbon content played a significant 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 fly and volcanic ashes in removing organic
pollutants from oxidation pond effluents [171]. Factors affecting
organic pollutant removals, such as concentrations and sizes of fly
and volcanic ashes, initial pond effluent organic concentrations,
washed and unwashed conditions of fly and volcanic ashes, were
investigated. The TOC (total organic carbon) removal efficiency
varied from 30 to 58%. The organic removal efficiency increased
with increased ash concentrations, with decreased initial pond
effluent 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 finishing 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 fly 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 fly ash for removal of
azo dyes from wastewater.
The adsorption of Congo red from solution was carried out using
calcium-rich fly ash with different contact times, concentrations,
temperatures, and pH [172]. Bagasse fly 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 fly ash as adsorbent for removal of
Chrysoidine R from aqueous solution was reported by Math-
eswaran 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-(2-
hydroxy-1 naphthylazo) benzene sulfonic acid] was removed by
adsorption onto bottom ash [175]. To assess the practical utility of
adsorbents, a fixed-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 fly ash [176]. The adsorption
kinetics of C.I. Reactive Black 5 onto high-lime fly 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 fly 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 Rifa-
cion Yellow) from aqueous solutions using fly 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 fly ash is probably indicating fly ash/dye complexation. XRD
pattern of fly ash consisted of mainly quartz, mullite with some
magnetite and calcite. Surface morphology of fly ash and dye
loaded fly ash were obtained with SEM. Adsorption of dye on fly ash
was described using pseudo-first 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].
 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363 341

Table 4
Comparison of dye adsorption on fly ash.

Dye Fly ash type Adsorption capacity (mol/g) Temperature ( C) Adsorption isotherm Kinetic model References
5
Methylene blue Coal FA 14.4  10 25 Langmuir [202]
FA-F 1.89  105 22 Langmuir [205]
FA-F 1.4  105 30 Redlich–Peterson [186]
FA-HNO3 2.2  105 30 Redlich–Peterson
FA 6.0  106 30 Langmuir and Freundlich [182]
FA-NaOH 8.0  106 30 Langmuir and Freundlich
FA-NaOH-sono (16–40) 106 30 Langmuir and Freundlich
FA 1.4  105 Redlich–Peterson [186]
FA-HNO3 2.4  105 Redlich–Peterson
FA 2  106 Langmuir
Carbon –enriched FA 1.2  104 Langmuir
FA 2  105 Pseudo-second order
Colombian FA >2  105 25 [189]
Thailand FA >1.6  106 25
Fly ash 2.20  105 [179]
Fly ash 2.01  105 [190]
Crystal violet Coal FA 9.76  105 25 Freundlich Lagergren first order [204]
Carbon-free FA 1.0  106 Langmuir [186]
Carbon –enriched FA 1.0  104 Langmuir
Fly ash 9.13  105 [177]
Rosaniline hydrochloride Coal FA 1.35  105 25 Freundlich Lagergren first order [204]
Rhodamine B FA-F 1.15  105 22 Langmuir [205]
Colombian FA 8.0  106 25 [189]
Thailand FA 2.5  107 25
Fly ash (CFA) 1.15  105 [205]
Egacid orange II FA-F 2.36  104 22 Langmuir
Egacid red G FA-F 1.40  104 22 Langmuir
Egacid yellow G FA-F 5.20  105 22 Langmuir
Midlon black VL FA-F 3.3  105 22 Langmuir
Acid blue 29 FA 3.25  106 – Freundlich [203]
Acid blue 9 FA 5.43  106 – Freundlich
Acid red 91 FA 2.34  106 – Freundlich
Acid red 91 Fly ash 1.46
Acid red 91 FA 7.26  106 – Freundlich
Congo red FA-C 4.47  105 20 Freundlich Pseudo-second order [172]
Baggase fly ash 1.70  105 [173]
Malachite green Baggase fly ash 4.67  104 [197]
Egacid orange II Fly ash (CFA) 3.05  104 [205]
Orange-G Bagasse fly ash 4.15  105 [198]

Heat treatment and chemical treatment have also been applied to
the as-received fly ash and red mud samples. Heat treatment
reduces adsorption capacity, whereas acid treatment by HNO3
induces a different effect on fly ash. Nitric acid treatment results in
an increase in the adsorption capacity of fly ash. The effect of
different methods for fly ash treatment using conventional chem-
ical, 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 fly ash varies. Microwave treat-
ment is a fast and efficient method while producing sample with
highest adsorption capacity. The fly 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 specific surface
area and dye-adsorption capacity was observed after acid treat-
ment. Fly ash samples modified by NaOH solution and sonochem-
ical treatment were examined for a basic dye (methylene blue)
adsorption in aqueous solution [182]. Sonochemical treatment of
fly ash can significantly increase adsorption capacity depending on
the concentration of NaOH and treatment time.
The adsorption of toluidine blue (TB) onto fly 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 fly ash for TB decreased in presence of CPC
as a result of competitive adsorption for same sites between same
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 acidified 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 fly ash surface by silica, alumina, and/or iron
oxide and, in acidified situation, coagulation of coloured colloids in
effluent dissolved from fly ash. Many of these materials can,
however, be removed by using a two-stage fly ash sorption process.
Fly ash and treated fly 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 fly 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 fly ash (2.4  105 mol/g).
Adsorption capacity of fly ash is dominantly contributed by porous
unburned carbon in fly ash, rather than fly ash itself [186]. There is
a significant linear correlation between carbon content and
342 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363
adsorption capacity. Further investigation show that unburned
carbon exhibits much high adsorption capacity than mineral parts
of fly ash [187]. Pseudo-second order kinetic model would be better
in describing kinetics of dye adsorption than first order kinetics
[188].
The use of coal fly 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 fly ashes. Bagasse fly 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
fly 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 fly ash. Bagasse fly 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 significantly. The effect of different
methods for fly ash treatment using conventional chemical, sono-
chemical 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 fly ash and
mixture of fly 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 fixed-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 fly 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 film and pore diffusion with film
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 fly 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 fly ash for the removal of dye (Victoria
Blue) from aqueous solution was first reported by Khare et al. [199].
Adsorption increased with dye concentration and that the
maximum removal was achieved at pH 8. Bagasse fly ash was also
used for the adsorption of brilliant green (BG) [200]. Adsorption of
BG on bagasse fly ash is favorably influenced by an increase in
operation temperature. The potential of fly ash for removal of
crystal violet dyes was reported [180]. The effect of different
methods for fly ash treatment using conventional chemical, sono-
chemical and microwave method on dye adsorption in aqueous
solution was investigated.
Adsorbents from coal fly 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 condi-
tions such as NaOH: fly ash ratio and fusion temperature with
optimal conditions being at 1.2:1 weight ratio of Na: fly ash at 250–
350  C. The synthesized materials exhibit much higher adsorption
capacity than fly 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 [202–204] investigated the
potential of fly ash for removal of dyes from wastewater. The
removal of each dye was inversely proportional to the size of fly ash
particle. Lime content in fly ash influenced the dye adsorption to
a significant degree – better adsorption was observed at lower
particle sizes because of increased external surface area available
for adsorption. Brown coal fly 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 (meth-
anol, 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 exhibi-
ted only a minor effect on dye sorption. Gupta et al. [195] investi-
gated 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 fly ash
was used as a heterogeneous catalyst in peroxidative decolorization
of aqueous solution of several reactive drimarene dyes using
hydrogen peroxide [206].
The efficacy of surface modification of fly ash by quaternary
ammonium cations in the removal of dyes from aqueous solution is
demonstrated [207]. A series of organo-fly ash materials were
synthesized by treating fly 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 modification. All above reports demonstrated
that fly 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 adsorp-
tion of dyes, metals and organic compounds from wastewater
[208–239]. 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
 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363 343

that make them excellent materials for environmental purposes, existence of competing organic or inorganic compounds in
such as high capacity and rate of adsorption, high selectivity for solution, initial adsorbent concentration, contact time and
different concentrations and also rapid kinetics. Some promising speed of rotation etc. The industrial effluents were found to
results could be found in the case of clays, peat and chitosan-based contain several pollutants simultaneously. However, little
materials [229,241,242]. Ahmaruzzaman [243] recently reviewed attention has been paid to the adsorption of pollutants from
the adsorption of phenolic compounds on low-cost adsorbents. the mixtures [244]. The development of the adsorption
Some promising results could be found in the case of fungal process requires further investigation in the direction of
biomass, bentonite, starch, petroleum coke, coal, residual coal, testing fly ash adsorbents with the real industrial effluents.
residual coal treated with H3PO4, charred sawdust, cyclodextrin, (iii) The competitive adsorption of organic compounds on fly ash
silica beads, and sludge materials. Table 5 reported the adsorption was reported in few cases. However, there is scarce data
capacities of phenol, dye, and metal on other adsorbents in order to available for the adsorption of organic compounds in presence
compare with fly ash. of metals and other contaminants. Therefore, more research
It is evident that fly ash has a great potential in the environ- should be conducted in this area.
mental applications. Fly ash is an interesting alternative to replace (iv) There is a lack of data concerning the reproducibility of the
activated carbon or zeolites for adsorption in the water pollution adsorption properties and the equilibrium data, commonly
treatment. Despite the number of published laboratory data, fly ash known as the adsorption isotherms. The design and efficient
adsorbent has not been applied at an industrial scale. There are operation of the adsorption processes also requires equilib-
several issues and drawbacks concerned on the adsorption of rium adsorption data for use in the kinetic and mass transfer
organic compounds that should be addressed: models. These models play an important role in predictive
modeling for analysis and design of adsorption systems.
(i) The applicability of fly ash as low-cost adsorbents for waste- Further work in this area is needed.
water treatment depends strongly on its origin. The
percentage of unburned carbon, SiO2, and Al2O3 content in the 10. Leaching of fly ash in water system
fly ash generally varies with regions and thus, adsorption
capacity. Utilization of fly ash in water involves the potential leaching of
(ii) The effectiveness of adsorption process depends on the some elements into water. This creates a problem of secondary
properties of the adsorbent and adsorbate. It also depends on environmental pollution. The surface layer of fly ash particles,
the environmental conditions and variables used for the probably of microns in thickness, contains a significant amount of
adsorption process such as pH, ionic strength, temperature, readily leachable material deposited during cooling after combus-
tion. Therefore, the charge on the surface of fly ash particle and
formation of diffuse double layer plays a significant role in leaching.
The elements present were divided into two groups based on their
Table 5
Comparison of adsorption on phenols, dyes and metals on various other adsorbents. 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
Organic Adsorbent Capacity References
volatile to a significant extent in combustion process. The volatility
compounds (mg/g)
for these elements is inversely proportional to particle size.
Phenol Coal 13.23 [215]
Residual coal 45.45
Elements, such as, Mg, Na, K, Mo, Ce, Rb, Cs and Nb possess
Residual coal treated with H3PO4 142.8 a smaller volatilized fraction during coal combustion [245]. The
Rice husk 4.508 volatility is directly proportional to particle size. The elements Si,
Coke breeze 0.172 As, Fe, Ca, Sr, La, Sm, Eu, Tb, Py, Yb, Y, Se, Zr, Ta, Na, Th, Ag and Zn are
Rice husk 4.508
either not volatilized or may show minor trends related to
Rice husk char 7.91
Petroleum coke 6.01 geochemistry of mineral matter. The volatility of trace elements
Lignite 10.0 [208] increased from larger to smaller particle size and establishes an
Neutralized red mud 4.127 [209] inverse relationship of volatility and particle size [246].
Sewage sludge 94.0 [210] Studies have shown that only about 1–3% fly ash material is
Dye Waste news paper 390 [222] soluble in water with lignite fly ash of higher proportion of water
(Basic blue 9) Coal 250 [220] soluble constituents [247]. The leaching of major elements from
Sewage sludge 114.94 [223]
CFA was extensively reviewed [11]. Analysis of water extracts
Rice husk 19.83 [221]
Straw 19.82 [248,249] showed that the principal cations in water extracts are
Date pits 17.3 [218] calcium and sodium, whereas anions are dominated by OH, CO3
Hazelnut shell 8.82 [217] with aqueous extracts of ash saturated with Ca(OH)2. The alkalinity
Coir pith 120.43 [219] and acidity controlled extractability of elements, such as, As, B, Be,
Banana peel 20.2 [216]
Cd, Cr, Cu, F, Mo, Se, V and Zn. Aqueous extracts of an acidic fly ash
Orange peel 18.6
contained concentrations of Cd, Co, Cu, Mn, Ni, Zn, As, B, Be, Cd, F,
Metal (Zn2þ) Blast furnace slag 103.3 [226]
Mo, Se and V [250,251]. Leachate waters have markedly different
Lignin 95 [227]
Lignin 73 [225]
compositions, depending on the surface of fly ash, flue gas process
Acid washed-tea industry waste 12 [233] conditions design of combustion systems, and whether lime or lime
Tea industry waste 11 [234] stone injection processes were implemented for desulfurization.
Powered waste sludge 168 [235] Total dissolved solid concentrations may vary from hundreds to
Sugar beet pulp 35.6 [236]
tens of thousands of milligram/liter. A small sample can show
Lignin 11.24 [228]
Solid residue of olive mill products 5.40 [237] marked differences in leachate water chemistry, depending on
Red mud 12.59 [224] reaction time and water/solid ratio in batch equilibration’s or with
Blast furnace slag 17.65 [225] column length, and flow rate in a dynamic leaching test. The
Coffee Husk 5.57 [238] mineral and glass phases constitute fly ash material, are formed
Clarified sludge 15.53 [63]
over a wide range of temperatures in furnace. All these phases are
344 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363
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 crys-
talline 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 fly ash were
reported by a number of researchers [245,253–255]. Leachability of
heavy metals from the coal fly ash is relatively low and leaching
extent is dependent on the conditions of water system. Trace metal
concentration in the leachate depends on fly 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 fly ash particles. The organic compounds identified in fly ash
extracts include known mutagens and carcinogens. There are
leaching procedures for the dissolution of the organic compounds
of FA in 30–40% hydrogen peroxide, concentrated nitric acid under
microwave conditions, or benzene. However, this chemical treat-
ment also leaches components associated with both organic and
inorganic compounds in FA. For example, some unstable minerals
from the chloride, sulfate, sulfide, oxide, and carbonate classes may
be leached, destroyed, or altered during this procedure. Formations
of artificial 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 miner-
alogical 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 inor-
ganic matrixes (especially glass).
There are traces of polycyclic aromatic hydrocarbons present in
the coal fly ash, typically up to 25 mg/kg. Due to the low solubility,
the leachate from coal fly ash contains very low concentrations of
polycyclic aromatic hydrocarbons (PAHs).
Several authors have investigated the capacity of fly 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 significantly reduced. Erol et al. [260] studied the
ability of fly ash to remove Cu2þ and Pb2þ in aqueous solutions.
These authors observed that the contaminant removal capacity of
the fly ash was directly proportional to the CaO content. Polat et al.
[261] investigated fly ash for neutralization of highly acidic heavy
metal-laden oily waste sludge while Potgieter-Vermaak et al. [262]
compared fly ash, limestone and fly ash as pre-treatment agents for
acid mine drainage. The authors observed that fly ash can be used
as a neutralization/fixation agent. It is expected that fly 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-precipita-
tion 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 fly 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 fly ash are anhydrous phases such as
aluminosilicates and salts such as sulphates, oxides and chlorides
formed at high temperatures in coal-fired 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 fly 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 avail-
ability to the leachate solutions and by their diffusive flux 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 fly 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 fly
ash leachate is controlled by mineral solubility is a challenge. In
reactions involving acid mine drainage with fly ash, the precipitates
formed are largely amorphous [263,270] and hence cannot be
detected by XRD. Dilution by the major phases of fly ash such as
glass, mullite and quartz could also account for their non-detect-
ability. Unlike equilibration of fly ash with demineralized water, the
AMD contains high concentration of SO42, Ca, Mg, Al, K and Fe
which are also present in fly 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 fly 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 non-
existence 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 significantly lower leaching abilities for two reasons: first, 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 10–7 m/s, there is no significant influence of hazardous
elements on the surrounding waters and soil due to leaching.
Therefore, it is suggested that following measures/steps should
be taken before fly ash is used as adsorbent for wastewater treat-
ment: (1) leaching behaviour test for water system; (2) forced
extraction of mobile substances from fly ash; (3) immobilisation of
mobile metals and other elements; (4) destruction of persistent
organic pollutants.
11. Synthesis of zeolite
Zeolites are crystalline aluminium–silicates, with group I or II
elements as counter ions. Their structure is made up of a frame-
work 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 define 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
 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363 345

Table 6
Zeolites and other neomorphic phases synthesized from fly ash and Joint Committee
of Powder Diffraction Standard (JCPDS) codes for XRD identification.

Zeolitic product Chemical formula JCPDS

NaP1 zeolite Na6Al6Si10O32$12H2O 39-0219
Nap zeolite Na3.6Al3.6Si12.4O32$12H2O 34-0524
Phillipsite K2Al2Si3O10$H2O 30-0902
K-chabazite K2Al2SiO6$H2O 12-0194
Zeolite F linde KAlSiO4.1$5H2O 25-0619
Herschelite Na2Al2Si1.68O7.44$1.8H2O 31-1271
Faujasite Na2Al2Si3.3O8.8$6.7H2O 12-0228
Zeolite A NaAlSi1.1O4.2$2.25H2O 43-0142
Zeolite X NaAlSi1.23O4.46$3.07H2O 39-0218
Zeolite Y NaAlSi2.43O6.86$4.46H2O 38-0239
Perlialit K9NaCaAl12Si24O72$15H2O 38-0395
Fig. 2. Idealized structure of zeolite framework of tetrahedral [SiO4]4- with a Si/Al Analcime NaAlSi2O6$H2O 19-1180
substitution ([AlO4]5-) yielding a negative charge, and consequently a cation exchange Hydroxy-sodalite Na1.08Al2Si1.68O7.44$1.8H2O 31-1271
capacity [7]. Hydroxy-cancrinite Na14Al12Si13O51$6H2O 28-1036
Kalsilite KalSiO4 33-0988
Tobermorite Ca5(OH)2Si6O16$4H2O 19-1364

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 Naþ/Kþ/Ca2þ for other cations
on the basis of ion selectivity.
Gas adsorption: selective absorption of specific 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 fly ash is to
convert it into low-grade zeolites. The compositional similarity of
fly 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 treat-
ment of fly ash [272]. This potential use of fly ash has an important
background, given intensive research on zeolite growth in geolog-
ical 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 specific surface area of fly 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 fly
ash. All methodologies developed are based on the dissolution of
Al–Si-bearing fly ash phase with alkaline solutions (mainly NaOH
and KOH solutions) and subsequent precipitation of zeolitic mate-
rial. Table 6 showed the types of zeolite synthesized from coal fly
ash. The potential industrial application of these zeolitic materials
is varied. The zeolite X has a large pore size (7.3 Å) and high CEC
(5 meq/g), which make it an interesting molecular sieve and high-
cation exchange material. The small pore size of hydroxy-sodalite
(2.3 Å) accounts for low potential application for both molecular
sieving and ion exchange. The main limitation of the processes for
synthesizing zeolites from fly ash is to speed up reaction, relatively
high temperatures (125–200  C) applied to dissolve Si and Al from
fly 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 consider-
ably and a very long activation time is required.
The synthesis of zeolites from fly ash is classified into direct and
non-direct synthesis. For direct synthesis [277–285], fly ash was
hydrothermally treated with an alkaline solution. At temperature,
(lower than 100  C), zeolites P, X and Na–P1 were obtained with
2–4 M NaOH solution, while hydroxy sodalite and zeolite-Y were
obtained with 4–10 M NaOH solution. At temperature, (higher than
120  C), zeolite Na–P1, hydroxy sodalite and analcime were
obtained with 4–10 M NaOH solution. For non-direct synthesis
[286,287], silica and alumina were extracted from fly 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 60–90  C and time period of two–
five days.
Fusion with sodium hydroxide prior to hydrothermal reaction
was applied by Shigemoto et al. [288–290] to improve the
conversion of fly ash into Na–X Zeolite. Several studies
[277,292,293] examined the efficiency of Na and K-Zeolite synthesis
after alkaline activation of fly ash in closed systems for short acti-
vation periods (8–100 h). The time of activation (from hours or days
to minutes) can be significantly reduced for zeolite synthesis using
microwave-assisted hydrothermal process [281]. This alkaline
conversion of fly ash is based on combination of different activation
solution/fly 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 fly ash
[284]. The zeolite contents of resulting material varied widely (40–
75%) depending mainly on activation solution/fly 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 single-
batch experiment [284].
To avoid the synthesis process with the generation of waste-
water, 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 fly 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 fly ash particles obtained from other strategies.
Moreover, high-pore volume zeolites, including zeolites X and A,
may be obtained in this process.
The lignite fly ash and rice husk ash were also used as raw
materials for ZSM-5 zeolite synthesis [295]. Factors affecting the yield
346 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363
of ZSM-5 zeolite synthesized from fly 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 2.8–200
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, fly 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
(3–48 h), solution concentration (0.5, 1, 2, 3 and 5 M), pressure (the
vapor pressure at the temperature selected), and solution/sample
ratio (1–20 ml/g). The zeolitic material is filtered and washed with
water, dried at room temperature and analyzed by XRD. The
determination of CEC value and comparison of pure zeolite is rec-
ommended for a semi-quantitative estimation of zeolite contents of
synthetic materials. Most studies showed that NaOH solutions have
higher conversion efficiency than KOH solutions under same
temperature. Most zeolites reported in the Table 6 obtained from
specific fly ash. Reaction time required for synthesis yield is
inversely proportional to aluminum–silicate glass content of fly
ash. The conversion efficiencies are dependent on non-reactive
phases (mainly hematite, magnetite, lime), and resistant
aluminum–silicate phases, such as mullite and quartz, and the grain
size distribution. Thus, for higher aluminum–silicate glass content,
shorter activation periods and lower solution/fly 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 fly
ash is zeolitized in short period (6–8 h), but longer reaction times
(24–48 h) are required to obtain similar synthesis yields from high-
mullite or quartz fly ash. The highest synthesis yields are obtained
in 12–24 h using a high-activation solution/fly ash ratio (10–20 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/fly 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
Fig. 3. Process flow of zeolitization plant (1.5 tons: hour) [6].
not achieved. Both temperature and concentration of the activation
agent have a very important influence 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 fly ash. They
provided an overview on the methodologies for zeolite synthesis
from coal fly ash, and a detailed description of conventional alka-
line conversion processes, with special emphasis on the experi-
mental conditions to obtain high cation exchange capacity (CEC)
zeolites.
A new process for converting coal fly ash into an artificial zeolite
is described [296]. The process is comprised of a high-temperature
operation and water removal during the operation. Suitable oper-
ational parameters of the process were investigated using a test
unit, and optimal conditions were found to be 2.5–3.5 mol/dm3 of
NaOH, and 0.88–1.10 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 conven-
tional 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 simplified process flow
diagram is shown in the Fig. 3.
11.1. Application of zeolite synthesised from fly ash
Simultaneously with the development of synthesis methods,
intensive research has been carried out on the potential application
of the zeolites synthesized from fly 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 fly ash can be utilized in the treatment
of wastewater. Zeolite synthesized from fly ash has the ability of
immobilizing phosphate from wastewater [298,299]. Therefore,
simultaneous removal of ammonium and phosphate from aqueous
 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363 347

solution by zeolite synthesized from fly ash (ZFA) is possible. The Table 7

existence of exchangeable Ca2þ on zeolite surface is critical to Summary of adsorption of metals on fly ash based zeolite.

precipitate phosphate in aqueous solution [298,299]. Phosphate Metals Adsorbent Adsorption Temperature ( C) References
immobilization capacity (PIC) of the synthesized zeolites and cor- capacity (mg/g)
responding raw fly ash was determined using an initial phosphate Zn2þ Fly ash zeolite 4A 30.80 [308]
concentration of 1000 mg/L [300]. Results showed that there was Cd2þ Fly ash zeolite 95.6 20 [307]
Fly ash zeolite X 97.78 [309]
a remarkable increase in PIC (from 1.2 to 7.6 times) following the
Pb2þ Fly ash zeolite 70.6 20 [307]
synthesis process. Although calcium and iron components were Fly ash zeolite X 420.61 [309]
mainly involved in phosphate immobilization, there was no Cu2þ Fly ash zeolite 4A 50.45 [308]
significant change of Ca and Fe content following conversion of fly Fly ash zeolite X 90.86 [309]
ash into zeolite. Increase in dissociated Fe2O3 and specific surface Ni2þ Fly ash zeolite 4A 8.96 [308]
Cr3þ Fly ash zeolite 4A 41.61
area probably accounted for enhancement in PIC of synthesized Co2þ Fly ash zeolite 4A 13.72
zeolites compared with corresponding fly ash. The specific surface Csþ Fly ash zeolite 443.9 25 [306]
area increased 26.0–89.4 times as a result of the conversion of fly
ash to zeolite. The maximum removal of phosphate occurred within
different pH ranges for zeolites which were synthesized from high,
medium and low-calcium fly ash and this behavior was explained method. The modified ZFA (ZFAAl50) with optimum alumina
by reaction of phosphate with calcium and iron components. loading showed an adsorption capacity of 34.5 mg/g, which was 2.1
To develop an effective technique to enhance removal efficiency times higher than activated alumina. The Toxicity Characteristic
of phosphate at low concentrations, ZFA was modified with acid Leaching Procedure (TCLP) leachability tests indicated that spent
treatment and simultaneous removal of ammonium and phosphate ZFA and alumina-modified ZFA complied with the EPA regulations
in a wide range of concentration was investigated [301]. Treatment for safe disposal. The removal of arsenic, from drinking water by
with more concentrated H2SO4 led to the deterioration of ZFA filtration through modified fly ash bed is also reported [304]. The
structure and a decrease in the cation exchange capacity. Treatment effects of different parameters like pH and presence of other
by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate constituents are described. The effectiveness of the modified fly ash
by ZFA at all initial phosphorus concentrations, while the treatment bed for the control of arsenic was demonstrated by taking different
by concentrated H2SO4 (>0.9 mol/L) resulted in a limited maximum quantities of arsenic(III) and arsenic(V) salts. The utilization of
phosphate immobilization capacity (PIC). It was concluded that zeolites synthesized from fly ash (FA), and related co-disposal
through a previous mild acid treatment (e.g. 0.01 mol/L of H2SO4), filtrates as low-cost adsorbent material, was investigated [305]. The
ZFA can be used in the simultaneous removal of NHþ 4 and phos- synthesized zeolite was explored to establish its ability to remove
phorus at low concentrations in simulating real effluent. In another Pb(II) and Hg(II) from aqueous solution. The synthesized zeolite
study, Na-ZFA (zeolite synthesized from fly ash) was converted into was effective in reducing the Pb(II) and Hg(II) concentrations by
Ca-, Mg-, Al-, and Fe-ZFA by salt treatment and the simultaneous 95% and 30%, respectively.
removal of ammonium and phosphate by ZFA saturated with Fly ash was converted to zeolites by hydrothermal treatment,
different cations was investigated [302]. It was shown that Al3þ- and used for the removal of metal ions, radiocesium [306], lead and
ZFA had the highest removal efficiencies (80–98%) for ammonium, cadmium [307]. Maximum uptake capacity was 3.34 mmol Cs/g,
followed by Mg2þ (43–58%), Ca2þ (40–54%), Naþ (<20%), and Fe3þ which was 2–3 times higher than those of synthetic zeolite P, and
(<1%). Both alkaline pH values (in the cases of Naþ, Ca2þ, Mg2þ) and natural mordenites. Adsorption capacity for lead and cadmium was
acidic pH value (in the case of Fe3þ) inhibited the sequestration of 70.58 mg lead/g-zeolite and 95.6 mg cadmium/g-zeolite, respec-
ammonium. At low initial phosphate concentrations, the efficiency tively, when the initial concentration for both ions was 100 mg/L.
of phosphate removal by Al3þ- and Fe3þ-ZFA approached 100%, The removal performance and the selectivity sequence of mixed
followed by Ca2þ(60–85%), Naþ (<25%), and Mg2þ(<5%). The metal ions (Co(II), Cr(III), Cu(II), Zn(II) and Ni(II)) in aqueous solu-
difference in phosphate removal efficiency was explained by the tion were investigated by adsorption process on pure and cham-
adsorption mechanisms. It was concluded that ZFA could be used in fered-edge zeolite 4A prepared from coal fly ash (CFA), commercial
simultaneous removal of NHþ 4 and phosphate at low concentrations grade zeolite 4A and the residual products recycled from CFA [308].
with presaturation by an appropriate cation such as Al3þ through The adsorption process is pH and concentration dependent. The
salt treatment. sorption rate and sorption capacity of metal ions could be signifi-
Zeolite synthesized from fly ash can also be utilized in the cantly improved by increasing pH value. The removal mechanism of
removal of heavy metals from wastewater. Several authors have metal ions was by adsorption and ion exchange processes. The coal
reported the utilization of fly ash synthesized zeolite for the fly ash (CFA) was modified to zeolite X, and used as an effective
removal of heavy metals from wastewater. Table 7 summarizes the adsorbent for the removal of Cu(II), Cd(II), and Pb(II) [309]. External
results of the important metals investigated using zeolite-synthe- mass transfer step seemed take part as a rate limiting step for
sized fly ash. sorption of Pb(II) at low initial concentration, and high adsorbent
Zeolite was synthesized from Class C fly ash by molten-salt dose. The process was controlled more significantly by intraparticle
method, and the product obtained, zeolite fly ash (ZFA) was used as diffusion step at high initial concentration, and low sorbent dose.
an adsorbent for removal of arsenate from water [303]. ZFA showed However, Cu(II) was found to be generally controlled by intra-
a higher adsorption capacity (5.1 mg/g) than activated carbon particle diffusion step at all concentration range examined in this
(4.0 mg/g), silica gel (0.46 mg/g), zeolite NaY (1.4 mg/g), and zeolite work. The sorption of Cd(II), on the other hand was controlled by
5A (4.1 mg/g). Relatively higher adsorption capacity of ZFA than both external mass transfer and intraparticle diffusion steps at all
zeolite NaY and 5A was attributed to the low Si/Al ratio and the range of initial concentration. Surface-modified zeolite material has
mesoporous secondary pore structure of ZFA. It was observed that been developed from commercial zeolite, and fly ash-based zeolite,
the adsorption capacity of zeolites was generally lower than acti- by treating it with surface modifiers, such as, hexadecyl-
vated alumina (16.6 mg/g), which is ascribed to small pores in trimethylammonium bromide and tetramethylammonium
zeolite frameworks. The adsorption capacity of ZFA was signifi- bromide [310]. The adsorbent was evaluated for removal of arsenic
cantly improved, after loaded by alumina via a wet-impregnation and chromate anions. High selectivity, faster kinetics and high
348 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363
adsorption capacity ensure cost effectiveness of these materials
compared to other conventional materials for dearsenification.
Surface modified zeolite from fly ash is being used for adsorp-
tion of phenol and o-chlorophenol from wastewater [311]. The
comparison of adsorption of phenol and o-chlorophenol on
commercial zeolite-Y, fly ash based zeolite (FAZ-Y) and surface
modified fly 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
efficiency is higher by a factor of 2.29 and 1.8 for FAZ-Y and
commercial zeolite-Y, respectively. This may attributed to hydro-
phobicity imparted by surfactant molecules on the surface of fly 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 fly ash based zeolites for adsorption of thio-
phene and benzothiophene from n-hexane solution was investi-
gated [312]. The zeolites obtained were sodalite (SOD), gismondine
(GIS), and cancrinite (CAN). It was found that GIS with higher
specific 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 fly ash for removal of refractory sulfur
compounds, such as thiophene, benzothiophene etc.
Fly ash was modified by hydrothermal treatment with NaOH to
hydroxysodalite zeolite [313]. The cation exchange capacity of the
modified ash was significantly increased over that of the raw fly
ash. Modified fly ash adsorbed a cationic dye (methylene blue) to
a much greater extent than an anionic dye (alizarin sulphonate).
Saturation adsorption revealed that capacity of fly ash for methy-
lene blue had increased 10-fold during modification 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 fly 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 fly ash appears to be technically feasible in the
cement industry. There are essentially three applications for fly 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 replace-
ment of cement with fly ash. The utilization of fly ash is partly based
on economic grounds as pozzolana for partial replacement of
cement, and partly because of its beneficial 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 fibre 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 fly 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 fly 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 fly ash in concrete. The
availability of high-lime fly ash containing compounds found in
cement has led to high-strength concretes produced by the addi-
tion of fly ash and plasticizers. High-strength and high-perfor-
mance concrete can also be made with Class F fly ash. The ball
bearing effect produced by the spherical fly ash particles has
resulted in better pumpability of concrete and easier finishing with
trowels and other tools. The utilization of fly 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 fly ash, there is a lower heat of hydration compared to
straight Portland cement concrete, particularly when Class F fly ash
is used. Class C fly ash may not lower the heat of hydration.
Traditionally, with bituminous-type fly ash, 15–25% of the cement
was replaced. The advent of cementitious, high-lime fly ash has
permitted normal replacements of 25–40% and up to 75% for
parking lots, driveways, and streets. Nowadays, chemical admix-
tures 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 fly ash
concrete can be accelerated to achieve the desired performance.
Generally, the long term ultimate mechanical properties of fly ash
concretes are higher than those of plain Portland cement concretes.
The setting and hardening rates of fly 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 fly ash concrete.
There has been much concern about sulphate resistance of
concrete containing high-lime fly ash. It was reported that Sas-
katchewan lignite fly ash concrete increases sulphate resistance
[314]. Research with other high-lime fly ash has produced con-
flicting results with respect to sulphate resistance. Dunstan [315]
has proposed a sulphate resistance factor, R, which is equal to CaO-
5/Fe2O3 oxide analysis percentages. When R is less than 1.5, fly ash
should improve sulphate resistance.
Mehta [316–319] has discussed the factors that contribute to
attack of sulphates on fly 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 mon-
osulfo-aluminate and calcium aluminate hydrate, which are
attacked by the sulphate ion to form ettringite and calcium tri-
sulfoaluminate. Acidic-type interactions between sulphate ions and
calcium hydroxide also lead to strength and mass loss.
Exhaustive research has been conducted on fly ash admixture
concrete and its properties. Research showed that fly 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 fly 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,
 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363
cementitious compound of calcium silicate hydrate. The original
calcium hydroxide was soluble, whereas the calcium silicate
hydrate is less soluble in fly 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 filling 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 fly 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 fly ash concrete exceeded the regulated
concentration levels specified in the toxicity characteristic leaching
procedure (TCLP) test.
High-volume fly ash concrete has emerged as a construction
material in its own right. This type of concrete contains more than
50% of fly ash by mass of total cementitious materials. Many
researchers have used high volume of Class C, and Class F fly ash in
concrete. Ravina and Mehta [321] reported that by replacing 35–
50% of cement with fly ash, there was 5–7% 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 [322–328] reported
extensively on high-volume fly ash concrete. Concrete, containing
high volume of Class F fly ash exhibited excellent mechanical
properties, good durability with regard to repeated freezing and
thawing, very low permeability to chloride ions [322–324], 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 fly ash
were highly effective in inhibiting alkali–silica reaction [325].
Superplasticized high-volume fly ash concrete, containing up to
60% of fly ash of total cementitious materials had poor abrasion
resistance than concrete without fly ash [326]. Air-entrained high-
volume fly ash concrete exhibited excellent characteristics
regardless of the type of fly ash and cements [327].
Addition of fly ash as an admixture increased early-age
compressive strength and long-term corrosion resistance charac-
teristics of concrete [328]. Abrasion resistance of concrete made
with Class C fly ash was better than both concrete without fly ash
and concretes containing Class F fly ash [329]. High volumes of
Class C and Class F fly ash can be used to produce high-quality
pavements in concrete with excellent performance [330]. Blending
of Class C fly ash with Class F fly ash showed either comparable or
better results than either of the control mixture without fly ash or
the unblended Class C fly ash [331]. Hwang et al. [332] examined
the effects of fine aggregate replacement on the rheology,
compressive strength, and carbonation properties of fly ash and
mortar. Test results showed that rheological constants increased
with higher replacement level of fly ash and that, when water-to-
cement ratio was maintained, the strength development and
carbonation properties were improved. Siddique [333] reported
that Class F fly 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 fly
ash as a partial replacement of cement in concrete decreased its 28-
day compressive, splitting tensile and flexural strengths, modulus
of elasticity, and abrasion resistance of the concrete.
Singh and Garg [334] studied the cementitious binder from fly
ash. The development of binder takes place through the formation
of ettringite, C–S–H 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
fly ash, and optimum usage of fly ash in concrete. Bouzoubaâ 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 fly ash and cement concrete. Antiohos et al.
[337] investigated the properties of a series of blended cements
prepared by mixing clinker with a fly 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 fly ash
enriched in sulphates. All samples tested exhibited satisfactory
initial and final setting times and decent compressive strength
values, when compared to the reference specimen containing only
gypsum and no fly ash.
The utilization of fly ash in the construction of concrete dams
was investigated [338]. The compressive strengths of dam concrete
with 50% of fly ash in 90 days are higher than those with 30% of fly
ash or without fly ash. Fly ash may decrease the deformation of dam
concrete with 50% of fly ash, and the shrinkage and expansive strain
was reduced significantly–about 33% and 40% less than the speci-
mens without fly ash, respectively. The low-lime fly 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 modified fly ash to increase the setting prop-
erties of cement. Lupu et al. [340] investigated the use of chemcially
modified fly ash to control the setting of cement. The chemical
treatment of Class C fly 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 fly ash particle
being provided with necessary Ca prior to hydration without being
dependant on cement-fly ash particle interactions. Thus, the setting
process is no longer dependent on the particle shape, packing and
dispersion of the fly ash and cement. They modified the class C, I
and F fly ash with water, HNO3 and aqueous CaCO3 [341]. It was
found that the setting properties of the cement/fly ash mixture
enhanced by changing morphology and surface chemistry of fly ash
particles. The treatment of C-FA with an aqueous CaCO3 solution
results in a dramatic improvement in the setting time and the
setting profile 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 conse-
quence 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 filler-like material, while acid treatment of
C-FA results in a material with completely undesirable setting
properties. Antiohos et al. [342] activated fly ash chemically by
adding industrially produced quicklime. The presence of quicklime
accelerated the reaction rate of high-calcium fly ash, whereas in
case of lower-calcium fly 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 fly
ash and lime [343]. These results in decreased setting time, accel-
erated strength development, and increased strength of materials
containing fly ash, especially with a high percentage of fly ash.
Thus, chemical activation of reactivity of fly ash is an effective
method to increase the use of fly ash in concrete.
350 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363
The typical use of fly ash in Indian Pozzolana Portland cement
(PPC) is in the range of 15–25%. Higher usage of fly ash is restricted,
due to a decrease in the strength of cement, especially the early
strength. This is attributed to the low reactivity of fly ash [344]. The
reactivity of fly 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 fly ash has
been exploited in developing the process of making PPC containing
higher proportion of fly ash [345–347]. Mechanical activation of fly
ash results into a significant increase in the early strength of cement,
as compared to commercial cement. It was found that 50–60% of
mechanically activated fly 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 fly 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 fixed amount of clinker (50%), and different proportions
of raw and mechanically activated fly ash was investigated. The
study revealed that mechanical activation of fly ash has an indirect
bearing on the hydration of cement phases, namely, tri-calcium
silicate (C3S) and tri-calcium aluminate (C3A). This was reflected by
change in the maximum hydration rate of the phases (Ri where
i ¼ C3S, C3A), and the time of maximum hydration rate (Ti, i ¼ C3S,
C3A). It was observed that compressive strength, after 3 days and 28
days of hydration, showed a high degree of correlation with calo-
rimetric results. The overall effect of mechanical activation of fly
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 fly ash.
Recently, Roller compacted concrete (ROCC) application showed
that usage of fly ash in ROCC production was a wide spread practice,
such as, roads, dams, and large floor construction [348–350]. Fly
ash modified the properties of concrete in both fresh and hardened
state including workability, strength and shrinkage [351,352].
Furthermore, using fly 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 fly 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 þ Al2O3 þ Fe2O3 (SAF) to 50% for high-calcium fly
ash, and 70% for low-calcium fly ash. It was shown that a non-
standard fly ash can also be used in concrete. Atis [356,360] showed
that Aberthaw fly ash did not conform to the relevant standard;
alhtough, it provided excellent strength. Zhang et al. [361] showed
that a non-standard fly ash could also be used in concrete.
Reactive powder concrete (RPC) is a rather new cement-based
material developed through microstructural engineering. Conven-
tional RPC is composed of cement and very fine powders, such as,
crushed quartz and silica fume. The basic principles for the devel-
opment of RPC have been explained by the Richard and Cheyrezy
[262–363]. Cement dosage of RPC is generally over 800–1000 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 (fly 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 reactive-
powder mortars reinforced with brass coated steel fibers. Autoclave
curing yielded flexural strength of 30 MPa and compressive
strength of 200 MPa. Shaheen and Shrive [366] investigated the
freeze–thaw resistance of RPC. RPC has excellent freeze–thaw
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 fine particles other than silica fume, such as, fly ash, limestone
microfiller or metakaolin. Lee et al. [368] found that RPC has a good
repair and retrofit potentials on compressive and flexural strength.
The effects of compressive and flexural 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 fly 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 ash–bottom ash
and fly ash, for lightweight concrete production was developed at
The College of Judea and Samaria (Ariel, Israel) [370–373].
As compared to typical fly ash, with a mean particle diameter
ranging from 20–30 micrometers, ultra fine fly ash can be produced
with a mean particle diameter of 1–5 microns. The reduced particle
size means that the pozzolanic reaction, which is normally a slow
process, is accelerated. Further, the finer particles may more
completely react than the coarser particles of fly ash. So, the
durability and strength benefits that one observes with a typical fly
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
fine fly ash.
Typically, ultra fine fly ash is used at a replacement rate of 5–15%
of the cement weight. At these dosage levels, it has been demon-
strated that ultra fine fly ash contribute more to concrete strength
gain and permeability reduction than common AASHTO M 295
(ASTM C 618) fly ash, and will perform comparable to highly
reactive pozzolans, such as silica fume. Concrete durability prop-
erties, such as resistance to alkali sulfate reaction, sulfate attack,
and corrosion are also enhanced by ultra fine fly ash.
Both AASHTO M 295 (ASTM C 618) Class C and Class F fly ash
have their own specific advantages when used as a cementitious
material in concrete. It may be ideal to have a fly 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 fly ash. The exact ratio of the blend will
depend upon the specific fly ash and their desired behavior in the
concrete.
HVFAC refers to concrete where fly 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 field 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 fly ash, and to
have a significant impact on the production of cement, it is
necessary to advocate the use of concrete that will incorporate
large amounts of fly 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
 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363
large volume of fly ash that has all the attributes of high-perfor-
mance concrete i.e. excellent mechanical properties, low perme-
ability, superior durability, and that is environmentally friendly.
McCarthy and Dhir [374] have demonstrated that fly 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 fly ash, materials of high LOI, and that
which has been treated with moisture. These provide considerable
potential for substantial increases in fly ash utilisation. Fly ash can
be used more effectively in concrete by simple adjustment of the
concrete constituent materials or through more refined 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 fly ash as a binder through post-production pro-
cessing if changes in the production process modify its properties. It
is demonstrated that fly 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, fly ash can be used and will give similar or improved
properties compared to neat Portland cement binders.
The composition and characteristics of fly ash have tended to
dictate the way the material is used in concrete. For example, in
structural concrete fly 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 fly ash.
Experience with fly 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 fly 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 fly ash contents in concrete for mainstream structural
applications. A possible means of achieving this lies in the combi-
nation of fly 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 fineness to provide
high early strength. The advantage of combining fly ash with these
materials is two-fold. The dilution of cement with slow reacting fly
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 fly ash concrete, potentially allowing greater levels of
material to be used.
Given the importance of efficiently using binders and the
increased availability and use of super plasticizing admixtures,
a possible route to minimising the increases in binder content
required with fly 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 [375–377], 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 5–6 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 char-
acter [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 air–water/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 freeze–thaw 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 fly ash in concrete has been reported to affect
the required dosage of AEAs to entrain the proper amount of air in
the concrete mixture [381–384]. Instead of stabilizing the air–
water/cement interface, the AEAs are strongly adsorbed by some
fractions of the fly 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 fly 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 fly ash,
appears to be responsible for the adsorption of AEAs [385–387].
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 Ca2þ and Mg2þ, which are able to form insoluble products
with surfactants. A significant decrease in surfactant adsorption of
a fly ash was observed, after it had been washed with deionized
water to remove soluble ions. Furthermore, the filtrate 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 fly ash was added to an
352 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363
AEA solution. However, in this case, the surfactants were simulta-
neously adsorbed by the fly 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 fly ash, which may influence 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 fly 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 fineness of fly 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 fly ash
quality. Ozonation, thermal treatment and physical cleaning of
carbon have been found to improve the fly ash performance for
concrete utilization. The capability of the residual carbon to adsorb
AEAs can be reduced by exposing fly ash to an oxidizing environ-
ment, which increases the oxygen population on the surface. Gao
et al. [392] discussed how both wet and dry methods can be applied
to improve fly 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, fly ash sales price, and disposal costs, Gao et al. [392] esti-
mated that development of a commercial post-treatment process
based on ozone appears to be profitable. 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 fly ash has
successfully been implemented in at least one case [393], where fly
ash with an average LOI on 12.5 wt% was treated in a fluidized 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 fly
ash quality by ozone treatment.
Separation processes can recover carbon from fly ash, making
the mineral-rich fraction suitable as concrete additive. Several
studies have been published describing how carbon in fly ash can
be reduced by physical cleaning [396–406] and many patents have
been drawn. However, none of the studies compared the AEA
adsorptivity of the fly ash before or after the cleaning process. The
recovered carbon product is often disposed in landfills [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 inter-
action between AEAs and fly ash appears to be related to the
residual carbon present in fly ash due to its capability to adsorb the
AEAs in the concrete mixture. Regulations for approval of fly ash as
concrete additive are typically based on the carbon content deter-
mined by the LOI test. However, the wide installation of improved
combustion technologies in order to reduce NOx emissions has lead
to generation of fly ashes containing residual carbon having
a higher adsorption capacity of AEAs (per unit mass of carbon).
Therefore, fly ashes can show poor performance in concrete utili-
zation even at LOI values within the established regulations. There
are still some unresolved issues within this field, 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 fly ash quality.
This could be beneficial in future design of combustion technolo-
gies, where both low NOx emissions and high-fly ash quality may be
achieved. The relative contribution of soot and char to poor fly 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 fly 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 fly
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 field and
additional experiments and case studies are necessary to uncover
whether there is a problem. Combustion of other alternative fuels
may also affect the fly ash quality, e.g. fly ash from coal/petroleum
coke co-firing 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 fly 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 fly ash is a problem. Various
methods have been suggested for the safe disposal of metal-laden
fly ash. Metal-laden fly ash can be incorporated into the cementi-
tious mixture to a great extent without the risks of unacceptable
delay of cement setting and excess heavy metals leachability from
solidified products. Further, the metal-laden adsorbent was
immobilized into cement for ultimate disposal and no significant
leaching was observed from the stabilized products. The proposed
technology (utilization of industrial wastes for effluent treatment
and then ultimate disposal of adsorbents laden with pollutants in
cementitious materials by fixation) provides a two-fold aim of
wastewater treatment and solid waste management. The coal fly
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
solidified 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 flexural
and mechanical strengths of the solidified specimens were opti-
mized with respect to the dosage of natural and metal-loaded solid
wastes. The fixed 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 þ CaCl2 at
optimal dosages so as to improve the setting, hardening and
mechanical properties of the final concrete block. Weng et al. [105],
indicated that for an extended curing time, it is possible to prepare
mortars with metal-laden fly 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 fly
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
 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363
appears that the fixation process can be environmentally safe.
Metal-laden fly ash should be considered for use in secondary
construction materials.
13. Lightweight aggregate
Use of fly ash as a by-product aggregate in the manufacture of
lightweight construction products presents itself as a logical utili-
zation 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 finished 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 consid-
ered. Fly ash bricks weigh, on average, one-third less than
conventional clay-fired bricks [410], enabling a truck to carry more
bricks per load, thus reducing shipping costs and improving profit
margins. The second economic reason is an abundance of low-cost
fly ash available to make the bricks, yielding an excellent product.
Even though pulverised fly ash brick at first instance may appear to
be costlier than conventional products, ultimate financial benefit
can be evaluated in terms of its increased physical and chemical
properties. Depending on the type of soil, fly ash (20–50%) is used
along with clay to produce clay bricks which are more porous (40–
50%) than fly ash bricks (20%). Though clay-fly ash bricks have high
strength and absorb less water than fly ash bricks.
Fly ash bricks manufacturing units can be set up nearby thermal
power stations, because the main raw materials fly 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 fly
ash bricks manufacturing unit. There is good demand for fly 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 [411–414]. Although fly ash is commonly used in
cements, it has rarely been applied to bricks. Recently it has been
shown that fly 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 fly
ash, sand and hydrated lime in the compressive strength of the
bricks. In the field of Architectural Heritage, there is almost no
research about fly 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 firing temperature, but
generally, bricks fired at high temperatures are more vitreous and
undergo the greatest changes in size and porosity [417]. It has found
that fly 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 40–70%. 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 fly ash brick is a far superior building
material than burnt clay brick. The use of fly ash brick provides
a stronger, more durable construction that is better protected from
efflorescence and salinity with meaningful savings in construction
costs. But the greater benefit lies in controlling two major
353
ecological problems of fly ash disposal and the reduction of culti-
vable 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 fine finish and
can be in different colours using pigments, cost effective, energy-
efficient and environment friendly (as avoids the use of fertile clay).
The technical quality of compositionally different groups of solid
bricks fired between 800 and 1000  C was evaluated [418]. The
textures of the bricks with fly ash were very similar to the textures
of those without it, except that the samples with the additive
contained spherical fly 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 fly 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 fired bricks [419]. The effect of fly
ash with high replacing ratio of clay on firing parameters and
properties of bricks were investigated. The results indicate that the
plasticity index of mixture of fly ash and clay decreased dramati-
cally with increased replacing ratio of fly 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 fly ash was about
1050  C, which is 50–100  C higher than that of clay bricks. The
properties of fired bricks were improved by using pulverized fly
ash. The fired bricks with high volume ratio of fly 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, fly ash has been utilized in the
manufacture of lightweight roofing products such as rigid roofing
tiles. The roofing tiles have the advantage of being both lighter than
clay products and providing a class A fire-rating making them an
excellent replacement for cedar shake roofing in high fire danger
areas. The manufacture of sintered fly ash light weight aggregates is
an appropriate step to utilize a large quantity of fly 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 fly ash lightweight aggregates
will reduce the dead weight and material handling cost for multi-
storeyed constructions.
14. Road sub-base
Utilization of fly ash as a material in the construction of road-
ways and associated peripheral projects has been a significant
outlet for fly ash. Fly ash has been used in embankment soil
stabilization, subgrade base course material, as an aggregate filler,
a bituminous pavement additive and as a mineral filler for bitu-
minous concrete. Fly ash used as a soil stabilizer along roadway
embankments has been a beneficial practice for a number of
reasons. In areas where borrow or fill and cover material are scarce,
fly ash may be in plentiful supply from nearby electric power
generation facilities. Ease of availability combined with positive
physical properties can make fly ash soil stabilization cost effective.
Shear strength is an important characteristic for soil stabilization
fly 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 fly ash having self-hardening or pozzolanic
354 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363
properties, which is a characteristic more common to class C fly ash
and ash from atmospheric fluidized bed boilers.
Construction of road embankments using fly ash, involves
encapsulation of fly ash in earthen core or with RCC facing panels.
Since there is no seepage of rain water into the fly ash core, leaching
of heavy metals is also prevented. When fly 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 fly ash particles. Hence chances of
pollution due to use of fly ash in road works are negligible.
Use of fly ash in road works results in reduction in construction
cost by about 10–20%. 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 fly ash. Hence, when fly ash is used as a fill material,
the economy achieved is directly related to transportation cost of
fly ash. If the lead distance is less, considerable savings in
construction cost can be achieved.
Similarly, the use of fly ash in pavement construction results in
significant 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 fly ash use will be
justified even for lead distances up to say 100 km.
15. Mine backfill
Mine back filling has demonstrated to be an attractive option for
those plants located near the coal mine. Back filling of underground
mines is technically vulnerable and especially holds good potentials
for those areas where sand is scarce. Open cast mine filling 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 influences. 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 filling has been carried out in both controlled
circumstances and in actual field applications. Mine void filling is
undertaken for numerous reasons, the first being for the control of
AMD, where the groundwater table intersects the mining rubble.
The second reason for fly ash grout injection compliments AMD
control by filling mine voids and providing support to areas where
standing coal pillars are crumbling and causing land subsidence on
the surface. The third use for fly ash injection is mine fire control.
Underground coal mining operations conducted many years ago
removed large volumes of coal, leaving only small pillars to main-
tain the structural stability of the surrounding land surface. Envi-
ronmental 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 filled with fly ash grout material to
prevent further subsidence, while disposing of large quantities of
fly ash at the same time. The procedures for conducting under-
ground mine void filling with fly ash for AMD control, subsidence
control and fire abatement are identical [422]. Two methods can be
used, dry fly ash injection or wet slurry injection. Dry fly ash
injection consists of drilling 6 inch diameter boreholes into the
mine void and placing steel casing down to that level. The dry fly
ash is then injected at relatively low pressure (12–30 psi) into the
mine void. The dry fly ash easily flowed 65 feet in either direction
from the borehole along the shaft as it filled to the mine roof. The
ash had an angle of repose of only 8 degrees from the horizontal
exhibiting excellent ‘flow’ characteristics. The eventual filling 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 fly ash with the water
needed for hydration and the fly 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 fly ash (25% water by total mix weight), produces a slurry
that pumps easily and does not shrink upon drying.
Bulk quantities of coal fly ash have been used to replace the
conventionally used sand for reclaiming underground mines.
During 1999–2000, the national Thermal Power Corporation
Limited (NTPC), India used about 60,000 ton of ash for backfilling
underground mines of Singareni Colliery Company Limited,
Southern India, in collaboration with Central Mining Research
Institute, India[423]. The potential application of coal fly ash in
reclaiming abandoned coal mine is of great practical significance.
Research and Development are still on for commercial use of such
huge quantum of fly ash as mine-filling 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 plan-
ning for fly ash back filling in the abandoned mines for eco-engi-
neering 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 configuration of the landscape [424]. Since there are
various limitations and threats to environmental degradation,
effective scientific work is to be done before a firm decision is taken
for bulk use of fly ash in reclaiming abandoned mines.
The technical feasibility of disposing coal combustion by-prod-
ucts 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 by-
products, 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 fly ash and require
additional research. A pilot study of fixated scrubber sludge injec-
tion 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 fly
 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363
ash. Waste baggase fly ash is available for $2 ton1, and considering
the cost of transport, chemicals, electrical energy, etc., used in the
process, the finished product would cost approximately $15
ton1[94].
In order to evaluate the financial implications of fly ash utili-
zation in road construction as an alternative, comparative costs of
conventional and fly ash based road construction for a given
geometry are needed. Kumar and Patil [425] assumed that fly ash is
available free of cost and in the form suitable for road construction.
The cost of fly ash based road construction depends mainly on the
cost of various resources replaced by fly ash and lead (trans-
portation distance). The fly ash transportation cost would have
some finite value depending upon the lead. The soil is locally
available in abundance whereas other materials like stone aggre-
gate, stone chips, etc., are to be transported to the work site. The
loading/unloading cost of the conventional material and fly ash is
also assumed to be the same. The construction cost of a given layer
of fly 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 fly ash utilization and (ii) transportation
cost of fly ash.
Based on cost data of different resources saved, the costs of fly
ash based road construction with flexible and rigid pavement for
different lead were calculated. It can be seen that the cost savings in
fly ash based embankment road construction is nearly 31% which is
in close agreement with the range of 30–40% 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 fly
ash. It was found that the total road construction cost savings
percentage decreases with lead due to increase in the fly ash
transportation cost. The effect of lead on construction cost savings
reveals that the investment on fly ash based road construction
would be financially attractive only for a lead less than 60 and
90 km for flexible and rigid pavements, respectively.
Use of fly ash in road works results in reduction in construction
cost by about 10–20%. Typically cost of borrow soil varies from
about Rs.100–200 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 fly ash. Hence, when fly ash is used
as a fill material, the economy achieved is directly related to
transportation cost of fly ash. If the lead distance is less, consider-
able savings in construction cost can be achieved. Similarly, the use
of fly ash in pavement construction results in significant savings
due to savings in cost of road aggregates. If environmental degra-
dation 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 fly ash use will be justified 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 fly ash. Technical
and economic barriers are not mutually exclusive in that techno-
logical advancements usually result in economic feasibility. Prin-
cipal technical barriers include issues related to coal fly ash
production, specifications and standards, materials characteriza-
tion, product demonstration and commercialization, and user-
related factors. Economic barriers to increased use of coal fly ash
can be key among all factors affecting by-product use. With proper
economic incentives, other barriers to increased use of coal fly ash
can be overcome. For coal-burning electric utilities, the revenues
from the sale of coal fly ash are often insignificant. The high cost of
355
transportation of low unit-value coal fly 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 defini-
tions of coal and coal combustion products (CCP)-related terms.
Subcommittee members evaluated the latest draft of the defini-
tions 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 definition 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 fly ash.
Fly ash transportation cost for reclamation of abundant mine
and road construction is a major constraint. Restriction of excava-
tion of earth for filling 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 fly ash in place of soil for such applications.
Lack of awareness on the advantages of fly 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 fly ash based products to meet the consumer
acceptability and increased marketability. In addition, in associa-
tion with scientists, policy makers and fly ash generators, aware-
ness of the quality parameters and beneficial effects of fly ash based
building materials and its utility should be made clear to the
general public for mass consumption and effective utilisation of fly
ash. There is a production of huge quantity of fly ash followed by
emission of green house gases and intrude significantly 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 fly ash management to reduce the adverse effect on
environment and ecology and future hypothesis by finding reme-
dial measures for the social development. Cost benefit analysis of
fly ash versus conventional building materials are needed to be
thoroughly evaluated for the concrete recommendation for max-
imising the use of coal fly ash.
Barriers to utilisation of coal fly ash on land occur in marketing,
transport, and through the potential for leachates containing trace
elements from fly 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 M. Ahmaruzzaman / Progress in Energy and Combustion Science 36 (2010) 327–363
performance of fly 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 over-
come in terms of high value and high volume utilization for the
industrial applications of fly ash. Generally, raw fly ash has low
adsorption capacity. Modification of fly 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 fly ash. Some investigations
have been made in the hydrothermal conversion of fly ash into
different types of zeolites using the extracted supernatant solution.
Few researchers have been succeeded in the conversion of the bulk
fly ash into pure zeolite [7]. The presence of silico-aluminate phases
in fly 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 quartz–cristobalite–tridymite. The amor-
phous aluminosiliate nature of fly 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 fly ash as soil amendment
has been studied, the full scale application of this technology has
not been implemented. In future, farmers may use fly ash rather
than lime to enrich their soil. The trace elements in fly 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 fly ash, whose
composition in fly ash varies with combustion efficiency. In fly ash,
unburned carbon contents generally range between 2% and 12%.
The higher percentage of unburned carbon in fly ash will lead to
efficiency 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 fly ash has a significant
potential of cost advantage over other activated carbon. Therefore,
separation of unburned carbon from fly ash will be beneficial to fly
ash application, either for carbon recycling or mineral fly 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 60–75% fly 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 specifications. 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 fly 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
field of fly ash.
19. Conclusion
This paper has attempted to cover a wide spectrum of infor-
mation so that the reader can better understand fly ash utilization.
Understanding coal formation and combustion processes provides
both a background and basis for the alternative uses of the resultant
fly ash. This review has shown that, in most cases, reported work to
date in this area has been of laboratory scale, and further devel-
opment work is needed.
Fly ash, although posing environmental pollution, it is an
important raw material for various applications. The utilization of
fly 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 benefit, new
technologies for the efficient utilization of fly ash should be made
use. To improve removal efficiencies and adsorption capacities,
chemical modifications of fly ash is needed. The unburned carbon
in fly 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
benefits 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 tech-
nology for efficient utilization of fly ash. Fly ash utilization pro-
gramme 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 fly
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 fly 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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