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Possible applications of coal fly ash in wastewater treatment

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DOI: 10.1016/j.jenvman.2019.03.054

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 Journal of Environmental Management 240 (2019) 27–46

Contents lists available at ScienceDirect

Journal of Environmental Management

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Review

Possible applications of coal fly ash in wastewater treatment T

a a,∗ a b c
Farwa Mushtaq , Muhammad Zahid , Ijaz Ahmad Bhatti , Saqib Nasir , Tajamal Hussain
a
Department of Chemistry, University of Agriculture, Faisalabad, 38040 Pakistan
b
Pakistan Science Foundation,1-Constiution Avenue G-5/2, Islamabad, Pakistan
c
Institute of Chemistry, University of the Punjab, Lahore, Pakistan

ARTICLE INFO ABSTRACT

Keywords: Management of coal fly ash as a particulate byproduct of coal burning has become an issue to be solved right
Coal fly ash away due to environmental concerns related to soil, water, and air pollution. Many attempts have been made by
Adsorption researchers for the conversion of coal fly ash into useful products while searching feasible avenues for its sus-
Fenton's process tainable utilization. Wastewater remediation using coal fly ash is one such attempt solving both waste man-
Photocatalysis
agement and water quality issues. The characteristics like morphology, surface area, porosity, and chemical
Wastewater treatment
composition (silica, alumina, iron oxide, titania, etc.) make coal fly ash amenable material for potential appli-
Coagulation
cation in wastewater treatment. Few reports have summarized the coal fly ash utilization in wastewater treat-
ment but solely discussed the adsorption. Besides adsorption, the current paper aims to highlight the possibilities
of using coal fly ash in wastewater treatment by different technologies that extend the utilization scope in the
domains of filtration, Fenton process, photocatalysis, and coagulation. The promising use of coal fly ash as an
adsorbent, membrane filter, Fenton catalyst, photocatalyst, and as an integral part of these structures is re-
viewed. Finally, the current trends and future prospects on utilization modes of coal fly ash in wastewater
treatment are stated.

1. Introduction
Coal is a major source of energy worldwide and a large fraction
(37%) of it is used in electric power generation in the US. The coal fed
power plants produce tons of fly ash (FA), bottom ash, and polycyclic
aromatic hydrocarbons (Harkness et al., 2015; Matzenbacher et al.,
2017). Coal fly ash (CFA) is 65–95% of the total ash generated
(Jayaranjan et al., 2014). It is a mineral mixture consisting of various
oxides such as SiO2, Al2O3, and metal oxides which can be alkaline,
alkaline earth, and transition metal oxides (Izquierdo et al., 2008; Liu
et al., 2016a).
Coal-based power stations in India generate 131 million tons of fly
ash per year (Banerjee et al., 2014). In China, > 600 million tons of
CFA was produced in 2015 (Ding et al., 2017). In Brazil, a total of ash
generated per year is 3 million tons. Discharge of fly ash causes serious
health hazards by inhalation of fine particulate matter influencing the
DNA repair mechanism due to PAHs (from unburnt organic matter) and
inorganic elements (mineral fraction) through the formation of reactive
organic species (Jayaranjan et al., 2014; Matzenbacher et al., 2017).
Improper disposal of CFA can interrupt environmental cycles posing
water and soil hazards. Moreover, it can be responsible for smog and
haze resulting in profound air pollution (Liu et al., 2016a). One of the
environmental concerns is leaching of heavy metals from CFA into the
soil when dumped in landfills (Haynes, 2009; Xue et al., 2014). Fly ash
disposal has become a burden on the environment and the economy
(Menéndez et al., 2014).
Finding sites for disposal, cost on long-lasting maintenance, un-
productive exploitation of land, and undesirable effects on the en-
vironment are the basis that discourages fly ash disposal. Fly ash used in
construction products forms relatively small percentage (10–20%).
Value addition to waste fly ash is paramount to expand alternate uti-
lization ways beyond the construction industry (Iyer and Scott, 2001).
The concern in promoting sustainable development has increased the
interest of recycling fly ash into value-addition products (Arif Kamal,
2016). CFA recycling is challenging (Little et al., 2008). Besides these
conventional methods of disposal and reuse, researchers are paying
attention to high-value novel methods.
Notably, a considerable amount of CFA is used for various appli-
cations especially in civil engineering (Aljerf, 2015; Hoy et al., 2016)
and construction (Xu and Shi, 2018), where it stands for a substitute to
cement in concrete (Ebrahimi et al., 2017; Wasserman and Bentur,
1997). Due to the larger surface area and presence of multiple com-
ponents in it, its application in amendments of soil improving texture,
water holding capacity, bulk density, and nutrients has been

∗
Corresponding author.
E-mail addresses: rmzahid@uaf.edu.pk, zahid595@gmail.com (M. Zahid).

https://doi.org/10.1016/j.jenvman.2019.03.054
Received 24 October 2018; Received in revised form 8 February 2019; Accepted 12 March 2019
0301-4797/ © 2019 Elsevier Ltd. All rights reserved.
F. Mushtaq, et al. Journal of Environmental Management 240 (2019) 27–46

appreciated (Bhattacharya et al., 2012; Ram and Masto, 2014; Shaheen
et al., 2014). Additionally, it is used as a precursor to prepare zeolites
(Fukasawa et al., 2017) and mesoporous silica (Li and Qiao, 2016). It is
also used as an adsorbent to capture CO2, SO2, NOx, and mercury (Ji
et al., 2017; Wang et al., 2016a; Yang et al., 2017a) from the air.
Furthermore, its applications include the production of FA-based geo-
polymers (Al-Harahsheh et al., 2015; Böke et al., 2015; Zhuang et al.,
2016b), recovery of valuable metals from CFA (Ding et al., 2017; Sahoo
et al., 2016), and synthesis of fly ash polymer composites for various
purposes like preparation of electromagnetic interference shielding
materials (Lu et al., 2015; Revanasiddappa et al., 2018). One of the
potential applications of fly ash is its use in wastewater treatment that
will help enhance the economy and reduce environmental pollution.
Addressing the problems related to water exclaim for incredible
research to be carried out in order to robust novel techniques for the
decontamination of water at a low price and at the expense of less
energy (Shannon et al., 2010). Certainly, the use of CFA in wastewater
treatment represents a convincing way to manage this byproduct which
otherwise symbolizes a major problem of pollution in many countries of
the world (Gitari and Akinyemi, 2018). Recycling hazardous waste CFA
for the development of value-added products of wastewater treatment
is helpful in both minimizing waste and maximizing productivity.
A number of reviews in literature have been dedicated to the re-
cycling of CFA for environmental protection, construction industry,
agriculture, ceramic industry, and for the purpose of useful component's
recovery (Blissett and Rowson, 2012; Yao et al., 2015). Few reports
(Ahmaruzzaman, 2009, 2010; Ge et al., 2018; Simate et al., 2016) have
discussed the applicability of CFA in wastewater treatment but these
reports exclusively focused on adsorption of pollutants from aqueous
solution. In this article, almost all of the aspects of CFA in wastewater
treatment are highlighted. To the best of our knowledge, this article is
first to review the role of CFA in advanced wastewater treatment
especially photocatalysis and Fenton's process. This article aims to
provide grounds for environmental friendly utilization of CFA as an
integral part of wastewater treatment. A survey of literature with the
purpose of using CFA for (waste) water treatment in different possible
ways as highly efficient and inexpensive adsorbents, coagulants, filters,
catalyst, and catalyst supports is presented. It will also provide insight
into directions to use CFA in water treatment by probable treatment
technologies like adsorption, membrane filtration, photocatalysis, and
Fenton process. Hopefully, this article will promote the development of
CFA-based architecture and composite materials for advanced waste-
water treatment with improved recycling of industrial waste. Before
proceeding further, it is to be clarified that as fly ash is a general term
which can belong to coal, biomass, bagasse, wood etc. Some authors
have used the term “fly ash” for coal-based fly ashes originating from
thermal stations. It is worth-mentioning for the convenience of readers
that the terms “coal fly ash” and “fly ash” or their abbreviations “CFA”
and “FA” in this article refer to coal-based fly ashes. The list of ab-
breviation along with full description is shown is Table S1.
2. CFA characteristics and its formulation for wastewater
treatment
The chemical components of raw CFA include silica, calcium oxide,
alumina, iron oxide, LOI, and many other inorganic constituents. Its
mineralogy is a typical representation of amorphous materials (glass)
and crystalline (true mineral constituents) as well as partially burned or
unburned carbon (UC) (Blissett and Rowson, 2012; Rubio et al., 2008;
Wang et al., 2017b). Usually, silica forms the major component of fly
ash and alumina the second largest component. The third largest
component in most of the fly ashes is Fe2O3 which vary from 1 to 20%.
FA contains various transition metal oxides which are active compo-
nents of many catalytic systems (Wang, 2008). The chemical compo-
sition of different CFA grades is summarized in Table 1. The proportion
of particular chemical constituents is different in CFAs from different
power stations, operating at different burning conditions, resulting in
different catalytic performance in wastewater treatment (Wang et al.,
2017a). The unburned carbon contents of FA vary in range from 2 to
12%, however, sometimes they can be more than 20% (Hsieh and Tsai,
2003). Owing to the high porosity, the UC contents have higher surface
area as compare to other inorganic matter of FA (Hower et al., 2017).
Thus, UC plays role in the adsorption of contaminants from aqueous
solutions.
The noteworthy potential of FA in wastewater treatment is due to
the properties of CFA such as particle size distribution, surface area,
hydrophilicity, and porosity stemming from its complex composition
(Karanac et al., 2018a; Visa et al., 2012). Classification of fly ash is
based on contents of CaO. When among the chemical constituents silica,
iron oxide, and alumina form more than 70% of the whole raw fly ash,
it is categorized as type F fly ash according to ASTM C 618. If silica, iron
oxide, and alumina form less than 70% of the whole raw fly ash, it is
categorized as type C fly ash (Wang et al., 2017b). Another criteria as
per ASTM standards is, FA obtained from combusting bituminous or
anthracite coal is ranked as Class F and that obtained from burning sub-
bituminous or lignite coal is ranked as Class C FA (Blissett and Rowson,
2012). Mostly F-type FA has been used by researchers for water treat-
ment applications. Very few studies have made the use of C-type FA
(Giribabu and Swaminathan, 2016). This is due to the variation of
calcium contents.
3. Utilization of coal fly ash in wastewater treatment (WWT)
The whole world is dealing with water scarcity issues owing to
discharge of partially treated or untreated wastewater from industries
and pollution of groundwater. The demand for clean water has become
increased to meet up the needs of a sustainable society (Akar and Uysal,
2010; Aljerf, 2018a). The growing concern for the development of ef-
ficient and cheap water treatment methods have increased the interest
in recycling waste fly ash. It has been widely explored as a low-cost
adsorbent. CFA can also be converted into a suitable catalyst for its use

Table 1
The chemical composition of different grades of CFA.
FA Origin Composition (%) Application in wastewater treatment Reference

SiO2 Al2O3 Fe2O3 CaO K2 O NaO MgO TiO2 P2O5 SO3 LOI

Poland 49.7 27.5 5.9 4.59 2.98 1.00 3.09 1.2 0.54 1.00 – Heavy metal adsorption Adamczuk and Kołodyńska (2015)
Romania 53.32 22.05 8.97 5.24 2.66 0.63 2.44 1.07 – – 1.58 Photocatalysis Visa et al. (2015b)
India 55.2 24.9 7.8 0.9 2.1 0.15 0.11 1.9 0.2 0.02 – Photocatalysis Mazumder and Rano (2018)
China 46.49 40.56 4.27 4.37 0.45 0.08 0.27 1.88 0.63 0.34 – Membrane filtration Wei et al. (2016)
USA 43.65 21.03 25.48 2.58 – 1.25 – – – 1.03 – Coagulation Li et al. (2009)
China 66.10 16.30 5.45 5.48 1.24 0.60 1.03 – – – 3.48 Fenton-like process Wang et al. (2017a)
Canada 35.46 18.16 10.35 15.53 0.74 – 3.68 1.15 0.25 6.49 – Heavy metal adsorption Appiah-Hagan et al. (2018)

28
F. Mushtaq, et al.
Fig. 1. A layout of wastewater treatment methods where and why CFA is applicable.
in advanced oxidation processes (AOPs). Fig. 1 illustrates a layout of
wastewater treatment methods where CFA can be used and its motive
for applicability to a particular method. Several published reports have
shown that the catalysts derived from CFA are environmentally
friendly, economical, and efficient.
The number of published documents extracted from Scopus since
2005 to 09-08-18 searched with the query string composed of “fly ash
and wastewater or waste water treatment or adsorption or photo-
catalysis or Fenton or filtration” in the field code (title-abs-key) are
presented in Fig. 2.a. The increasing trend of the results depicts that the
application of CFA in wastewater treatment is gaining momentum. In
this field, CFA is extensively utilized as an adsorbent. Adsorption is
being carried out for decades but from the last decade, other treatment
methods are becoming more popular than adsorption. Besides adsorp-
tion, CFA has also been tried in photocatalysis, Fenton-process, and
membrane filtration. The percentage of references corresponding to
different wastewater treatment methods using CFA is demonstrated in
Fig. 2.b with the help of a pie chart. CFA has been rarely used in
membrane filtration and Fenton's process. Its potential usage in pho-
tocatalysis is realized recently. The role of CFA in these treatment
Fig. 2. (a) No. of publications on the use of coal fly ash in wastewater treatment take out from Scopus since 2005 to Aug 2018. (b) Demonstration of percentage
publications on wastewater treatment methods using coal fly ash.
29
Journal of Environmental Management 240 (2019) 27–46
processes is reviewed under each corresponding section.
In some studies, CFA has been directly applied as adsorbent or
catalyst. Obviously, its direct application is beneficial in the sense that
resource is utilized but this is at the cost of effectiveness. The variation
in morphology, chemistry, and mineralogy of CFA samples is a hin-
drance in its direct usage (Blissett and Rowson, 2012; Ram and Masto,
2010). In order to get the required formulation for selected wastewater
treatment technique, pristine CFA is subjected to many kinds of pre-
liminary treatments such as mechanical activation, chemical mod-
ification, impregnation, and thermal or heat treatment (calcination at
high temperature) for better performance. Moreover, to fully add the
values to CFA in water treatment, it has been converted into various
ceramic products, zeolite materials, and geopolymers which in turn are
used for wastewater treatment.
3.1. Coal fly ash application in adsorption
Unburned carbon in FA allows adsorption of organic compounds
like dyes, phenols, herbicides, toxic metals, petroleum constituents,
polychlorinated biphenyls, and many other inorganic contaminants
F. Mushtaq, et al.
from wastewater (Hower et al., 2017). Herein, we have reviewed ad-
sorption of metal ions and dyes onto CFA (either pristine or modified
and transformed by several ways into other products) from wastewater.
3.1.1. Adsorption of toxic metal ions from wastewater using coal fly ash
Heavy metals are the most toxic pollutants in wastewater and a
severe threat to public health (Aljerf, 2018b; Tauanov et al., 2018;
Wang and Wu, 2006). Among several removal methods adsorption has
been an effective and simple technique for heavy metal ions uptake by
FA as a cost-effective adsorbent. The removal of heavy metals using FA
from industrial water was first reported by Gangoli et al., in 1975
(Wang and Wu, 2006). Fly ash dispersed in water is alkaline and ex-
hibits pH from 10 to 13. At high pH values, the surface of FA is nega-
tively charged with the potential to remove heavy metal ions from
water by electrostatic adsorption and precipitation (Cho et al., 2005).
Ayala and co-workers have found FA an effective adsorbent for Cd and
Cu while studying the effect of initial metal concentration on adsorp-
tion capacity. FA neutralized the metal solution due to its basic nature
and adsorption capacity increased as the initial concentration of metal
was decreased (Ayala et al., 1998).
When engrossed in water, the oxides form hydrated complexes like
Fe(OH)+ and Al(OH)+ on FA surface (Chaudhary and Balomajumder,
2014). Highly active Al2O3, SiO2, and other oxides act as adsorption
sites (Visa et al., 2015b). Fly ash high affinity for metal ions is ascribed
to the silica surface. Silicates central ion Si4+ strongly attracts elec-
trons. Therefore silicon bonded oxygen has low basicity, letting silica
surface function as a weak acid. pH dependence of surface charge is
determined by SiOH group acidity. Similarly iron and alumina show pH
dependence of surface charge. Under alkaline conditions, active sites on
FA are thought to form as in equations (1) and (2) (Mohan and
Gandhimathi, 2009).
CFA SiOH + OH CFA SiO + H2 O
CFA AlOH + OH CFA AlO + H2 O
− − − −
The SiO , FeO , AlO and TiO as adsorption sites for metal
ions removal were also reported by (Appiah-Hagan et al., 2018). These
negative active sites on the surface are credible to form complexes with
the metal ions (M2+) (Visa and Duta, 2013b). Equations (3) and (4)
shows metal complexing on active sites.
2(CFA SiO ) + M 2 + M (CFA Si O )2
2(CFA AlO ) + M 2 + M (CFA Al O)2
M2+ ions under alkaline conditions can also bound with hydroxyl
groups to form M(OH)2 which undergo adsorptive interaction with
isolated -OH groups on silica removing two water molecules Fig. 3 a).
Hydroxyl group of AleOH interacts with Bronsted assisted acid centers
Fig. 3 b) or metal bounded -OH groups interact with Lewis acid centers
like tertiary coordinated Al of CFA framework Fig. 3 c) (Sočo and
Kalembkiewicz, 2013). Here M can be any bivalent metal ion.
To further enhance the adsorption capacity of raw CFA, it can be
modified by many ways discussed in the next section.
Fig. 3. Coal fly ash surface chemical structure showing aluminosilicate model
(Sočo and Kalembkiewicz, 2013).
Journal of Environmental Management 240 (2019) 27–46
3.1.2. Modification of CFA for metal ions adsorption
Class F fly ash is suitable for conversion to substrates with high
adsorption capacity due to the high content of SiO2 and Al2O3. It has
been altered chemically by hydrothermal treatment into a substrate
having highly polar surface and investigated for the complex process of
adsorption from a multi-cation pollutant system containing zinc, cad-
mium, and lead cations together (Visa et al., 2012). Hydrothermally
modified CFA involved both adsorption and ion exchange processes for
metal ions removal with 2–25 times higher adsorption capacity than
original ashes (Nascimento et al., 2009). It was due to the formation of
zeolite phases during hydrothermal treatment. Microwave-assisted al-
kali modified FA for the adsorption of hexavalent chromium ions from
water has been used (Deng et al., 2018).
Chemically modified CFA has a high potential for the removal of
pollutants from wastewater. Nitric acid etched CFA, functionalized with
thioglycolic acid and 2-mercaptoethanol, have retention efficiency of
91–99% and 90–97% respectively for Cd, As, Cu, Al, Mn, Ni, Fe, Hg, Zn,
and Pb ions from aqueous solution. This is due to the chemical char-
acteristics of mercaptans (presence of OH and SH groups for co-
ordination with metal ions). Some metal ions (Pb, As, Zn, Ni) co-
ordinated to mercaptan group, while other (Mn, Cu, Al, Hg, Fe, Cd)
were reported to coordinate with the oxygen atoms from the framework
of CFA (Muñoz et al., 2014). CFA can be modified with mesoporous
siliceous materials by incorporating different organic functionalities to
enhance metal uptake. The new matrix material synthesized by CFA
modification with 3-aminopropyl-triethoxysilane functionalized meso-
porous silica has larger specific surface area, greater number of active
sites, and pore volume with high Cu2+removal capacity from 95% to
98% (Pizarro et al., 2015). Organically functionalized mesoporous
molecular sieves modified with amine and thiol groups (having lone
pair electrons), form complexes with metal ions Pb2+, Cd2+, Zn2+,
Cu2+, and Hg2+. Li and co-workers achieved 97.22% lead ions removal
(1) rate from contaminated water and 131 mg/g saturated adsorption ca-
pacity of amino-functionalized fly ash-based SBA-15 mesoporous mo-
(2) lecular sieve (Li et al., 2017).
Mechanically activated fly ash has enhanced surface reactivity, in-
creased silica contents, and reduced particle size for metal ions removal
resulting in improved adsorption capacity of Mn(II), Pb(II), Cu(II), Zn
(II), and Ni(II) from aqueous solutions (Xiyili et al., 2017). In addition
to modifications by organic molecules, some researchers modified CFA
by inorganic nanoparticles. Modified FA by magnetite for As(V) re-
(3) moval from water has been done (Karanac et al., 2018a) Loading
magnetic nanoparticles over FA solves the difficult separation. De-
position of AgeFe3O4 nanoparticles onto CFA for effective Pb2+ions
(4)
removal is tried (Joshi et al., 2015). FA provided nucleation sites for the
growth of metal oxide and metal nanoparticles. The protonation/de-
protonation of surface metal oxides of CFA developed charged moieties
which underwent electrostatic attraction of Pb2+ions. The adsorption
capacities of various fly ash-based adsorbents are compared in Table 2
for mostly encountered metal ions.
3.1.3. CFA transformed materials for metal ions adsorption
Synthetic zeolites derived from CFA and modified with various
hydroxides, metals, and metal oxides further expand the application
area (Goscianska et al., 2018; Tauanov et al., 2018). CFA derived
zeolites contain zeolite and non-zeolite fractions which can be func-
tional in removing heavy metals, cationic, and anionic pollutants. The
zeolite fraction (carrying negative charges) is responsible for removal of
cationic pollutants and non-zeolite fraction (containing Al2O3, CaO, and
Fe2O3 originally derived from CFA) is responsible for the removal of
anionic pollutants from water (Xie et al., 2014). Zeolites have unique
chemical and physical properties like ion exchange capacity, thermal
stability, molecular size pore structure, and crystallinity (Nascimento
et al., 2009).
Removal of metal ions by synthetic zeolite (Nascimento et al.,
2009), zeolite X from CFA (Jha et al., 2009), zeolite NaeP1 synthesized
30
F. Mushtaq, et al.
Table 2
Adsorption capacities of Zn, Cu, Cr, Pb, Cd, and As ions onto FA and modified or transformed FA adsorbents.
Heavy metal ion Adsorbent
Zn (II) FAZ
Chitosan/FA
Lime modified FA
Hydrothermally activated FA
Cu (II) Chitosan/FA
TiO2-FA
FA geopolymer
Cr (II) Chitosan/FA
Pb (II) FA
FAG
FAZ
CFA nanozeolite
Lime modified FA
AgeFe3O4/FA
Cd (II) FAZ
TiO2-FA
As (IV) FAMa
Chitosan/FA
Lime modified FA
a
FAM: fly ash magnetite.
by Brazilian coal fly ash (Cardoso et al., 2015), zeolite material syn-
thesized by hydrothermal modification of coal fly ash (Visa, 2016), and
Ag-doped CFA derived zeolite (Tauanov et al., 2018) has been reported
in literature. Itskos et al. tested artificial aqueous samples of (Cd, Cu,
Ni, Pb, Cr, and Zn) heavy metals with known concentration and also
tested water sample from lignite mines in Greece using fly ash-based
synthetic zeolites. The uptake efficiency of zeolitic material for poten-
tial pollutants was up to 100% (Itskos et al., 2015). 94% Hg2+ removal
by developing a low-cost zeolite from CFA with comparable perfor-
mance to activated carbon have been reported (Attari et al., 2017).
CFA derived amorphous geopolymer displayed higher Pb(II) ad-
sorption capacity than RFA (Al-Zboon et al., 2011). The adsorption of
Cu2+ ions by FA, FA-based geopolymer, and zeolite was studied. The
adsorption capacity of geopolymer was better than FA and zeolite
(Wang et al., 2007). Geopolymers exhibit heterogeneous micro-
structure, amorphous structure, and better surface properties (Siyal
et al., 2018). Liu and co-workers found the Pb2+ adsorption capacities
of FA and geopolymer to be 49.8 and 118.6 mg/g respectively at
pH = 3. The raw FA reached adsorption equilibrium in 240min while
150 min was sufficient to reach adsorption equilibrium for geopolymer.
The best fit kinetic model for RFA was first order and for geopolymer
was second order revealing the chemisorption happening for geopo-
lymer (Liu et al., 2016b). The adsorption characteristics of cadmium,
zinc, lead, and copper with different metal concentrations at pH values
varying from 3 to 10 using different concentrations of fly ash were
investigated (Cho et al., 2005). The optimum pH of maximum Zn, Pb,
and Cd adsorption was 5.5 and 6.6 found by (Visa et al., 2012). Higher
pH favor adsorption as positively charged species H3O+ at lower pH
competes with the metal ions for adsorption (Rahimi et al., 2015).
Readers further interested in the application of zeolites for heavy metal
and dyes removal should refer to the article cited herein (Koshy and
Singh, 2016).
Going through these studies, we can state the CFA potential for
uptake of metals can be increased by the acid, base, and mechanical
activation or chemical and hydrothermal modification. In addition, the
transformation of CFAs to zeolites, mesoporous materials, and geopo-
lymers has the much-improved performance for heavy metal removal
from wastewater.
3.1.4. Adsorptive removal of dyes from wastewater using CFA
Discharge of dyes into the water leads to reduced aesthetic value,
water clarity, and photosynthetic activity posing a serious threat to
organisms as well as human beings (Gupta, 2009; Lin et al., 2016;
31
Journal of Environmental Management 240 (2019) 27–46
Adsorption capacity (mg/g) Reference
18.87 Visa et al. (2012)
55.52 Adamczuk and Kołodyńska (2015)
33.13 Karanac et al. (2018b)
7.89 Visa (2016)
28.65 Adamczuk and Kołodyńska (2015)
21 Visa and Duta (2013b)
113.41 Duan et al. (2016)
36.22 Adamczuk and Kołodyńska (2015)
48.03 Liu et al. (2016b)
74.48 Liu et al. (2016b)
2000 Visa et al. (2012)
196.24 Sivalingam and Sen (2018)
26.06 Karanac et al. (2018b)
526.5 Joshi et al. (2015)
30.21 Visa et al. (2012)
35.80 Visa and Duta (2013b)
19.14 Karanac et al. (2018a)
19.10 Adamczuk and Kołodyńska (2015)
29.71 Karanac et al. (2018b)
Yagub et al., 2014). CFA can efficiently remove dyes and pigments
discharged by textile and dye manufacturing industries into water
bodies. If we search in the literature about the removal of dyes by ad-
sorption, it will be clear that from the last two decades CFA has been
scantily used for the adsorption of dyes (Banerjee et al., 2014). In order
to remove colored impurities from wastewater both raw and modified
CFA has been used (Hsu, 2008). Modified FA is more efficient adsorbent
for the removal of pollutants. CFA has been stated to be modified with
alkali (Gao et al., 2016), acid (Chen et al., 2010b; Lin et al., 2008),
surfactant (Talman and Atun, 2006) and salt (Gu et al., 2015) to en-
hance removal characteristics of various dyes. Wang and Zhu modified
CFA sonochemically for enhanced dye adsorption (Wang and Zhu,
2005). The influence of chemical (Acid), microwave and sonochemical
treatment of fly ash for MB, RhB, and CV adsorption has been studied.
Acid-treated FA showed increased adsorption behavior (Wang et al.,
2005).
Modification of CFA with NaOH solution by hydrothermal treat-
ment resulted in increased pore volume and surface area significantly
enhancing the adsorption capacity of Rhodamine B and Methylene blue
from water (Wang et al., 2006). Hydrothermal processing involves
dissolution and then recrystallization of FA constituents developing
new components (Visa et al., 2015a). It also leads to a more uniform
distribution of particle size (Visa et al., 2015b). NaOH-FA has increased
surface roughness and irregularly shaped particles as compared to
chemically inert pristine FA having glassy beads of small size, particles
of compact surfaces, and regular spherical shapes. Hydrothermal en-
vironment leads to breakage of AleO and SieO bonds in FA, thereby
improving the dye adsorption performance (Gao et al., 2016). Com-
bined modification with Ca(OH)2 and Na2FeO4 enhanced the adsorp-
tion capacity of FA for methyl orange owing to an increase in surface
area, mechanical strength, and porosity (Gao et al., 2015). All mod-
ifications not necessarily improve the adsorption ability of CFA. For
example, Hsu (2008) did not find the increased adsorption of Acid red 1
onto heat and alkali modified CFA. So, it depends upon the type of
adsorbate too. Table 3 summarizes the adsorption capacity of various
dyes onto CFA and CFA-based adsorbents.
Dash and co-workers (Dash et al., 2018) functionalized CFA with
sulphonic acid groups which allowed both hydrogen bonding and
electrostatic interactions of the adsorbent with the Rhodamine 6G and
Malachite green. Investigation of the adsorption behavior of methylene
blue onto mechanochemically modified CFA has recently been reported
(Li et al., 2018a). Ball milled CFA showed high adsorption capacity than
raw CFA. Different FA classes have different adsorption capacity for
 F. Mushtaq, et al.

Table 3
Summary of adsorption capacity of CFA and CFA-based adsorbents for dyes.
Adsorbent Dye Adsorbent Dose Contact time pH Temperature (◦C) Initial dye Adsorption Adsorption Removal Adsorption Reference
(g/L) (min) concentration (mg/L) kinetics isotherm capacity (%) capacity mg/g

CFA Acid Red 1 1 180 6 30 400 Pseudo second Langmuir – 92.59–103.1 Hsu (2008)
CFA/600 order 32.79–52.6
CFA/NaOH 12.66–25.1
Ca(OH)2eNa2FeO4 modified Methyl Orange 4 40 10 Room 50 Pseudo second Freundlich 99.2 14.76 Gao et al.
fly ash temperature order (2015)
Fly ash Reactive Red 23 50 60 7.5–8.5 20 100 Pseudo second Langmuir – 2.202 Sun et al.
Reactive Blue 50 5–6 order Langmuir 1.860 (2010)
171 10 Freundlich 10.937
Acid Black 1 10 Freundlich 10.331
Acid Blue 193
Fly ash Acid Orange II 83.33 30 – 20 – Pseudo second Langmuir – 1.10 Zheng and Pi

32
Acid Red BG order 3.15 (2010)
CFA Acid Blue 25 2 60 11 20 1000 – – – 410 Ferrero (2015)
Basic Blue 9 500 142
CFA Disperse Blue 80 120 6 45 26.8 Pseudo second Langmuir 71 – Kisku et al.
Disperse 60 100 31.8 order 75 (2015)
Orange
Hydrothermally modified CFA Methylene Blue 10 90 10 40 5 Pseudo second Langmuir 94.3 – Mor et al.
order (2018)
CFA/NiFe2O4 Congo Red 1.5 180 7 25 ± 2 25 Pseudo second Langmuir – 23.32 Sonar et al.
order (2014)
CFA/CoFe2O4 Malachite 4 5 7 25 25 – Freundlich – 89.3 Zhang et al.
Green (2016)
Fly ash zeolite Amido Black 10 360 4 20 20 Pseudo first Freundlich 74 – Garg et al.
10B order (2015)
FA-based Al-MCM-41 Methylene Blue 0.5 120 10 Room 150 Pseudo first Langmuir – 277.78 Zhou et al.
temperature order (2015)
Journal of Environmental Management 240 (2019) 27–46
F. Mushtaq, et al.
different categories of dyes like azo, acidic, basic, direct, non-direct,
and non-azo dyes (Mor et al., 2018). Adsorption of cationic and anionic
dyes is pH dependent phenomenon (Sun et al., 2010). The pH of the
initial solution influences the surface charge of FA which, in turn, in-
fluences the degree of dye adsorption over its surface (Zhou et al.,
2015). All type of traditional modifications (alkali and acid) results in
the generation of basic or acidic wastewater and do not activate fly ash
fully (Gao et al., 2017). To increase its surface charge and area many
alternatives are used for surface modification (Duta and Visa, 2015). FA
surface can be modified to make its use in polymers as filler (Yang et al.,
2006). Visa et al. modified FA/TiO2 nanocomposite by hexadecyl-tri-
methylammonium bromide (HTAB) for the purpose of controlling sur-
face charge (Visa et al., 2015a).
The surface of modified fly ash can be further modified by hydro-
philic or hydrophobic groups to fully activate the surface and enhance
its interaction with polar and non-polar pollutants (Gao et al., 2017).
Hydrophilic fly ash hybrid composites having positively charged sur-
face interact electro-statically with anionic dyes. Modified fly ash
composite built up hydrophobic surface character which further en-
hanced the interaction of fly ash with oily substrates.
It can be seen from Table 2 that the commonly fit adsorption ki-
netics and adsorption isotherm are pseudo-second-order kinetic model
and Langmuir isotherm signifying the homogeneous active sites dis-
tribution and monolayer formation of adsorbate dyes. Another best fit
model for most of the CFA-based adsorption studies for dyes is the in-
traparticle diffusion model.
In addition to modification of CFA, integration of adsorption process
with another removal method is also effective. Combined fly ash ad-
sorption and electrochemical oxidation treatment removed all color and
decreased COD and intermediate toxicity of Methylene blue with
4000 mg/L fly ash (Wang et al., 2010). Fly ash alone is needed in larger
quantity for similar results. For the decolourization of Reactive Yellow
dye, combined fly ash sorption and biodegradation using fly ash as
immobilization material for Pseudomonas sp. has been used (Roy et al.,
2018). The integral approach was effective than both individual
methods.
3.2. Fly ash-based membrane filters for wastewater treatment
Porous inorganic ceramic membranes have received more attention
because of their high thermal, mechanical and chemical stability, low
energy consumption, rugged structure, environmental friendliness, se-
paration efficiency, membrane regeneration efficiency by back flushing,
long time of operation, and high selectivity (Abadi et al., 2011; Cao
et al., 2014; Dong et al., 2006; Jedidi et al., 2009a; Lim et al., 2009).
But the limited availability of raw materials like Al2O3, SiO2, TiO2,
ZrO2, and other oxides for ceramic membranes and their associated
high cost over polymeric membranes have restricted their practical
applications (Cao et al., 2014; Van Gestel et al., 2008). In view of the
fact that SiO2 and Al2O3 form the major part of CFA, many efforts have
been made for the preparation of porous filter media especially in-
expensive micro-porous inorganic membranes from it for effluents
treatment in large volume (Cao et al., 2014; Dong et al., 2009, 2010).
Higher oil removal efficiency is the major benefit of these membranes.
The pore size of the membrane is a key factor in the application of
filtration. Different types of additives such as calcium carbonate (Kaur
et al., 2016), starch (Lorente-Ayza et al., 2015), activated carbon (Das
et al., 2016), and graphite (Birol et al., 2006) are used to control the
permeability and porosity of the membrane. Membrane support using
fly ash and CaCO3 was employed as pore former (Wei et al., 2016).
CaCO3 undergo in-situ decomposition to CO2 developing pores in the
membrane (Siriruang et al., 2016). CFA can also be used as a pore-
forming agent to enhance the permeability and porosity of ceramic
membranes.
Permeable porous support is essential for resourceful membrane
(Feng et al., 2013). In addition to mechanical strength, the support also
33
Journal of Environmental Management 240 (2019) 27–46
provides flow transport (Biesheuvel and Verweij, 1999). The separation
process is favored by the asymmetric configuration of the membrane by
coating of single or multiple membrane layers onto macro-porous
support (Aust et al., 2006). A multilayered composite membrane was
fabricated from CFA as preliminary material (Zhu et al., 2016). They
developed an asymmetric mullite-based hollow fiber support and de-
posited hydrophilic titania layer by a dip coating method to facilitate
the repellence of oil droplets thereby, weakened the membrane fouling.
Fabrication cost is decreased to a significant extent by the choice of
support material because the main cost of the entire membrane is due to
support/layer mass ratio and sintering expenses (Cao et al., 2014;
Sarkar et al., 2012). Due to the low sintering temperature than metal
oxide precursors, fly ash can replace commonly used support materials
including mullite, alumina, and cordierite which are expensive
(Almandoz et al., 2015). CFA can also be converted into various
ceramic products like mullite (Li et al., 2018b). In many studies other Al
sources like bauxite, alumina, and aluminum hydroxide are added to
CFA for the preparation of mullite based membranes. Mineral supports
from CFA and calcined bauxite along with the addition of titania (Dong
et al., 2010), fly ash, and bauxite (Dong et al., 2009) and anorthite-
cordierite based support to recycle CFA by the addition of dolomite (Liu
et al., 2016a) have been developed. A whisker structured ceramic
membrane was fabricated and its efficiency in oily wastewater se-
paration was evaluated (Chen et al., 2016). They used a mixture of
natural bauxite and CFA with the addition of WO3. Oil/water emulsion
microfiltration showed much improved (99%) oil rejection.
FA-based ceramic membranes have many merits like chemical and
thermal stability, catalytic properties, long lifetime, and pressure re-
sistance derived from their inherent nature (Jedidi et al., 2009a). Mi-
crofiltration membranes of different configurations from CFA were
prepared and their fouling behavior by aeration effect was studied in
addition to testing the efficiency of membranes for municipal waste-
water treatment. Due to their brittle nature, CFA membranes cannot
resist pressure. However, the performance can be enhanced using in-
ternal support (Namburath et al., 2015). The spherical fraction of fly
ash was used to fabricate a novel ceramic membrane (Fang et al., 2013).
The ideality of spherical particles for membrane material is ascribed to
the formation of regularly shaped pores in ceramic membranes. This
membrane showed lower fouling, higher permeate flux, and higher
pollutant rejection in suspension having rigid particles and oil in water
emulsion. Rejection efficiency of oil can be calculated by following
expression in equ 5.
Cf Cp
R (%) = × 100
Cf (5)
Here, Cf refers to the concentration of oil in the feed and Cp refers to
the concentration of oil in permeate. R (%) is the rejection efficiency.
The performance of CFA-based filtration membranes from some docu-
ments are discussed in Table 4.
FA was utilized with organic additives like amijel and methocel to
manufacture ceramic membranes for effluent treatment (Jedidi et al.,
2011). FA (> 50 wt%) with various inorganic precursors like sodium
metasilicate, calcium carbonate, and boric acid was used to prepare a
microfiltration membrane for the separation of O/W emulsion (Singh
and Bulasara, 2015). They found FA membrane has high chemical
stability in acidic and basic conditions over a range of sintering tem-
perature and has high mechanical strength of 8–20 MPa over those of
kaolin-based (3–8 MPa) membrane.
Elaboration of a ceramic membrane having CFA-based macro
porous support and CFA-based active membrane skin layer has been
tried for the decolourization of dye wastewater (Jedidi et al., 2011).
Recently, the applicability of CFA has endeavored as a filter in WWTP
in Morocco (Taoufiq et al., 2018). CFA filter was integrated as an im-
portant step in the treatment process. The porosity and surface area of
FA led to the removal of heavy metals (Okada and Tomikawa, 2012).
Due to the presence of natural uranium in coal, CFA from coal
F. Mushtaq, et al. Journal of Environmental Management 240 (2019) 27–46

incineration can have some natural radioactivity (Kant et al., 2010;

Singh et al., 2015). Taoufiq and coworkers evaluated the water treated

Jedidi et al. (2009b)

by coal ash filters in each stage of WWTP to confirm that these ha-

Suresh et al. (2016)

Suresh et al. (2016)
Suresh et al. (2016)
Singh and Bulasara

Chen et al. (2016)

Fang et al. (2013)
Zhu et al. (2016)

Zou et al. (2018)

zardous materials could not pose radioactivity in the treated water
(Taoufiq et al., 2018). In addition to porosity and surface area, surface
Reference

functionality also affects the retention of pollutants (Kim et al., 2018).

(2015)
This is because the membrane surface charge is affected by pH value
which in turn influences the pollutants retention (Fang et al., 2013).
Moreover, the coating of the membrane surface with hydrophilic na-
Rejection (%)

noparticles like TiO2, ZrO2, and Al2O3 enhance the hydrophilicity of the
membrane because of surface hydroxyl groups. Hence, fouling and re-
95.30

99.94
99.99
96.12

> 99
99.2

tention (%) are influenced by CFA membrane functionality (Zhu et al.,

97
90

99

2016).
CFV (ms−1)

Besides ceramic membranes, fly ash particles can be incorporated

into polymer matrixes as filler to modify the properties of polymeric
0.15
1.76

membranes. A multifunctional nanocomposite membrane, exhibiting

4

–
–
–
–

–
–

high water flux, good adsorption for metal ions, and remarkable photo-
degradation of dyes, was fabricated by incorporating fly ash and titania
Trans membrane pressure

nanoparticles to polyurethane (Kim et al., 2014). A lot of research is to

be carried out in this field to realize the true potential of fly ash-based
microfiltration membranes.
Membrane configuration, pore sizes, water flux values and percent rejection of fly ash derived ceramic membranes from some literature reports.

3.3. CFA application in coagulation

0.025
(bar)

0.69
0.69
0.69
1.38

CFA has also been used to form coagulants for wastewater treat-
1

1
–

ment. Appropriateness of CFA as a coagulant is due to the proper

weight ratio of oxides of aluminum and iron which form complex
Rejected pollutant from

coagulants (Chen et al., 2010b; Fan et al., 2003; Suo et al., 2013). CFA-
based coagulants by fly ash leaching were prepared using hydrochloric
acid (Yan et al., 2012). The resulting composite coagulants were as-
sessed for treating wastewater from coal washing. The SS and COD
removal was 99.61% and 96.48% respectively. Thus, leaching of Fe3+
water

Dyes
Oil
Oil

Oil
Oil
Oil
Oil

Oil
Oil

and Al3+ from CFA was used to get a helpful chemical reagent for
wastewater remediation.
Pure water flux (L m−2 h−1 bar−1)

In comparison to commercial coagulants which require ores as raw

material, the CFA-based coagulants are inexpensive with performance
comparable to conventional coagulants and polymer coagulants. The fly
ash associated metal salts like Al3+, Fe3+, Fe2+, Ca2+, and Mg2+ are
solubilized and hydrolyzed by CFA-based coagulant. Different methods
like charge neutralization, adsorption, entrapment, and complexation
CFA was used as a precursor to prepare mullite support, CFV: cross flow velocity.
4.751 × 103

1.234 × 103

into insoluble aggregates are used to remove organic matter in case of

1.56 × 104

ferric or alum as hydrolyzing coagulants. On the other hand wastewater

1800
2342
3430
150

450

coagulation by CFA-based coagulant is derived by integrated processes

–

taking place. Chemically modified CFA with increased adsorption po-

tential improve the coagulation performance by adsorbing pollutants
Average pore size

on residual FA particles. Activated silica from CFA aids coagulation by

forming larger and strengthened flocs (Hu et al., 2016). Other ad-
vantages include short time essential for flocs formation and increased
settling rate of flocked particles (Viraraghavan and Dronamraju, 1992).
(μm)

0.77
0.11
0.25
1.41
1.36
1.53

0.48
1.2

0.1

A complex coagulant having Fe2(SO4)3 and Al2(SO4)3 was prepared

by FA (Fan et al., 2005). Following chemical reactions take place as per
Membrane configuration

equations (6) and (7)converting oxides into Fe3+ and Al3+ ions of
coagulant.
Fe2 O3 + 3H2 SO4 Fe2 (SO4 )3 + 3H2 O (6)
Hollow fiber
Asymmetric

Asymmetric
Disk type
Tubular

Al2 O3 + 3H2 SO4 Al2 (SO4 )3 + 3H2 O (7)

–
–
–

CFA-based coagulants effectively remove turbidity and other water

Membrane 1 (80 wt% CFA)
Membrane 2 (80 wt% CFA)
Membrane 3 (70 wt% CFA)

impurities. The performance of few CFA coagulants is enlisted in

Table 5 with focus on CFA Fe and Al contents and leaching conditions.
It is clear from the table that the conversion efficiency of CFA oxides
Membrane material

into coagulants is dependent on leaching time and temperature. The

CFA/alumina
TiO2-mullitea

CFA/bauxite

ratio of Fe3+ and Al3+ mass in coagulant to the iron or aluminum mass
in CFA is the conversion efficiency (Hu et al., 2016; Li et al., 2009).
Table 4

Polymeric aluminum ferric chloride coagulant using CFA as a raw

CFA

CFA

CFA

material was synthesized and treated wastewater containing a high

34
F. Mushtaq, et al. Journal of Environmental Management 240 (2019) 27–46

amount of oil and suspended solids (Zhang et al., 2018a). CFA extracted

Hu et al. (2016)

Li et al. (2009)
iron and aluminum oxides were converted into PFS and PAF coagulants

Zhang et al.
with concomitant flue gas scrubbing for SO2 removal along with was-
Reference

Fan et al.

(2018a)
(2005)
tewater coagulation (Li et al., 2009). The performance of coagulant at
even low concentration was better than conventional ferric and alu-
minum sulphate coagulants. Sun et al. extended the use of FA compo-
nents in coagulation by preparing poly ferric-aluminum-silicate-sul-

Turbidity 98.7–98.9%
phate which also involved alkali leaching followed by polymerization
Wastewater removal
characteristics (%)

step in addition to acid leaching (Sun et al., 2011). This polymeric

Turbidity 98.9%

coagulant was tested for oily wastewater remediation. The conversion

Oils 91.5%
efficiency of oxides into coagulants is increased with increase in the
COD 47%

COD 65%

4 98%

SS 96.1%
TSS 99%
As 97%

SS 92%

ratio of acid volume to FA mass, leaching temperature, and H2SO4

PO3-

concentration (Hu et al., 2016).

Coagulation conditions

3.4. CFA application in photocatalysis

(min)
Time

25

10

10

15

Photocatalysis is one of the most authentic solutions among AOPs

Stirring (rpm)

for clean-up of a broad range of pollutants. In photocatalysis, electron-

Moderate

hole pairs are generated by bandgap excitation. These electrons and

holes participate in redox reactions along with oxygen, water, and or-
30

60

ganic molecules (pollutants). An efficient photocatalyst should have a

high surface area, efficient light absorption, appropriate band gap, easy
CFA Coagulant

recovery, and high carrier mobility (Reddy et al., 2016). The photo-
Complex

Complex

catalytic system should be made cheaper to deal with a large volume of

PFS-PAF
sulphate

sulphate

PAFC

industrial wastewater (Shi et al., 2016). Several studies have stated the
Type

ways for the modification of fly ash into value-addition products for
their applicability in photocatalytic wastewater treatment. Depending
The conversion efficiency

on ash quality, CFA has been used as photocatalyst alone or in com-

37.48
Al3+

55.1

35.1

bination with other photocatalytic materials. In some studies, CFA has

–

been reported as photocatalytic support and some studies have high-

of oxides (%)

lighted the use of CFA as sole photocatalytic material. CFA has also
been converted into high-value zeolites and geopolymers for photo-
42.75
Fe3+

84.8

catalytic applications.
PAFC: Polymeric aluminum ferric chloride, PFS-PAF: Polymeric ferric sulphate-polymeric aluminum sulphate.
73
–

3.4.1. CFA as photocatalytic support

The concentration of ions in

1.88 wt%

Photocatalyst separation from water requires post-treatment to re-

0.137M
0.93M
Al3+

duce catalyst loss (Wang and Lim, 2012). Immobilization of photo-

–

catalysts on inert supports exterminates the additional separation step

(Thiruvenkatachari et al., 2008). The characteristics of photocatalytic
supports are stated in the literature (Srikanth et al., 2017; Ahmad et al.,
3.37 wt%
0.0464M
Wastewater treatment efficiencies of CFA-based coagulants prepared by acid leaching.

leachate

0.58M

2016). The support material should be stable to light illumination and

Fe3+

oxidative radicals of the photocatalytic system, should have a high

–

surface area after immobilization of catalyst, should adhere strongly

with the photocatalyst, the catalytic activity must not decrease after
temperature (◦C)

immobilization, and should increase the adsorption affinity of a pho-

tocatalyst for contaminants. Many transparent or opaque materials in-
Leaching

Boiling

cluding glass, quartz, silica, and activated carbon have served this role.
120

130

Since almost all of the above-mentioned characteristics are fulfilled by

95

CFA and it contains these phases especially silica, it can also act as
Leaching time

important low-cost support to photocatalysts. In this section, the pro-

cess efficiency of CFA supported photocatalysts is summarized.
Highly dispersed photocatalysts over such kind of supports make
(min)

240

360

300

photocatalytic properties unique to cause local excitations (Reddy et al.,

30

2016). The aggregation of photocatalytic particles can reduce the in-

teraction of catalytic sites with the photons (Zhao et al., 2017). Particles
Leaching

of FA offer an appropriate surface for the deposition and growth of

H2SO4

H2SO4

H2SO4
agent

metal or metal oxide nanoparticles (Fe, Ag, ZnO and TiO2) and increase
HCl

the surface area of composite material making availability of dyes in the

Al2O3 %

vicinity of photocatalyst due to its high adsorption capacity (Ayanda

21.03

30.62
22.9

et al., 2012; Kim et al., 2015; Pant et al., 2013; Yeole et al., 2014). The
21

aggregation of nanoparticles into a massive particle is thus prevented

CFA characteristics

Fe2O3 %

and the rate of pollutant degradation is enhanced by increased contact

25.48
15.6

3.28

2.89

of photocatalyst with the pollutant (Dastan et al., 2017; Kim et al.,

2015). Nanoparticles supported on FA agglomerate less. Fly ash was
Table 5

Origin

China

China

employed as a support for immobilization of TiO2 and found effective

USA

USA

for removal (94.4%) of phenol from water (Shi et al., 2011). Fig. 4 d)

35
F. Mushtaq, et al.
Fig. 4. Pictorial illustration of photocatalytic performance up-gradation by CFA through different strategies (a) coupling of CFA constituent oxides with themselves or
with externally introduced photocatalyst (b) doping of photocatalysts with metals from CFA (c) surface features and porosity of CFA-based catalysts for light
absorption (d) photocatalyst coated on CFA.
shows a general illustration of a photocatalyst supported on CFA.
The pronounced photocatalytic degradation by lignite FA supported
titania nano-catalyst have been obtained. Due to the presence of ZnO,
Fe2O3, and TiO2, the surface of FA has heterogeneity associated. This
phenomenon and porosity allow weak interaction between the catalytic
substrate and MO dye (Ökte et al., 2014). The effect of percentage
content of TiO2 loaded over CFA surface and calcination temperature
on photocatalytic performance and structural properties of substrates
were studied by degradation of MO (Shi et al., 2010a, 2010b).
Coated ZnO nanoparticles onto lignite fly ash were evaluated for the
degradation of MO in UV rays. Almost all of the dye was degraded
before 10 min of UV irradiation (Ökte and Karamanis, 2013). Ag-doped
ZnO-fly ash composites have high photocatalytic efficiency as wells
enhanced antibacterial activity (Kim et al., 2015). The FA/ZnO com-
posite was successfully used in UV and visible light for the degradation
of azo dyes including Reactive orange 4, Trypan blue, and Rhodamine B
(Thirumalai et al., 2016). Chen and coworkers prepared a novel pho-
tocatalyst using CFA as support. The photocatalyst has unique core@
shell structure having a core of CFA and shell of alternate layers of
reduced graphene oxide and titania nanosheets. Merging the excellent
adsorption, conductivity, and transparency of reduced graphene oxide
and the settling benefit of CFA, they obtained a novel photocatalyst.
CFA carrier favored the separation of nano-structures anchored on it
(Chen et al., 2018). FA has been used as support for carbon doped ti-
tania for visible light photodegradation of MO (An et al., 2018). This
new approach opened possible pathways for application of CFA with
other materials in photocatalysis.
3.4.2. CFA as a photocatalytic material
Fly ash as heterogeneous inert material contains many photo-
reactive oxides like Fe2O3, TiO2, and CaO in small quantities. Doping of
fly ash with photoactive metals can enhance its photo-reactivity.
Cobalt-doped lignite fly ash has been successfully employed as an ef-
ficient photocatalyst for the degradation of Acid Red 1 (Giribabu and
Swaminathan, 2016). Fly ashes from four different power stations have
been used as photocatalysts for the degradation of reactive dyes (Babu
and Swaminathan, 2016). They used pristine fly ashes as photo-
catalysts. Degradation efficiency of different fly ash samples varied
according to the percentage contents of Fe2O3, TiO2, and CaO in them.
36
Journal of Environmental Management 240 (2019) 27–46
CFA-based photocatalysts act as strong oxidizing agents due to their
ability to generate hydroxyl radicals to degrade large organic molecules
(Wang et al., 2015).
Separation of photo-generated charges of the semiconductor during
light irradiation is one of the key factors for photocatalytic promotion
(Zhang et al., 2018b). Recombination of the photo-generated charge
reduces the quantum efficiency of the process. Recombination can be
reduced by using co-catalysts, adding dopants, and by semiconductor
coupling (Bora and Mewada, 2017). Adding transition metals like Cr,
Fe, Co, Mn, Ni, Cu, Ru, Mo, V etc. extend the spectral response. These
metals are believed to introduce an intermediate energy level between
CB and VB (Bora and Mewada, 2017). Several studies have shown that
adding up Fe2+/Fe3+ ions and hydrogen peroxide as an oxidizing agent
remarkably affects the photo-catalytic effectiveness reducing the reac-
tion time (Bansal and Verma, 2017; Meriç et al., 2003;
Muruganandham and Swaminathan, 2004). Photocatalytic reactions
are influenced not only by light intensity, pH, and oxidant dosage but
also by transition metal ions (Asl et al., 2018). The doping of photo-
catalysts with Fe3+ ions could improve photocatalytic activity by in-
troducing an impurity level near CB. The Fe3+ ions functioned as
charge carrier preventing the recombination of e− and h+(Song et al.,
2017). Instead of doping with expensive metals and coupling with
metal oxides, employing cheap FA containing various trace metals, non-
metals, and metal/non-metal oxides functioning as an impurity, is a
resourceful rout to enhance photocatalytic activity (Thirumalai et al.,
2016). Thus, it can boost up the photocatalytic process. Fig. 4 illustrates
the role of CFA in photocatalysis to up-grade the system efficiency by
semiconductor coupling, doping with metals, acting as support, and
making light illumination better.
CeTiO2 was coupled with FA and a positive shift was found in VB of
CeTiO2 with enhanced oxidation of MO in visible light but no photo-
catalytic activity of FA was found (An et al., 2018). CuO was modified
by F-type FA and photocatalytic degradation efficiency in direct sun-
light was estimated. The modification of CuO by FA shifted its band gap
energy from 1.2 eV to 2.09 eV favoring the visible light absorption
(Mazumder and Rano, 2018). Thirumalai and coworkers confirmed the
suppression of photogenerated charge recombination observing the
reduction in intensity of photoluminescence of FA/ZnO composite. The
composite exhibited high photocatalytic activity than ZnO nanorods
F. Mushtaq, et al. Journal of Environmental Management 240 (2019) 27–46

Table 6
Selected examples of CFA-based photocatalysts and their application in degradation of contaminants.
Photocatalyst Pollutant pH Initial pollutant Catalyst Irradiation Irradiation Degradation (%) Reference
concentration (mg/L) dosage (g/L) source Time (min)

Fly ash Thionine 2.5 2.63 2 VIS 240 61 Chatterjee et al.

Rhodamine B 4.79 22 (2001)
Eosin Y 6.47 21
Fly ash 1 Acid Red 1 2.5 10 1 UV 60 40 Babu and
Fly ash 2 60 Swaminathan (2016)
Fly ash 3 67
Fly ash 4 95
Lignite fly ash (LFA) Acid Red 1 – 10 1 UV 60 95 Giribabu and
Co-LFA 99 Swaminathan (2016)
ZnO/FA nanocomposite Methyl Orange – 3.27 1 UV < 10 ∼100 Ökte and Karamanis
(2013)
TiO2/FA nanocomposite Methyl Orange 8.5 3.27 1 UV 150 > 70 Ökte et al. (2014)
Ag/ZnO/FA nanocomposite Methylene Blue – 10 0.5 UV 180 > 95 Kim et al. (2015)
FA-TiO2nanofiber Methylene Blue – 10 0.8 UV 120 100 Saud et al. (2015)
TiO2/fly ash Phenol 4 80 1 UV 240 94.35 Shi et al. (2011)
FA/CuO Methyl Orange – 10 8 mg Sunlight 40 99.1 Mazumder and Rano
(2018)
FA-based geopolymer Methylene Blue 11 1.3 2 UV 240 92.79 Zhang and Liu
(2013)
Graphene/FA geopolymer Indigo Carmine – 10 1 UV 90 Zhang et al. (2018b)
Poly-3,4-ethylenedioxythiophene/ C.I. Reactive 5 30 1 Simulated solar 30 ∼100 Katančić et al.
TiO2-FA Red 45 radiation (2018)
ZFAB/TiO2 Rhodamine B – 10 0.5 UV 60 85 Yang et al. (2017c)

alone. FA reduced its band gap to 2.81eV. FA loaded ZnO has less
electron-hole pair recombination as PL intensity is decreased at 418 nm
(Thirumalai et al., 2016). Fly ash showed capability towards enormous
photo-degradation of dyes. Red shift in the band gap of Fe3O4 loaded FA
was found, for it showed light absorption enhancement in 400–800 nm
range while UV–Vis spectrum of raw FA intensely absorbs in UV region
(Joshi et al., 2015). Thereby, introducing CFA to other materials change
their light absorption properties to a significant extent.
Some studies on combined photocatalysis and adsorption have been
carried out by researchers employing tungsten oxide and fly ash (Visa
et al., 2015b), TiO2 coated fly ash (Duta and Visa, 2015; Visa et al.,
2011, 2015c), fly ash derived geopolymers (Zhang and Liu, 2013), and
fly ash polymer composite membranes (Kim et al., 2014). Adsorption
and photocatalysis synergistically enhance the removal rate from was-
tewater (Pizarro et al., 2015). Properties of CFA can be enhanced by
incorporating different metal and metal oxide nanoparticles to it. Saud
et al. incorporated fly ash into Titania nanofibers to form composite
nanofibers and investigated the photocatalytic activity using methylene
blue under UV irradiation (Saud et al., 2015). Table 6 enlisted some
examples from literature for degradation of various organic pollutants
by CFA-based photocatalysts.
Fly ash and TiO2 nanoparticles were incorporated into polyurethane
to fabricate multifunctional polyurethane composite membrane. The
improvement in water purification activities is credited to adsorption
by fly ash and photocatalysis by TiO2 NPs. The affinity of fly ash par-
ticles towards polyurethane is much better than TiO2 NPs. The quantity
of FA incorporated into polymer fiber can be up to 70% by weight. On
the other hand, TiO2 alone is not possible to be incorporated through
polymer in large amount. Degradation ability of prepared membrane
was tested using methylene blue dye under UV irradiation (Kim et al.,
2014). To increase the overall efficiency of wastewater treatment, an
inorganic material (TiO2-FA) can also be blended with conductive
polymer (poly 3,4-ethylene dioxythiophene) (Katančić et al., 2018).
The high adsorption capacity of nanocomposite quickly saturated the
photocatalyst and enhanced the removal effectiveness.
One more benefit of CFA is its ability to treat multi-pollutant was-
tewater. Many authors have studied complex simulated wastewater
using CFA. TiO2 alone is not encouraging owing to its poor selectivity to
eliminate toxic contaminants from mixed pollutant system. The
selectivity of photocatalysts is to be improved because several pollu-
tants coexist in the aquatic environment (Lu et al., 2013). FA alone or
with other photocatalysts symbolize a complex substrate for simulta-
neous remediation of heavy metals, surfactants, and dyes (Visa et al.,
2015a). A composite substrate was developed by combining TiO2 with
FA and their efficiency tested by adsorption and photo-degradation
against simulated wastewater containing multiple pollutants including
dye, copper ions, and surfactant (sodium dodecyl benzene sulfonate)
(Visa et al., 2015c, 2016). TiO2 alone is UV active but FA/TiO2 com-
posite degraded 74% of surfactant and 80% of MO when irradiated by
simulated solar radiation composed of UV 15% and Vis 85%. The for-
mation of tandems between various metal oxides of FA and TiO2 were
reported (Visa et al., 2015c). The FA-TiO2 substrate possessed higher
surface regulation (homogeneity), surface area, and surface roughness
than composite components favoring active adsorption and hetero-
geneous photo-degradation processes (Visa et al., 2016). Thus, CFA is
capable of enhancing the affinity of titania for polyurethane and se-
lectivity of titania for complex wastewater.
No straightforward mechanism can be assigned to enhanced FA-
based photocatalytic degradation. It could be due to the formation of
new (intermittent) energy levels reducing band gap energy of photo-
catalyst. The constituent trace metals could trap electron as in case of
metal-doped photocatalysis. The constituent oxides could inhibit the
photogenerated charge recombination by coupling (Thirumalai et al.,
2016; Visa et al., 2015b). Various reports have stated the enhancement
of photocatalysis by coupling of oxides (Fe2O3, MgO, SiO2, TiO2, and
Al2O3) (Nasirian et al., 2017; Wang et al., 2011). Fig. 4 a) illustrates the
coupling of semiconductor oxides which can be from fly ash or ex-
ternally composited photocatalyst can couple with FA oxide. Another
possible mechanism of CFA photocatalysis is dye sensitization.
After being adsorbed on the catalyst surface, dye molecules are also
said to behave as antenna molecules capable of absorbing visible light
and the excited electron is injected into the conduction band of the
photocatalyst. Thereby, the oxidized dye molecule brings charge se-
paration widening the photo-response of catalyst from UV to visible
region. A unique path to capture visible light from the sun is created
(Chen et al., 2010a; Ökte et al., 2014). Fe3+ ions reduction to Fe2+ ions
can also occur by intermolecular transfer of an electron from excited
colored substances including dyes. This dye-sensitized photo-Fenton

37
F. Mushtaq, et al.
process enhances the generation rate of OH% radicals which enhance
the pollutant removal (Bokare and Choi, 2014). Environmental friendly
photo-degradation of textile dyes adsorbed on the surface of fly ash has
also been carried out in visible light. Surface adsorbed dyes in their
excited states in equation (8) reduced Fe3+ species present in fly ash
into Fe2+ ions, functioning like electron donors as in equation (9).
Further, Fe2+ ions can undergo redox reactions with oxygen generating
superoxide and hydroperoxide radicals described in equation (10)
which start decomposition of dyes ultimately into CO2. Thus, the Fe3+
ions leached from fly ash into dyes solution show a convincing role in
photo-decomposition of dyes (Chatterjee et al., 2001).
CFA (D) + visible light CFA (D ) (8)
CFA−(D∗)+ Fe3+→CFA−(D%+)+Fe2+ (9)
(10)
Size distribution influences the interaction of ash particles and dif-
ferent solutions, as trace elements mobilization on FA surface is affected
by particle size. Smaller size particles have greater surface area (Wang,
2008). For example, different size fractions (35, 45, 63, 75 and 150 μm)
of Lignite fly ash were tested to analyze the effect on degradation
(Giribabu and Swaminathan, 2016). The optimum degradation was
found at 150 μm. Large sized particles settle easily (poor dispersion)
making less contact with the solution and too small particles can hinder
light penetration. In another example, fly ash with finer particles
(15.2 μm) showed high adsorption capacity and subsequently high de-
gradation than fly ash with larger particle size (21.3 μm) (Al-Hamadani
et al., 2017). Fly ash-based photocatalysts are reusable and stable ma-
terial for water purification. The higher photocatalytic degradation of
FA supported catalysts can be credited to enhanced condensation of
contaminants on the support and least electron-hole recombination on
catalyst surface (Kim et al., 2015; Ökte and Karamanis, 2013). CFA
recovery from reaction media can be tricky. Filtration and centrifuga-
tion methods have been used to separate CFA (Thirumalai et al., 2016;
Visa et al., 2015c). In an attempt to regenerate CFA, photocatalytic
degradation efficiency was found reduced from 95 to 88% (Giribabu
and Swaminathan, 2016). However, the reusability and stability of
CFA-based catalysts are enhanced than pristine CFA.
3.4.3. Coal fly ash transformed materials in photocatalysis
Alkali activation of fly ash bead resulted in the growth of zeolite
phases having porous surface characteristics that exhibit high photo-
catalytic activity. Penetration of light and intra-particle diffusion rate of
pollutant molecules are also essential parameters in addition to ad-
sorption during photocatalysis. ZFAB-TiO2 composite as photocatalytic
material has been investigated for surface features. The open pore vo-
lume of photocatalytic material allowed easy diffusion of RhB mole-
cules to the surface (Yang et al., 2017b). CFA zeolite has been com-
posited with AgeTiO2 for bisphenol-A photo-degradation (Hlekelele
et al., 2018). Transporting molecules within cage network in porous
materials is a significant parameter in photocatalysts (Reddy et al.,
2016). Fig. 4 c) show the convenience of light penetration to porous
CFA-based photocatalyst.
Alkali-activated CFA-based geopolymer was first used as a novel
photocatalyst to degrade methylene blue by Zhang et al. introducing a
new approach for the degradation of organics from wastewater. Metal
oxides (TiO2 and Fe2O3) present in fly ash geopolymer functioned as
semiconductor particles when irradiated under UV light (Zhang and
Liu, 2013). In another study, the geopolymer electroconductivity was
improved utilizing graphene as a charge carrier. The composite mate-
rial combining the graphene and fly ash geopolymer exhibits high
photocatalytic activity for dye wastewater treatment. Coupling Fe2O3 of
FAG with graphene increased the separation efficiency of photo-
generated charge. The photogenerated e− by Fe2O3 is quickly trans-
mitted to graphene. The band gap of FAG is derived from Fe2O3 which
38
Journal of Environmental Management 240 (2019) 27–46
is 3.47. After coupling with graphene the band gap of FAG photo-
catalyst is narrowed (Zhang et al., 2018b). Fly ash was used as an in-
expensive precursor to obtain silica and prepared TiO2/SiO2 composites
for photocatalytic degradation of Rhodamine B (Cheng et al., 2018).
Silica was extracted by hydrothermal treatment of fly ash with an acidic
solution followed by base treatment in the heated kettle. Disc-shaped
ceramic substrates were synthesized recently by lignite FA and TiO2
slurry with effective decolourization of MB and MO under visible and
UV irradiation (Katsika et al., 2018). The CFA transformation to these
materials is a novel approach in photocatalysis.
3.4.4. Fly ash cenospheres (FACs) as photocatalysts
Some of the high-value components of CFA can be separated to
conduct research on many alternative utilization ways. Cenospheres are
one of the precious components of CFA. Since the formation of ceno-
spheres occur under special conditions and is influenced by coal char-
acteristics, only a few fly ashes have cenospheres. The contents of
cenospheres in CFA are usually very low (0.3–1.5%) (Acar and Atalay,
2016). These granular multifunctional ceramic particles of alumino si-
licate nature are separated by floatation method from CFA (Huo et al.,
2010a). FACs are mainly composed of alumina, silica, iron oxide, cal-
cium oxide, and potassium oxides as these are CFA derived (Huo et al.,
2010b). The density of cenospheres is lower than water due to their
hollow structure. The stability and good dispersion make FACs amen-
able in photocatalysis as carrier material.
These unique micro-particles have been given a great deal of at-
tention because of their low density, chemical inertness, non-toxicity,
stability, strong filling capacity, and thermal resistance (Huo et al.,
2010b; Ngu et al., 2007). Regarding the practical utilization of photo-
catalysts, stability and reusability are two important parameters (He
et al., 2014). The powder catalysts sink and suspend in the solution.
FACs as carrier solves the issue (Huo et al., 2010a). The size of spherical
FAC particles is 1–100 μm (Shi et al., 2016). Immobilized photo-
catalysts have improved utilization rate of catalysts because the pho-
tocatalytic reactions are surface catalyzed and FAC supported catalysts
are exposed directly to light as well as reactants (He et al., 2014).
Floating photocatalysts also have enhanced oxygenation due to their
presence at the surface of the water (Song et al., 2016). Participation of
oxygen in redox reactions during photocatalysis is important. Fig. 5
shows the pictorial illustration of the convenience of FACs to take light
and oxygen for photocatalysis at water's surface. Readers further in-
terested in the assimilation of FACs in photocatalysis can refer to the
supplementary information and Table S2 enlisted the FAC-based pho-
tocatalysts for degradation of pollutants in visible light.
Fig. 5. Pictorial depiction of floating FACs conveniently absorbing direct solar
light at water's surface.
F. Mushtaq, et al.
3.5. CFA application in the fenton process
Potential usage of various metals (Mn, Cu, and Ni), their oxides, and
supported metal oxides in combination with H2O2 has been investigated
by many researchers. Metals or their oxides supported over silica and
alumina for H2O2 decomposition in the aqueous phase are well known
from literature studies (di Luca et al., 2012; Soon and Hameed, 2013).
CFA contains different catalytically active constituents of Fenton's
process like iron oxides, magnetite, hematite, and several metals like
Mn, Cu, and Ni or/and their oxides (Chaudhuri and Sur, 2000). Cata-
lytic potential of fly ash in wastewater abatement has been less ex-
plored in comparison to adsorption studies. Recently, attention is di-
verted towards applicability of fly ash as a catalyst in the Fenton
process. FA has been tested in combination with H2O2 in the presence of
light, ultrasonic radiations, electricity or other catalysts. In this section
different Fenton processes utilizing CFA for wastewater remediation,
are discussed.
3.5.1. Combined homogeneous Fenton and sorption
Fenton oxidation is relatively economical technique among AOPs in
which Fenton reagent (Fe2+ and H2O2) is used for the generation of
hydroxyl radicals. When Fenton reagent is used alone, intermediates of
pollutants are often found after degradation. In order to achieve de-
gradation to a significant extent a high dosage of Fenton's reagent is
consumed (Chang et al., 2009a). To decrease the dose of Fenton's re-
agent, Chang et al. combined fly ash sorption and Fenton oxidation for
the investigation of Rhodamine B removal efficiency. Fly ash has low
sorption potential for some dyes requiring high dose for sorption stu-
dies. Fenton pre-oxidation can change the properties of dyes such that
the sorption capacity of fly ash is increased. A low dose of fly ash will
then be needed for sorption of dyes. The combined process showed
effective removal as compared to fly ash or Fenton reagent alone
(Chang et al., 2009b). Combination of Fenton reagent with H2SO4
modified CFA removed 99.46% phenol from simulated wastewater.
Vitriol modified CFA removed phenol in short reaction time by low
catalyst loading (Wang et al., 2014).
3.5.2. Heterogeneous Fenton-like process
Trouble in catalyst recovery, pH dependence, sludge formation, and
acidification cost are some demerits encountered during the homo-
geneous process (Pouran et al., 2014). To overcome the limitations of
homogeneous Fenton process, heterogeneous Fenton-like catalysts are
introduced. Replacement of Fe2+ by Fe3+ avoids the formation of a
large quantity of sludge making the heterogeneous process more eco-
nomical (Chen and Du, 2014). CFA can be transformed into Fenton like
catalyst due to its feasible composition. Fe2+ can be replaced by crys-
talline phases of CFA containing an iron element (Wang et al., 2017a).
Active metallic elements (like iron and manganese) and porous surface
of fly ash make it possible to explore its application in heterogeneous
Fenton-like processes. Various studies show the potential of CFA-based
Fenton-like catalysts to decontaminate the organic wastewaters. Under
optimal conditions of experiments up to 85% of the contaminants have
been degraded (Wang et al., 2016b).
Fly ash containing Fe3+ ions (heterogeneous catalyst) can activate
hydrogen peroxide. H2O2 reacts with fly ash forming a Fenton-like re-
action media (Song and Li, 2009). The catalytic performance of CFA's
from two different origins were compared and CFA was transformed
into three different kinds of heterogeneous Fenton-like catalysts namely
(1) modified coal fly ash (MCFA) by heat, acid and alkali modifications,
(2) granular MCFA to make recycling and separation of catalyst easy
and (3) Fe2O3-granular MCFA to further enhance the performance. CFA
activated, by all means, promote the catalytic activity in Fenton-like
process. The acid modification resulted in high catalytic capacity
(64.3%) then alkali activation (41.1%) and heat modification (44.9%)
due to different possible mechanisms of modifications (Wang et al.,
2017a). The surface catalyzed reactions take place as in equation
39
Journal of Environmental Management 240 (2019) 27–46
(11)–(13).
CFA Fe3 + + H2 O2 H+ + CFA Fe (OH )2 + (11)
(12)
CFA≡Fe2+ + H2O2 → CFA≡ Fe3+ + OH− + OH% (13)
The degradation of p-nitrophenol by HNO3 modified fly ash (HFA)
in heterogeneous Fenton-like process has been studied. Large number of
active sites over the surface of HFA and Fe dissolution from HFA surface
allow degradation of pollutant over the surface and in the solution
(Wang et al., 2017b). AFA has better physicochemical characteristics
than raw fly ash. It is preferable for heterogeneous Fenton-like process
due to increased adsorption and catalytic capacity. The contents of si-
lica and iron oxide got increased while the contents of calcium oxide
and alumina got decreased in acid activated fly ash. AFA showed better
settling and separation capability. Fe2O3 formed 5.73 wt% of that CFA
(Zhang et al., 2012). Modified CFA by H2SO4 for the degradation of
AO7 dye was used (Wang et al., 2018b). Fe2O3 formed 5.1% of the
catalyst with greater than 95% of the dye removal in 60 min.
The acid modification could generate large number of grooves or
pores by dissolving alkali substances in CFA and expose the surface (of
magnetite and hematite) for catalytic reactions. Since Fenton and
Fenton-like processes proceed efficiently in the acidic environment due
to the stability of H2O2 in acidic conditions, acid modification of CFA is
always preferred to promote its use in Fenton process (Wang et al.,
2017a, 2017b). Heterogeneous H2O2-Fly ash catalyst showed a strong
oxidation activity against n-butyl xanthate (Chen and Du, 2014). The
oxidative decolourization of drimarene dyes using CFA as a catalyst in
the presence of H2O2 was studied. The leachability of various active
metal ions from CFA matrix into the reactive dye solutions catalyzing
homogeneous process has also been investigated (Chaudhuri and Sur,
2000). The concentration of Fe, Cu, and Mn leached into solution were
found less than 1 mg/L, revealing that whole decolourization was
mainly due to heterogeneous catalysis. Thus, CFA represents a viable
option in heterogeneous Fenton oxidation. Dark catalysis has been re-
cently developed process for remediation of organic dyes from aqueous
media. Pd/fly ash non-magnetic and Fe3O4/Pd/fly ash magnetic com-
posites have been used as a Fenton-like catalyst for the removal of basic
and reactive azo dyes through the hydrogen peroxide activation in dark
conditions. In the pursuit of less costlier support, such demonstration
offered a new strategy of fly ash utilization in AOPs (Narayani et al.,
2017). Table 7 enlists the degradation performance of CFA-based
Fenton catalysts under heterogeneous and other processes.
The co-catalytic activity of oxides of Si and Al is also obvious from
few studies. The oxygen atoms of siloxane bridges in silica undergo
hydrogen bonding with H2O2 making its adsorption easy and increasing
the opportunity of contact between iron oxides and H2O2. Likewise, Al
behaves as Lewis acid attracting the electron density towards it from
Fe3+ ions. It also facilitates the reduction of ferric to ferrous ions by
H2O2, which is otherwise considered a rate-limiting step of the Fenton-
like process (Tu et al., 2012; Zhuang et al., 2016a).
Alkali modified CFA could destroy crystal structure and increase the
wastewater pH. Heat modification could badly affect the catalytic ca-
pacity by phase transitions and structural readjustments during dehy-
dration destroying the space structure (Wang et al., 2017a, 2017b).
Hence, these are less favorable modifications to the Fenton process.
3.5.3. Heterogeneous Photo-Fenton process
Since minor oxides in fly ash like TiO2 and Mn2O3 can participate in
the photodegradation of dyes. The crystalline oxides, for example,
bixbyite Mn2O3 can form in situ Fenton type system. More than 75% of
methyl orange has been removed by the photo-Fenton system con-
taining fly ash, H2O2, and UV irradiation (Visa and Duta, 2013a). MnO
and Fe2O3 from FA act as Fenton precursors (Visa et al., 2015b). The
scope of Fly ash and foundry sand has been evaluated as heterogeneous
 F. Mushtaq, et al.

Table 7
Performance evaluation of CFA-based Fenton catalysts in Fenton, Fenton-like, Photo-Fenton, and ultrasonically assisted Fenton processes take out from published reports.
Catalyst Pollutant Treatment Process pH Time Temperature (◦C) H2O2 dosage Catalyst dosage Degradation (%) COD removal Ref
(min) (mM) (g/L) (%)

H2SO4-CFA and Fenton Phenol Combined sorption and Fenton 5 60 – 6.23 0.2 99.46 – Wang et al. (2014)
reagent process
CFA n-butyl Xanthate Heterogeneous Fenton-like process 3 120 30 1.176 1 96.90 96.66 Chen and Du (2014)
3+
Fe /CFA Reactive Black 5 Heterogeneous Fenton-like process 2.8 120 Room temperature 4.56 1 ∼100 80 Flores et al. (2008)
discoloration
CFA Reactive Black 5 Photo-Fenton degradation 3 30 – 2.2 2.5 90 – Rajput et al. (2016)
Foundary sand-CFA 0.75 99
CFA derived Amorphous Methyl Orange Photo-Fenton degradation 7 80 25 15.8 2.5 ∼100% – Li and Zhang (2010)
FeOOH Discoloration
CFA C.I.Direct Black 168 Ultrasonic assisted Fenton-like 3 90 40 ± 2 2.94 2 99 – Song and Li (2009)

40
reaction
Coal ash Phenol Ultrasonic assisted Fenton-like 6 300 25 1.5 1 83.4 – Liu et al. (2009)
reaction
CFA Acid Orange 3 Ultrasonic assisted Fenton-like 3 160 Room temperature 5.4 2.5 96 – Li et al. (2010)
reaction
CuO/FAZ p-nitrophenol Fenton-like oxidative degradation 6.5 180 Room temperature 98 0.5 96 – Subbulekshmi and
p-nitroaniline 84 Subramanian (2017)
Raw fly ash p-nitrophenol Heterogeneous Fenton-like process 4 60 25 4.99 20 32.1 – Wang et al. (2017a)
Alkali-fly ash 41.1
Acid-fly ash 64.3
Heat-fly ash 44.9
HNO3-CFA p-nitrophenol Heterogeneous Fenton-like process 2 60 25 5 10 98 – Wang et al. (2017b)
Rice straw-CFA composite Real Azo dyes Electro-Fenton process 7 – 25 ± 5 In-situ 2 90.5 73.5 Zhuang et al. (2017)
wastewater generation
CFA/SC Phenolic pollutants Heterogeneous Fenton oxidation 6 120 30 4.4 10 86.1 74.9 Zhuang et al. (2016a)
H2SO4-CFA Acid Organic 7 Fenton-like process (simultaneous 2.5–5.5 60 25 15 10 > 95 – Wang et al. (2018b)
heterogeneous and homogeneous)
Journal of Environmental Management 240 (2019) 27–46
F. Mushtaq, et al.
photo-Fenton catalysts for decolourization and degradation of reactive
black 5 dye in sunlight. FA, FS, and FA-FS combined were used as a
catalyst. The photo-Fenton activity of above catalysts is attributed to
hydrogen peroxide activation by ions of iron leached from FA and FS
into the solution. This study proposed a beneficial reuse of wastes as
alternative iron sources (Rajput et al., 2016). Photo-Fenton catalysts
undergo iron recycling at the surface without substantial dissolution
into the solution. An amorphous catalyst FeOOH using fly ash con-
taining high contents of iron (17.52%) was prepared and the photo-
Fenton activity of the catalyst for degradation of methyl orange under
UV irradiation was studied (Li and Zhang, 2010). Being amorphous,
FeOOH exists as a suspension in solution. To make its separation easy
from aqueous media, the catalyst was supported on fly ash. Fly ash
played the dual role, acted as a source of iron and also supported the
amorphous catalyst. FeOOH was formed by rearrangement of ferric
oxide from CFA.
The pairing of two processes i. e photo-Fenton and photocatalysis
has been reported by some authors (Bansal and Verma, 2017). The
photo-excited electron is further engaged in ferrous ions regeneration
by reduction of Fe3+ ions leached from waste materials. The re-
combination of photo-excited charges is thus limited in dual process. FA
and FS not only acted as catalyst (TiO2) support but also worked as an
iron source for a dual process involving enhanced degradation of Ce-
phalexin. The photo-Fenton activity was confirmed as the degradation
response was maximum at pH 3.5 and in situ iron leaching from FA/FS
beads of the novel substrate.
3.5.4. Ultrasonically assisted Fenton process
Ultrasonic irradiation for the disintegration of molecules deterior-
ating environment in aquatic systems has recently gained attention
(Wu, 2008). The ultrasonic process can enhance the degradation effi-
cacy of organic contaminants and reduce the time needed for the re-
moval of pollutants. Solid surfaces like TiO2, Al2O3, glass beads, quartz,
carbon nanotubes, and poly aluminum chloride can enhance the so-
nochemical degradation (Al-Hamadani et al., 2017). The effectiveness
of CFA and H2O2 system in the presence of ultrasound radiations is
summed up in Table 7. Song and coworkers carried out experiments to
study the contribution of ultrasonic irradiation on the degradation of
Direct Black 168 dye. Direct black 168 degraded rapidly in the presence
of H2O2 and fly ash with ultrasound. They found fly ash resulted in
higher degradation effectiveness than diatomaceous, activated carbon,
and kaolinite (Song and Li, 2009). AO7 decolourization up to 76.75%
has been achieved by sonocatalytic process. Decolourization efficiency
by ultrasonic irradiation alone reached 3.8% only. Ultrasonic irradia-
tion in combination with fly ash has high potential for degradation of
organic contaminants in wastewater. Theoretical analysis revealed that
FA particles served as the nucleus for the generation of cavitation
bubbles (Li et al., 2016). The influence of coal ash on sonochemical
degradation of phenol has also been studied. Coal ash increased the
nucleation site for bubble cavitation owing to its surface roughness and
enhanced the phenol degradation. Iron accounts 7.34 wt% of coal ash
(Nakui et al., 2007). Liu and coworkers investigated the catalytic po-
tential of coal ash in the presence of H2O2 or O3 for phenol degradation
in Fenton-like process. The percent degradation of phenol using coal
ash under ultrasonic irradiation was found 83.4% and 88.7% in the
presence of H2O2 and O3 respectively (Liu et al., 2009). The active
metal components (Mn+) from CA are said to undergo catalytic reac-
tions as described in the following equations (14)–(19):
H2O+ ))) → OH%+ H+ (14)
2H2O2+ Mn++ H++ ))) →OOH%+M(n−1)++2H2O (15)
H2O2+M(n−1)++H++)))→OH%+Mn++H2O (16)
n+ 2+
2H2O2+M → OOH%+M−O2H (17)
2+ (n−1)+
M−O2H + ))) →OOH%+M (18)
41
Journal of Environmental Management 240 (2019) 27–46
2OOH%+ ))→ 2OH%+O2 (19)
“)))” is a representation to ultrasound waves. An important para-
meter affecting the sonochemical degradation is ultrasonic frequency.
Ultrasonic irradiation ruptures the FA particles leading to a decrease in
particle size and increase in surface area of FA. Thus, favoring more
adsorption and better dispersion (Song and Li, 2009). Ultrasonic fre-
quency has a direct effect on the formation of cavitation bubbles, size of
bubbles, lifetime of bubbles, and cavitation threshold. Lower frequency
produces fewer larger bubbles with high growth period. Hence, fewer
hydroxyl radicals are formed. While the cavitation bubbles produced
under higher frequency are more in number and collapse in a short time
generating more hydroxyl radicals (Al-Hamadani et al., 2017).
3.5.5. CFA as catalyst support in heterogeneous Fenton process
Metal oxides incorporated within or immobilized on supports are
superior heterogeneous catalysts than unsupported ones due to limited
leaching of metal components, ease of recovery and commercialization
of catalysts (Liotta et al., 2009; Subbulekshmi and Subramanian, 2017).
Supports for Fenton-like catalysts having high stability, specific surface
area, and porosity are recommended (Wang et al., 2016b). Various
active components can be impregnated on FA support to catalyze the
heterogeneous process. In some studies, the iron catalysts are im-
mobilized on CFA. When anchored on CFA surface, iron loss is inhibited
and catalyst recovery is guaranteed (Soon and Hameed, 2011). FA-
based catalytic supports have good thermal stability (Wang, 2008).
Flores et al. investigated the activation of H2O2 by CFA containing
heterogeneous Fenton-type catalyst for reactive black 5 removal. Five
different catalysts were prepared by Fe3+ ions immobilization on CFA
through thermal procedures. Ion exchange between metal ions like Ca,
Mg, Ti, and K of fly ash and Fe from outside allowed the ferric ions to
anchor on CFA surface (Flores et al., 2008).
Coal fly ash-based zeolites can serve as appropriate supports for
loading of metal oxides. Subbulekshmi et al. studied the degradation of
p-nitroaniline and p-nitrophenol making use of novel fly ash converted
to copper oxide incorporated-zeolite catalyst (CuO-FAZ) in hetero-
geneous Fenton like reaction (Subbulekshmi and Subramanian, 2017).
The synthesis of coal fly ash-sewage sludge carbon composite was first
reported as Fenton-like catalyst for the treatment of British Gas-lurgi
coal gasification wastewater followed by biological treatment (Zhuang
et al., 2016a). The integration of these two processes the percentage
removal of total phenols and COD is 86.1% and 74.9% respectively.
Catalytically active constituents of fly ash can enhance the catalytic
properties of sewage sludge. Application of this novel catalyst in
Fenton-like process can be economically beneficial and effective waste
management strategy.
3.5.6. Electro-Fenton process
In electro-Fenton EF process reduction at the cathode by electricity
produces in situ H2O2. The process is further enhanced by ferrous ions
in pH range 2–4 (Cruz-Rizo et al., 2017; Zhuang et al., 2017). As stated
earlier homogeneous process has demerits and there is need to use a
heterogeneous catalyst in the EF process. Catalytic particle electrode
CPE is a useful alternative to this solution. Utilizing coal fly ash can
meet up the challenges of developing cost-effective and efficient CPE to
enhance the performance of the electro-Fenton process. Feasibility of
CPE prepared from coal fly ash and rice straw has been tested in the EF
process for azo dyes wastewater treatment. The results show tre-
mendous electro-Fenton activity up to 90.5% discoloration achieved
(Zhuang et al., 2017). The novel CFA/biogas residues composite was
investigated as heterogeneous electro-Fenton catalysts (Ping et al.,
2018). The catalyst could operate over wide pH range with the catalyst
dose of 1 g/L and current density 10 mA/cm2.
In addition to degradation, Fenton process has also been used to
regenerate fly ash-based adsorbents after treatment of coking
F. Mushtaq, et al.
wastewater (Wang et al., 2018c) and removal of organics from water
(Wang et al., 2018a). Hydrothermally treated CFA is transformed into
zeolite having high iron contents and surface area as a viable option for
the Fenton process (Ramírez et al., 2018). Hence, the amply available
industrial waste containing valuable active metallic components is
highly fruitful in organic wastewater remediation.
4. Current scenario and future prospects
If we go two decades back looking for WWT by CFA, it would be
merely found as an adsorbent. However, the limited capacities of FA as
adsorbent encouraged scientists to activate, modify, and transform it
into efficient adsorbents. Since the potential activity of CFA as a cata-
lyst in WWT is realized, it has been used as heterogeneous Fenton,
Fenton-like, and photo-catalysts in advanced wastewater treatment.
Currently, its application in WWT is broad but still inadequate. CFA has
tremendous potential for wastewater treatment. The utilization of CFA
in water treatment in near future is quite promising. Depending on the
CFA quality selection of the right treatment method should be done. For
example, iron-rich CFA can be used for heterogeneous Fenton process in
wastewater treatment. For some applications, it is to be pretreated to
enhance its adsorption capacity.
Successful assimilation of CFA in photocatalysis, Fenton process,
and microfiltration by ceramic membranes seems prosperous but
challenging environmental technology. However, these methodologies
are in the early stages still. There are many important aspects to be
investigated in this field. The leaching of iron from CFA during het-
erogeneous catalysis could be questioned. CFA-based catalyst for WWT
should be sustainable and stable. More investigation is to be carried out
to form heterogeneous catalysts with limited leaching of ions to pro-
mote reusability of CFA-based adsorbents and catalysts. CFA applica-
tion in wastewater treatment can be addressed with extensive sys-
tematic research and deeper understanding of the topic. Scaling up of
the systems and process design should be the focus of research to
promote the value-addition to CFA in the field of sustainability, parti-
cularly water quality management. Exploring CFA for its application in
wastewater treatment may open a dynamic path for future research.
CFA can be composited with different semiconductor materials or
conducting polymers to explore its photocatalytic degradation potential
for wastewater pollutants. So far it has been combined with titania in
most of the studies. Combination of CFA with other photocatalytic
materials including oxides, sulfides, and ferrites is to be explored. It
contains a variety of non-metal and metal oxides that are a precursor of
ceramic membranes. Accordingly, it can be exploited to prepare fil-
tration beds and inorganic ceramic membranes.
5. Conclusion
In context to recycle solid waste containing useful components for
environmental remediation, this article highlighted the valuable di-
rections to achieve the successful integration of CFA in water or was-
tewater treatment processes especially advanced methods. To conserve
the environment, such a strategy of waste treatment by waste is pri-
celess and copes up with dual economical and environmental issues.
The physicochemical properties of CFA are extremely dependent on its
composition which is unfixed. Therefore, the adsorption capacity,
Fenton activity, photocatalytic performance, and filtration potential
vary greatly from ash to ash. The chemical composition of CFA can be
adjusted to get the desired contents by pretreatment with acid, alkali or
heat treatment.
a) The adsorption capacity of CFA is limited by variable composition
and being required in a large amount as an adsorbent. Chemical
modifications of CFA by different means are requisite for improve-
ments in removal efficiency of contaminants.
b) The use of CFA in the fabrication of ceramic membranes is fruitful
42
Journal of Environmental Management 240 (2019) 27–46
for the development of low-cost ceramic membranes and broad-
ening the fly ash applications in water treatment. CFA-based
ceramic filtration membranes are inexpensive, hydrophilic, have
low sintering temperature. In addition to high filtration potential,
fly ash membranes also exhibit high adsorption capacity. In addition
to color and oil removal, fly ash membranes can remove a range of
metal ions from aqueous media.
c) CFA offers an inexpensive alternative to various dopants, semi-
conductor oxides and support materials in photocatalysis. CFA-
based photocatalysts are environmentally friendly and low-cost. For
comprehensive recycling separation of FACs from CFA and their use
in photocatalysis is a new approach.
d) Iron-rich fly ashes have played role in the removal of wastewater
pollutants for novel application in Fenton's process. Recycling CFA
provides economical benefits of developing environmentally benign
Fenton catalysts. Fly ash containing Fe3+ oxides and various other
metallic components has been investigated as active Fenton catalyst
in the presence of H2O2.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.jenvman.2019.03.054.
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