Journal of Cleaner Production 208 (2019) 1131e1147

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Journal of Cleaner Production

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Review

Porous adsorbents derived from coal fly ash as cost-effective and

environmentally-friendly sources of aluminosilicate for sequestration
of aqueous and gaseous pollutants: A review
Seyed Mostafa Hosseini Asl a, Hamedreza Javadian b, *, Maryam Khavarpour a,
Claudia Belviso c, Mehdi Taghavi d, Mehdi Maghsudi e, f
a
Department of Chemical Engineering, Ayatollah Amoli Branch, Islamic Azad University, Amol, Iran
b
Universitat Polit

ecnica de Catalunya, Department of Chemical Engineering, ETSEIB, Diagonal 647, 08028 Barcelona, Spain
c
Istituto di Metodologie per l’Analisi Ambientale IMAAeCNR, Tito Scalo, PZ, 85050, Italy
d
Department of Chemistry, Faculty of Science, Shahid Chamran University of Ahvaz, Ahvaz, Iran
e
Department of Material Engineering, Iran University of Science and Technology, Tehran, Iran
f
Blast Furnace Department, Esfahan Steel Company, Esfahan, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Coal fly ash (CFA) is an industrial by-product generated during coal combustion process in power plants.
Received 21 April 2018 Due to its chemical and mineralogical composition, CFA is considered as an abundant and cheap source of
Received in revised form aluminosilicate to produce valuable advanced materials, such as zeolites, catalysts, photocatalyts, and
13 October 2018
geopolymers, with high adsorption capacity towards pollutants. In this review, the preparation methods
Accepted 15 October 2018
and characterization of CFA-based adsorbents, as well as their application in removing aqueous pollut-
ants, such as petroleum compounds, dyes, heavy metals, radioactive contaminants, COD and SS, and
gaseous pollutants, such as carbon dioxide, sulfur dioxide, sulfuric acid, hydrogen sulfide, mercury, nitric
Keywords:
Environmentally-friendly adsorbents
oxide, benzene, toluene, and o- and p-xylene were summarized. The studies prove CFA-based adsorbents
Coal fly ash to be efficient and cost-effective alternatives to remove aqueous and gaseous pollutants. Recent in-
Aqueous and gaseous pollutants vestigations on the application of various surface modification techniques to improve the adsorption
capacity of CFA-based adsorbents were also covered. The results indicate higher adsorption capacity of
CFA-based adsorbents compared to raw CFA after surface modification.
© 2018 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1132
2. Research methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1133
3. Coal fly ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1133
4. Opportunities and challenges of CFA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1134
5. Preparation methods and characterization of CFA-based adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1135
6. Removal of aqueous and gaseous pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1136
6.1. Removal of dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1136
6.2. Removal of heavy metals and agricultural nutrients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1137
6.3. Removal of petroleum compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1139
6.4. Removal of radioactive pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1141
6.5. Removal of COD and SS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1142
6.6. Capturing gaseous pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1142

* Corresponding author.
E-mail addresses: Hamedreza.javadian@yahoo.com, Hamedreza.javadian@upc.
edu (H. Javadian).

https://doi.org/10.1016/j.jclepro.2018.10.186
0959-6526/© 2018 Elsevier Ltd. All rights reserved.
1132 S.M. Hosseini Asl et al. / Journal of Cleaner Production 208 (2019) 1131e1147

Acronyms BPA Bisphenol A

BR Bemacid Rot
CA Coal Ash BTX Benzene, Toluene, o-Xylene and p-Xylene
CBA Coal Bottom Ash CV Crystal Violet
CFA Coal Fly Ash 2-4 DCP 2-4 Di-Chloro-Phenol
COD Chemical Oxygen Demand MB Methylene Blue
CS Capture and Storage MCSM Mesoporous Calcium-Silicate Material
EIA Energy Information Administration 3-4 MDP 3-4 Methylene-Dioxy Phenol
GC Gas Chromatography NP Nonyl-Phenole
HMAS Hybrid Mesoporous Aluminosilicate OII Orange II
MMIPs Magnetic Molecularly Imprinted Polymers OIV Orange IV
MNIPs Magnetic Nanoparticles Imprinted Polymers OMP O-Methyl Phenol
OECD Organization for Economic Cooperation and PEI Poly-Ethylene-Imine
Development PTOP P-(Tert-Octyl) Phenol
OFA Oil Fly Ash RhB Rhodamine B
QBTU Quadrillion British Thermal Unit RO Reactive Orange 4
SS Suspended Solid SHA Sulfonated Humic Acid
TCD Thermal Conductivity Detector SN Solophenyl Navy
TDS Total Dissolved Solids SNH Solophenyl Navy Hydrolysed
TOC Total Organic Carbon ST Solophenyl Turquoise
AO8 Acid Orange 8 STH Solophenyl Turquoise Hydrolysed
BB Bemacid Blau TB Trypan Blue

7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1144
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1144

1. Introduction production. Therefore, the wastewater treatment of textile in-

dustries is considered as one of the hardest operations due to
In the last few years, the great development of industrial ac- presence of heavy metals in the structure of dyes, leading to
tivities has caused environmental hazards (Wilson, 2013) with competitive separation process (Visa et al., 2015). These toxic ele-
irreparable damages to the ecosystems plus harmful consequences ments entrance to the food chain leads to serious risks for human
on human health (Gomes et al., 2017; Cong, 2018). The effluents and animal health (Mathur et al., 2007). Visa et al. (2012) under-
released by many industries, such as textile, steel, metallurgy, lined the way some heavy metals, such as copper, cobalt, and
electroplating, leather, paints and pigments, paper, plastics, and manganese are accepted for living organisms at low concentrations,
tannery are considered as the main sources of wastewaters. while their excessive levels can be detrimental to the organisms.
Textile industry uses a large amount of chemicals during wet Moreover, the data reported elsewhere (e.g Albanese et al., 2008)
processing stages and delivers considerable quantities of colored indicated that non-essential heavy metals, including cadmium,
organic compounds and other chemicals (Lin et al., 2016). Arora lead, and copper are dangerous for living organisms creating
(2014) estimated that approximately 2% of dyes are discharged serious health effects, due to their tendency to bio-accumulate.
directly into effluents, and 10% subsequently lost during the Wastewaters from petroleum refineries are specifically haz-
coloration process. According to the author, it is reasonable to as- ardous to the ecosystem (Al-Majed et al., 2012). Petroleum refining
sume that approximately 20% of colorants enter the environment process requires a large quantity of water. Recently, De Abreu
through effluents from the wastewater treatment plants. Many Domingos and Valeria da Fonseca (2018) mentioned a report pub-
studies have also reported the fixation percentage of dyes on lished by PETROBRAS (2015) stating that the Brazilian petroleum
different substrates and relative loss percentage in textile effluents refinery consumes an average of 0.9 m3 water per m3 of the pro-
(Carmen and Daniela, 2012). The presence of such toxic organic cessed oil, thus, generating a high volume of wastewater. The in-
compounds in the industrial wastewaters creates serious environ- formation reported by PETROBARS shows that a large amount of
mental problems due to their negative effects on the biological life polluted wastewater containing oil, ammonia, phenols, sulfides,
of pounds and rivers. Colored effluents are resistant to biological heavy metals, and organic compounds is generated during petro-
oxidation and cause high oxygen demand and pH fluctuation. They leum refining process (Coelho et al., 2006; Nacheva, 2011) that are
also prevent sunlight penetration, thus, decrease the photosyn- resistant against biodegradation. For instance, the chemical oxygen
thetic activity in aqueous environment (Alca ^ntara et al., 2016). demand (COD) in the raw wastewater of Abadan petrochemical
Heavy metal ions in wastewaters are one of environmental is- complex in Iran was reported to be 20,000 mg O2/L (Bahri et al.,
sues caused by natural sources such as rocks and various industries, 2018; Shokrollahzadeh et al., 2008). The effluents of this complex
like metallurgy, steel production, electroplating, leather tanning, and two other major petrochemical complexes together are dis-
paints, pigments, and textile (Adamczuk and Kolodynska, 2015). For charged into the Persian Gulf (Davodi et al., 2011), posing serious
instance, in textile industries, heavy metals are considered as health hazards to all inhabitants and endangering the biological
constituent structural elements with catalytic role during dye ecosystem of the region if not properly treated.
 S.M. Hosseini Asl et al. / Journal of Cleaner Production 208 (2019) 1131e1147
Some industrial wastewaters contain radioactive pollutants
(Lauer et al., 2018; Wen et al., 2016) making them even more
hazardous to the human and ecosystem. Radioactive wastewaters
with total activity of around 19% and high concentrations of iso-
topes, like 137Cs, 134Cs, and 90Sr are categorized as high-level wastes
(HLW) and considered perilous due to the presence of long-lived
actinides. The ecological risks of wastewaters containing
medium-level radioactive wastes are precisely measured by the
calculation of the main fraction of total activity in total volume of
the polluted streams (Lavrentyeva et al., 2014).
Other than wastewaters, air and gas pollution seriously affect
human health and life. The World Health Organization (WHO)
mentioned in 2014 that air pollution caused about 7 million deaths
worldwide in 2012, bolding it as one of the largest environmental
health risks globally. The emission of greenhouse gases, like carbon
dioxide, methane, nitrous oxide (N2O), water vapor, hydro-
fluorocarbons, perfluorocarbons, and sulfur hexafluoride, as results
of fossil fuels combustion, are considered as the main cause of
global warming (Solomon et al., 2007). In addition, some industrial
sites are faced with emission of toxic gases, such as SO2 (Kisiela
et al., 2016), H2S (Wu et al., 2018), the vapors of BTX (Bandura
et al., 2017), H2SO4 (Shu et al., 2015), and Hg (Yang et al., 2016).
Capture and storage (CS) is a technology used in the industries that
utilizes separation process like adsorption to treat such gaseous
pollutants. (Panek et al., 2017).
There are some conventional methods for the removal of pol-
lutants, such as chemical coagulation, precipitation, oxidation,
reverse osmosis, membrane, biological treatment, gamma radia-
tions, adsorption that each of them has its own strengths and
weaknesses (Golbad et al., 2017). Unlike most of these expensive
treatment methods, adsorption techniques are much more favor-
able due to their cost-effectiveness, simplicity of operation and
equipment, and significant removal efficiency. In addition, an
extended series of natural, synthetic, and waste materials, with
high adsorption capacities can be utilized as adsorbents (Javadian
et al., 2018). Materials with mesoporous properties and regular
pore structures are the best adsorbents for air, gas, and water pu-
rification (Liu et al., 2013). Besides various porous materials, CFA as
a by-product of coal combustion process in power plants has
attracted many researchers, particularly in the field of wastewater
treatment and separation of pollutants from gaseous flows,
depending on its chemical, mineralogical, and physical properties.
Moreover, CFA is considered as an abundant and low-cost source of
aluminosilicate to produce efficient porous adsorbents like zeolites.
This article provides an at-a-glance review of the latest in-
vestigations conducted on the application of CFA-based adsorbents
to remove aqueous and gaseous pollution, and a comparison of
their removal performances. The preparation methods and char-
acterization of CFA-based adsorbents, as well as the application of
CFA to fabricate zeolites, catalysts, photocatalysts, and geopolymers
by chemical synthesis methods, including hydrothermal treatment,
fusion, microwave, and ultrasonic are reported. In addition, the
most common surface modification techniques reported in the
literature, such as functionalization, impregnation, coating, co-
precipitation, chemical activation and polymerization are
comprehensively discussed.
2. Research methodology
The main objective of this paper is to review the published
literature on the adsorbents derived from CFA in the field of
chemistry, chemical engineering, material engineering, and envi-
ronment engineering. The valid databases, such as “Scopus”,
“Elsevier”, “Web of Science”, and “Researchgate” were used to
gather the information and sources, including original articles,
1133
review papers, and chapters. Also, the international databases of
Energy Information Administration (EIA), British Petroleum (BP),
and PETROBRAS were employed to examine the latest predictions
of CFA production rate in the world. The contents reported in this
study were extracted from the scientific papers plus three technical
reports, with more than 90% of the references from 2010 to 2018,
and about 60% from 2015 to 2018.
The literature related to using raw fly ash and other CFA-based
adsorbents such as zeolites, catalysts, photocatalysts, and geo-
polymers for the removal of aqueous and gaseous pollutants, were
categorized based on their contents and analyzed further. The
structure of the review paper was defined according to several
major subjects including the environmental problems of CFA, rep-
resented solutions, preparation methods of the synthesized CFA-
based adsorbents, characterization of the CFA-based adsorbents
and ultimately their performances for the sequestration of aqueous
and gaseous pollution. The adsorption conditions and capacity of
each modified CFA-based adsorbent were inserted in Tables 2e5 In
addition, some innovative methods were remarked as the best
patterns for further research, like the proposed adsorption mech-
anisms by a type of photocatalyst and the adsorption process of CO2
and H2SO4 using a new design of gas setup.
3. Coal fly ash
Coal is the second major fossil fuel source for energy production.
It is largely distributed worldwide with approved reserves of
approximately 1000 billion tones in total. Despite the Paris climate
agreement, coal still plays a key role for power generation in the
foresighted future considering the growing demands for energy,
particularly in the developing countries. Globally, with around 28%
of total generated energy reported in 2016, coal has the second rank
among other energy sources (Fig. 1a) (BP Statistical review). The
latest report published in 2017 by the U.S. Energy Information
Administration (EIA) evaluates the worldwide coal consumption
since 1990 to 2040 (International Energy outlook, 2017). EIA
outlook reported a coal consumption of around 160 quadrillion Btu
(a quadrillion Btu roughly equals to the amount of energy in 45
million tons of coal) from 2015 to 2040. The consumption rate in
China and US will decrease but it will be compensated by India.
Fig. 1b shows that China will still remain the largest consumer of
coal with a partial reduction in 2040 (about 73 QBTU), while India's
coal consumption will grow with an average rate of 2.6%/year from
2015 to 2040. It is predicted that before 2020, India will surpass the
US and will be the second largest coal consumer. The consumption
of coal in Organization for Economic Cooperation and Development
(OECD) countries will decrease by an average of 0.6%/year during
2015e2040 due to the growing competitions for natural gas and
renewable sources. In other places, such as Africa, the Middle East,
and non-OECD Asia, the rate of consumption will gradually enhance
until 2040 (International Energy outlook, 2017). In addition, the EIA
predicts that the amount of coal utilization for the generation of
power will remain stable, and then drop slightly due to the
replacement of coal by natural gas and renewable and nuclear
power in the OECD countries (Fig. 2a). EIA's projections show that
the amount of electricity generation will grow up to 2040 (with a
growth rate of 2% annually), implying that coal is a significant
portion in this growth (Fig. 2b) (International Energy outlook,
2017).
The continuous demands for coal lead to more coal extraction,
and subsequently more coal ash (CA) production (Fig. 3a and b). In
detail, during the coal combustion process in power plants, 80% of
CFA and 20% of coal bottom ash (CBA) are generated whose accu-
mulation in landfills lead to destructive effects on living organisms
and eco-system (Fig. 3c and d). Focused on CFA, the world annual
1134 S.M. Hosseini Asl et al. / Journal of Cleaner Production 208 (2019) 1131e1147
Fig. 1. (a) World primary energy consumption by BP Statistical Review of World
Energy (2017) and (b) worldwide coal consumption (International Energy Outlook,
2017).
Fig. 2. (a) World energy consumption by energy source and (b) EIA's projection of
electricity generation based on the fuel types (International Energy Outlook, 2017).
rate of its generation in 2012 was reported to be around 800 million
tons, from which China, India, US & EU generated 500, 140 and 115
million tons, respectively (Belviso, 2018a).
The major parameters affecting CFA quality are chemical
composition of coal burned and combustion conditions, i.e. the rate
of oxidation and pulverization. Besides the presence of oxides, like
SiO2, Al2O3, Fe2O3, CaO, MgO, K2O, Na2O, and TiO2, CFA is also
composed of variable amounts of trace elements (e.g. As, Se, Cd, Cr)
(Querol et al., 1996; Jegadeesan et al., 2008) that make it potentially
toxic. Therefore, the direct use of CFA leads to hazardous effects on
the ecosystem (Huggins et al., 2016). Table 1 displays different
compositions of CFAs collected from various sites. The chemical-
mineralogical composition of CAF allows its usage in many fields.
The utilization rates of CFA in US, EU, India and China were esti-
mated to be around 50%, 90%, 60%, 67%, respectively (Yao et al.,
2015). Also, the global average utilization rate of CFA is 25% that
is not adequate. CFA as a pozzolanic material has been prevalently
employed in manufacturing cement as a supplement to save its
Fig. 3. (a) Production of coal ash in a coal mine site (The mountain contains coal ash
more than two million tons) and (b) The negative effects of CFA accumulation on the
environment (destruction of natural eco-system), Savadkouh, Mazandaran, Iran, (c)
CFA emission into the air and environment by coal-fired power plant in Georgia, and
(d) Accumulation of coal fly ash in the landfills around Georgia coal-fired power plant
(https://en.wikipedia.org/wiki/Plant_Scherer).
consumption. Due to its alkaline features with negatively charged
surface, the investigations have also indicated its ability for the
adsorption of metal ions from solutions. Moreover, in the last few
years, CFA usage as a cheap source of aluminosilicate has attracted
scientists who have shown the successful transformation of this
waste material into zeolites, depending on its mineralogical
composition characterized by the presence of a large amount of
amorphous materials as well as crystalline phases, such as quartz,
hematite, magnetite, anhydrite, and lime. In our previous papers,
transformation of CFA into zeolite was investigated (Belviso et al.,
2010a, 2011; Belviso, 2018b). Also, the successful application of
the synthetic products from CFA to remove toxic elements from
both water and polluted soil was demonstrated (Belviso et al.,
2010b, 2011; 2012). The most prevalent applications and proper-
ties of CFA are reported in Fig. 4.
4. Opportunities and challenges of CFA
It is predicted that the increase in demand for energy generation
leads to an increase in the production rate of CFA. However, there is
no comprehensive plan to utilize this generated CFA for the fabri-
cation of value-added products. Unlike coal factories and coal-fired
power plants that are inattentive to this valuable by-product, re-
searchers have been working on the possibility of CFA conversion to
a series of effective products, such as zeolites, catalysts, photo-
catalysts, and geopolymers. Due to the aluminosilicate content of
CFA and also the high price of commercial types of mentioned
products, CFA can be used for the production of competitive
products with lower cost. The production path of CFA-based ad-
sorbents can consist of physical process, chemical process, quality
control, packaging and distribution. This is a golden opportunity for
both coal factories and coal-fired power plants to support and use
profitable plans by establishing an independent or lateral unit for
the production of value-added products from CFA. The imple-
mentation of profitable plans in both coal factories and coal-fired
power plants not only helps them to get rid of upcoming chal-
lenges of CFA (CFA environmental problems), but also increases
 S.M. Hosseini Asl et al. / Journal of Cleaner Production 208 (2019) 1131e1147 1135

Table 1
Chemical composition of CFA by XRF in different zones or sites.

SiO2 37.88 55.54 57 28.5e59.7 37.8e58.5

Al2O3 28.73 35.84 30.51 12.5e35.6 19.1e28.6

Fe2O3 18.07 4.24 5.71 2.6e21.2 6.8e25.5
CaO 11.54 2.99 0.83 0.5e28.9 1.4e22.4
MgO 1.79 0.59 0.6e3.8 0.7e4.8
K2O 0.34 1.26 0.4e4 0.9e2.6
Na2O 0.29 0.19 0.1e1.9 0.3e1.8
TiO2 1.23 1.61 0.5e2.6 1.1e1.6
P2O 0.42 0.1e1.7 0.1e0.3
SO3 0.38 0.14 0.1e12.7 0.1e2.1
LOI 0.98 0.13 1.4 0.8e32.8 0.2e11
Ref. (Hosseini Asl et al., 2013) (Qi et al., 2015) (Shyam et al., 2013) (Blissett and Rowson, 2012) (Blissett and Rowson, 2012)

ray diffraction (XRD) is the technique in practice. The major

Fig. 4. Prevalent applications and properties of CFA.
their incomes by selling CFA-based products to gain their market
through competing with the similar commercial products. In fact,
the most suitable way for the generation of clean energy from fossil
fuels like coal is the renovations of available technologies in the
related industries for the reduction of air and water pollutants.
Controlling the dose of gaseous and aqueous pollutants is imper-
ative to prevent their negative effects on the aquatic organism,
ecosystem, and particularly the human health that can be carried
out by cost-effective and efficient products like CFA-based adsor-
bents with acceptable reusability properties in comparison with
the similar commercial products. Thereby, investing on research
and development projects can provide remarkable income for coal
industries besides solving the global environmental crises of CFA.
diffraction peaks in various CFAs are quartz, hematite, magnetite,
anhydrite, and lime. Appearance of new peaks in XRD result after
chemical synthesis confirms the modification in the structure.
Fig. 5a illustrates the XRD patterns of a raw CFA (RFA) and its
synthesized zeolite (ZFA) (Javadian et al., 2015). Unlike the RFA,
there were no diffraction peaks and crystalline phases in the XRD
pattern of the ZFA. The disappearance of the most phases, partic-
ularly the magnetite diffraction peak, suggests the formation of an
amorphous phase (geopolymer) on the ZFA surface.
The main bonds between elements and their stretching vibra-
tions on the surfaces of CFA-based adsorbents are determined by
Fourier transform infrared spectrometry (FTIR). For example, Wen
et al. (2011) synthesized an adsorbent composed of chitosan and
CFA and characterized the structure of the substances (CFA, chito-
san and chitosan-coated CFA composite) using FT-IR. The results in
Fig. 5b depict the specific peaks at 3423, 2877, 1597, 1383, and
1325 cm
1 corresponding to frequent stretching vibrations of eOH
and eNH2, eCH and eCH2, eNH2, CeN, and CeO bonds, respec-
tively. The skeletal vibrations observed at 1090 and 1041 cm
1 are
related to CeO bonds. After acidic treatment with H2SO4, the
adsorbent revealed the peaks at 1035, 777, and 482 cm
1 that are
assigned to the frequencies of SieOeSi bonds plus the asymmet-
rical and symmetrical stretching and vibration of aluminum oxide,
respectively (Gandhi et al., 2010). After the coating process, the final
composite contained most of the functional groups of both CFA and
chitosan, like SieOH, eNH3þ, and Alþ3 which were useful for the

5. Preparation methods and characterization of CFA-based

adsorbents

Most CFA-based adsorbents are synthesized by conventional

methods, such as chemical modification through acidic and basic
treatment and impregnating with metallic or non-metallic com-
pounds. In addition, hydrothermal treatment, fusion method, mi-
crowave method, ultrasonic method, and a combination of them
are used to produce various zeolites, catalysts, photocatalysts, and
geopolymers (Hosseini Asl et al., 2018). Some CFA-based adsorbents
synthesized via different preparation methods are reported in
Tables 2e5
Characterization is an important step to identify the properties
of adsorbents and is mainly carried out by mineralogical, physical,
and morphological analyses. To identify various compounds on the Fig. 5. (a) X-ray diffraction patterns of RFA and ZFA (Javadian et al., 2015), (b) FT-IR
surface of CFA-based adsorbents, their crystalline phases, the spectra of fly ash, chitosan and chitosan-coated fly ash (Wen et al., 2011), (c) Particle
average size of crystals, and changes in the structure of crystals, X- size distributions of NaeP1, Na-X, Clinoptilolite and Absodan (Bandura et al., 2015).
1136 S.M. Hosseini Asl et al. / Journal of Cleaner Production 208 (2019) 1131e1147
adsorption process. According to the FT-IR spectra, the authors
concluded that an inter-penetrating network were formed due to
the interactions between silicon matrix (CFA) and polysaccharide
(chitosan) and, as a result, the chitosan particles were immobilized
on the CFA surface (Wen et al., 2011).
Since particle size has a direct impact on the velocity of aqueous
movement or gaseous flow through solids, particle size distribution
(PSD) is used to determine the efficiency of CFA-based adsorbents
in the adsorption process. Smaller particle size creates higher sur-
face area hence higher adsorption capacity. Bandura et al. (2015)
performed PSD analysis for Clinoptilolite, Absodan, and NaeP1
and Na-X zeolites in the range of 0.01e100 mm. The results of PSD in
Fig. 5c illustrate that NaeP1 and Abdosan are homogeneously
distributed with the average particle size of about 20 mm. The
particle size in Na-X and Clinoptilolite is around 50 and
20e250 mm, respectively. They concluded that NaeP1 had higher
adsorption efficiency compared to the other adsorbents due to its
small particle size (Bandura et al., 2015).
Scanning Electron Microscopy (SEM) is a powerful analysis tool
that reveals useful information, such as external morphology and
orientation of materials making up the sample. The main
morphology results for CFA particles obtained from SEM indicate
their irregular, spherical, and cenospherical solid shapes, plus
porous structure due to the existence of unburned carbons. In some
SEM images, it was observed that the particles of minerals, like
quartz, corundum, and magnetite were agglomerated. (Hosseini Asl
et al., 2013; Javadian et al., 2015). The investigations on the
morphology of various CFA-based adsorbents show that it is
fundamentally changed, particularly after the coating process,
confirming the formation of novel and porous materials on the
surface of adsorbents. The SEM images of the synthesized CFA and
CFA-based adsorbents are indicative of their different amorphous
shapes, cubic and spherical particles in comparison with initial ash
as depicted in Fig. 6ael. The SEM image reported in our previous
work (Fig. 6b) clearly demonstrates the porous network structure
of the ZFA. After surface modification of the ZFA by hydroxyl
groups, the size of the particles sharply increased. In another study,
SEM analysis was used to recognize the surface changes in the
synthesized FA-TiO2 before and after adsorption (Fig. 6l). The size of
particles considerably increased (3e9 mm) compared with the raw
Fig. 6. SEM images of (a) RFA, (Hosseini Asl et al., 2013), (b) ZFA, (Javadian et al., 2015),
(c) ZFA/HZ, (Lin et al., 2016), (d) NaeY, (Izquierdo et al., 2016), (e) NaeP1, (Bandura
et al., 2015), (f) Na-X, (Bandura et al., 2015), (g) FAICS, (Adamczuk and Kolodynska,
2015), (h) FA-CS, (Wen et al., 2011), (i) FAA-CS48, (Visa and Chelaru, 2014), (j) FA-
HCleY3, (Yan et al., 2012), (k) MT-Z, (Itskos et al., 2015) and (l) FA-TiO2, (Visa and Duta,
2013).
CFA. After direct contact with heavy metals solution, the adsorbent
particles were agglomerated, and larger clusters of cubic and
spherical crystals were formed on the surfaces of the CFA particles
(Visa and Duta, 2013).
6. Removal of aqueous and gaseous pollutants
Comprehensive investigations on CFA-based adsorbents have
demonstrated their considerable performance in degradation of
various aqueous pollutants, such as organic and petroleum com-
pounds, dyes, heavy metals, radionuclides, chemical oxygen de-
mand (COD), and suspended solid (SS) (Alinnor, 2007; Cho et al.,
2005). Furthermore, CFA-based adsorbents have been used to
capture multifarious gaseous pollution, including CO2, SO2, and
H2SO4, resulting in favorable removal efficiency (Jha and Singh,
2016). All the mentioned contaminants have been removed effec-
tively by different types of CFA-based adsorbents, such as rawand
modified types, zeolites, catalysts, photocatalysts, and geopolymers
(Belviso, 2018b). The results have clearly illustrated that the
removal efficiency of CFA-based adsorbents is remarkably higher
than that of the raw CFA (Zhuang et al., 2016). The following sec-
tions discuss the latest achievements regarding the environmental
applications of CFA-based adsorbents.
6.1. Removal of dyes
Industrial wastewaters with variety of dyes are one of the most
important world concerns. Due to the carcinogenic and mutagenic
properties of dye contaminants, the release of colored wastewaters
into the environment seriously damages the aquatic organism,
ecosystem, particularly the human health. The studies on CFA have
indicated that it can be effectively used as an efficient adsorbent for
the degradation of dyes from industrial wastewaters and also as a
raw material for the synthesis of micro and mesoporous
adsorbents.
Zhou et al. (2015) used CFA as a support to produce mesoporous
Al-MCM-41, and further applied it to remove Methylene Blue (MB)
from aqueous solutions. At pH ¼ 10, the maximum uptake of the
catalyst reached 277.78 mg g
1 within 2 h. The experimental data
were fitted well by pseudo-second-order kinetic and the Langmuir
isotherm models, indicating a monolayer chemisorption. Also, the
spontaneous and exothermic entropy-reduction properties of MB
adsorption were confirmed by thermodynamic studies. The pho-
tocatalytic degradation of MB was reported by a type of CFA-based
nano-zeolite photocatalyst (Fe2þeNa-X). The Fe2O3eNa-X photo-
catalyst exhibited 90.53% degradation efficiency for MB at pH ¼ 6.9
within 3 h (Sudha et al., 2015). The excellent photocatalytic
degradation of MB (around 98%) was obtained using a stable Ag-
doped ZnO/CFA nanocomposite (Kim et al., 2015). Jin et al. (2014)
evaluated the depolarization of MB by means of the CeO2/FACs
photocatalyst and showed that the degradation efficiency reached
60% within 5 h. In another research, Fe2O3eTiO2/CFA composite
was used for the photocatalytic oxidation of MB. The maximum
degradation efficiency was reported to be 86.81% within 1 h under
the visible light (Zhu et al., 2016). Saud et al. (2015) also performed
the decomposition of MB by CFA/TiO2 nanofiber. It was observed
that the prepared photocatalyst completely removed MB from
aqueous solutions within 2 h. Two kinds of CFA composites,
including the zeolite/hydrous iron oxide and zeolite/hydrous zir-
conia were employed for MB adsorption. Both composites exhibited
an excellent adsorption efficiency (~100%) at pH ¼ 7 (Lin et al.,
2016). MB was effectively removed from aqueous solutions with
90% adsorption efficiency by the hydrothermally modified CFA
(Visa and Chelaru, 2014). A similar research was carried out using
hydroxysodalite synthesized from CFA. The maximum adsorption
 S.M. Hosseini Asl et al. / Journal of Cleaner Production 208 (2019) 1131e1147
efficiency of 94% for MB was obtained at pH ¼ 5 (Fungaro et al.,
2011). The Bromo sodalite synthesized from CFA illustrated rela-
tively good performance for the adsorption of MB with the removal
efficiency of around 90% (Borhade et al., 2017). The efficiency of a
geopolymer synthesized from CFA (FAG) for MB removal from
aqueous solutions was also investigated (Novais et al., 2018).
Alouani et al. (2018) used FAG as an efficient adsorbent with
adsorption capacity of 37.04 mg g
1 whose adsorption process was
well described by Langmuir isotherm model. The adsorption effi-
ciency and photodegradation of Rhodamine B (RhB) were studied
using the FeeNeTiO2/CFA photocatalyst, and the photocatalyst
with the Fe/Ti ratio of 0.71% exhibited the best performance for the
photocatalytic degradation of RhB (89%) under the irradiation of
the visible light for 4 h. The elimination rate of total organic carbon
(TOC) was estimated to be 75.3% after irradiating for 4 h (Song et al.,
2016). The authors proposed a three-step mechanism of photo-
catalytic degradation process by the FeeNeTiO2/FAC as shown in
Fig. 7. Firstly, Fe and N contents of the photocatalyst generated
photo-induced electron-hole pairs to be reacted with RhB. Sec-
ondly, FeeOeTi and TieN were formed, and the band gap was
narrowed. Under the visible light, the photocatalyst was excited
and generated the electron-hole pairs, causing the water molecules
to decompose to OH and H. H2O2 was formed from the recom-
bination of OH reacted (photonic reaction) with Fe3þ contents of
the catalyst as well (Pang and Abdullah, 2012). Finally, the floata-
tion of FAC on the surface of water occurred without any aggre-
gation. Thus, the adsorption efficiency increased, since more
catalyst particles were exposed to the visible light (Wang et al.,
2011). Recently, RhB dye was efficiently degraded under the irra-
diation of the visible light using TiO2/ZnFe2O4/AFAC nanocomposite
photocatalyst with the maximum removal efficiency of 97.1% (Fan
et al., 2018). Lin et al. (2014) investigated the degradation of RhB
by a novel CFA photocatalyst (PVP/BiOBr/FACs). Under the visible
light irradiation, RhB removal efficiency reached 87%. In another
study, the hetero-structured CFA-ZnO semiconductor photocatalyst
was applied for the degradation of RhB, Reactive Orange 4 (RO), and
Trypan Blue (TB) dyes from aqueous solutions. Under the natural
UV light within 90 min, degradation percentages for RhB, RO, and
TB reached 99, 98, and 96, respectively (Thirumalai et al., 2016). The
tungsten oxide-CFA composite was used as an adsorbent for the
removal of Bemacid Blau (BB) and Bemacid Rot (BR) dyes from
aqueous solutions. Removal percentages for BB and BR were up to
80% and nearly 80%, respectively (Visa et al., 2015). Wang et al.
(2015b) studied the catalytic performance of the CuAg-FAC for
the degradation of Orange IV (OIV), Orange II (OII), and Reactive
Fig. 7. Three-step mechanism of photodegradation process by means of the Fee-
NeTiO2/FAC photocatalyst (Song et al., 2016).
1137
Black 5 (RB5). The study showed that the catalytic activity led to the
satisfactory removal of dyes within 20 min with the efficiencies of
98.4%, 97.5%, and 98.8% for OIV, OII, and RB5, respectively. Two types
of modified zeolites prepared from CFA were employed for the
adsorption process of Crystal Violet (CV). The maximum adsorption
capacities of the modified zeolites for CV were calculated to be
36.7 mg g
1 and 21.1 mg g
1 (Bertolini et al., 2013). A similar
research carried out by Bertolini et al. (2015) on two types of CFA-
based zeolites indicated that CV was efficiently removed by both
adsorbents. Fungaro and Magdalena (2014) surveyed the adsorp-
tion efficiency of Acid Orange 8 (AO8) by means of a modified
nanozeolite synthesized from CFA. A good adsorption performance
of the synthetic product was observed with the removal efficiency
of 98%. Another type of nanozeolite fabricated from CFA was used to
remove Solophenyl Navy (SN), Solophenyl Turquoise (ST), Solo-
phenyl Navy Hydrolysed (SNH), and Solophenyl Turquoise Hydro-
lysed (STH) from simulated textile wastewater. The maximum
removal percentages for SN, ST, SNH, and STH were attained to be
78, 85, 66, and 91, respectively (Cunico1 et al., 2015). All the
aforementioned examples clearly indicate that CFA-based adsor-
bents are effective for the adsorption and degradation of hazardous
industrial dyes (Table 2).
6.2. Removal of heavy metals and agricultural nutrients
A CFA modified by functionalized mesoporous silica was suc-
cessfully used to adsorb Cu(II) ions from aqueous solutions. The
large surface area of the functionalized adsorbent led to high
removal efficiency of Cu(II) ions (~98%), and the experimental data
were fitted well by Freundlich isotherm model (Pizarro et al., 2015).
In another attempt, Cu(II) ions were removed successfully by means
of a porous CFA-based geopolymer modified by iron ore tailings
with the uptake capacity of 13.41 mg g
1 at 40  C and pH ¼ 6. The
study reported that both Langmuir and Freundlich isotherm
models fitted the adsorption data of the spontaneous and endo-
thermic adsorption process (Duan et al., 2016). Al-Harahsheh et al.
(2015) conducted a series of experiments for the adsorption of
Cu(II) ions using a geopolymer prepared from CFA. The authors
reported that under the experimental conditions of pH ¼ 6,
T ¼ 45  C, contact time ¼ 2 h, and adsorbent dose ¼ 2 g L
1, Cu(II)
ions were efficiently removed with 93.9% removal efficiency. The
kinetic and isotherm studies illustrated that the pseudo-second-
order kinetic and Langmuir isotherm models fitted the adsorption
data. Another type of mesoporous aluminosilicates was synthe-
sized from CFA using cetyltrimethylammonium bromide
(C16TMABr) under alkaline conditions, and then applied in the
adsorption process of Cu(II) ions from aqueous solutions. Evalua-
tions showed that the increase in Si/Al ratio improved the
adsorption rate considerably with the maximum adsorption ca-
pacity of Cu(II) ions around 221 mg g
1 (Wu et al., 2012). In our
previous report (Javadian et al., 2015), the adsorption efficiency of
Cd(II) ions from aqueous solutions was examined by a type of
geopolymer synthesized from CFA. Under the optimum conditions,
the maximum Cd(II) ions removal efficiency of 84% was achieved.
The isotherm and kinetic studies indicated that the Langmuir and
pseudo-second-order models were in good agreement with the
adsorption data. We also converted CFA to zeolite by the fusion
method and used it as an adsorbent to remove Cr(VI) ions from
aqueous solutions. More than 80% of Cr(VI) ions were removed, and
the equilibrium data were well described by both Freundlich and
Langmuir isotherm models. The adsorption kinetic followed
pseudo-second order, and the thermodynamic studies confirmed
the spontaneous and endothermic nature of the process (Hosseini
Asl et al., 2013). Recently, we studied the adsorption capacity of a
hydrous iron oxide/aluminumhydroxide composite loaded on CFA
1138 S.M. Hosseini Asl et al. / Journal of Cleaner Production 208 (2019) 1131e1147

Table 2
Summary of adsorption conditions of various dyes by the CFA-based adsorbents.

Dyes Adsorbent Preparation method pH Time Dosage C0 Removal Ref.

(h) (ppm) efficiency

Methylene blue (MB) Al-MCM-41-10 Hydrothermal 10 2 10 mg 150 ~85% (Zhou et al., 2015)
treatment
Fe2O3eNa-X photocatalyst Hydrothermal 6.9 3 100 mg 10 90.53% (Sudha et al., 2015)
treatment
AgeZnO/FA photocatalyst Hydrothermal 3 15 mg 10 ~98% (Kim et al., 2015)
treatment
CeO2/FACs photocatalyst Coating technique 5 0.2 g 10 60% (Jin et al., 2014)
Fe2O3eTiO2/FA photocatalyst Sol-gel process 1 0.1 g 2 86.81% (Zhu et al., 2016)
FA/TiO2 nanofiber Electrospinning 8 2 20 mg 10 100% (Saud et al., 2015)
process
ZFA/HIO Zeolite Hydrothermal 8 4 5 g L
1 250 ~100% (Lin et al., 2016)
ZFA/HZ Zeolite treatment ~100% (Lin et al., 2016)
FAA-CS24 Hydrothermally 5 2 0.15 g >90% (Visa and Chelaru, 2014)
modified
Zeolite HS Hydrothermal 5 0.33 1g 50 94% (Fungaro et al., 2011)
treatment
Bromo sodalite Hydrothermal 5 1 0.5 g 40 ~90% (Borhade et al., 2017)
treatment
FAG Alkaline activation 5 2 0.1 g 98.5% (Alouani et al., 2018)
FA-Geo Alkaline activation 30 0.57 g 50 ~65% (Novais et al., 2018)
Rhodamine B (RhB) FeeNeTiO2/FAC photocatalyst Sol-gel process 4 0.2 g 8 89% (Song et al., 2016)
TiO2/ZnFe2O4/AFAC Hydrothermal 0.5 0.2 g 10 97.1% (Fan et al., 2018)
nanocomposite treatment
PVP/BiOBr/FACs photocatalyst Hydrothermal 0.5 0.1 g 15 87% (Wang et al., 2017)
treatment

1
FA-ZnO photocatalyt Hydrothermal 7 1.5 3gL 5 99% (Thirumalai et al., 2016)
treatment
SMZBA Hydrothermal 2 0.1 g 20 50% (Alc^
antara et al., 2016)
treatment
Reactive Orange 4 (RO) FA-ZnO photocatalyt Hydrothermal 7 1.5 3 g L
1 5 98% (Wang et al., 2015b)
treatment
Bemacid Blau (BB) FAWO3 Alkali treatment 2 2g 50 >80% (Visa et al., 2015)
Bemacid Rot (BR) FAWO3 Alkali treatment 2 2g 50 ~80% (Visa et al., 2015)

1
Trypan Blue (TB) FA-ZnO photocatalyt Hydrothermal 7 1.5 3gL 5 96% (Thirumalai et al., 2016)
treatment
Orange IV CuAg-FAC Coating technique 0.33 0.1 g 100 98.4% (Wang et al., 2015b)
Orange II CuAg-FAC Coating technique 0.33 0.1 g 100 97.5% (Wang et al., 2015b)
Reactive Black 5 CuAg-FAC Coating technique 0.33 0.1 g 100 98.8% (Wang et al., 2015b)
Acid Orange 8 (AO8) SMZ-Br nanozeolite Hydrothermal 5 2 2g 25 98% (Fungaro and Magdalena,
activation 2014)
Crystal Violet (CV) MZSF Zeolite Hydrothermal 5 0.33 1g 185 77% (Bertolini et al., 2015)
treatment
MZSB Zeolite Hydrothermal 5 0.33 1g 185 52% (Bertolini et al., 2015)
treatment
ZFA Zeolite Hydrothermal 5 0.5 0.25 g 185 99% (Bertolini et al., 2013)
activation
ZBA Zeolite Hydrothermal 5 0.5 0.25 g 185 96% (Bertolini et al., 2013)
activation
Solophenyl Navy (SN) ZMF Hydrothermal 5 2 0.1 g 31 78% (Cunico1 et al., 2015)
treatment
Solophenyl Turquoise (ST) ZMF Hydrothermal 5 2 0.1 g 31 85% (Cunico1 et al., 2015)
treatment
Solophenyl Navy Hydrolysed (SNH) ZMF Hydrothermal 5 2 0.1 g 31 66% (Cunico1 et al., 2015)
treatment
Solophenyl Turquoise Hydrolysed ZMF Hydrothermal 5 2 0.1 g 31 91% (Cunico1 et al., 2015)
(STH) treatment

to remove Cr(VI) ions from aqueous solutions. At optimum condi-
tions, the maximum adsorption capacity of 33.3 mg g
1 was ob-
tained, and pseudo-first-order kinetic and Freundlich isotherm
models fitted the experimental data. In addition, the adsorption
process was predicted well using a fuzzy logic modeling with a low
deviation from the experimental data (R2 ¼ 0.95) (Hosseini Asl
et al., 2017). Zhou et al. (2016) investigated the polypyrrole/CFA-
iron composites. They used the final magnetic adsorbent to
remove Cr(VI) ions from wastewater streams. This was successfully
accomplished and the maximum adsorption capacity of the
adsorbent was reported to be 119.33 mg g
1. CFA was also con-
verted to zeolite X and used to adsorb Cr(VI) ions from aqueous
solutions. The maximum adsorption capacity was 1.549 mg g
1
under the optimum conditions of C0 ¼ 40 ppm and contact
time ¼ 2 h (Wang et al., 2017). Wen et al. (2011) investigated the
adsorption of Cr(VI) ions from aqueous solutions by means of a
chitosan-CFA composite. The maximum capacity of the bio-
adsorbent was 33.27 mg g
1 at pH ¼ 5 within 50 min. Recently,
Zeolite LTA was synthesized from CFA and employed to remove
Hg(II) ions from industrial wastewaters. Hg(II) ions were effectively
removed with the maximum adsorption efficiency of 94%. The
adsorption data showed the best affinity with Freundlich isotherm
and pseudo-second-order kinetic models (Attari et al., 2017). In
another recent research, a synthetic zeolite from CFA was utilized to
 S.M. Hosseini Asl et al. / Journal of Cleaner Production 208 (2019) 1131e1147
remove Hg(II) ions from wastewater. The maximum adsorption
percentage of 91.27 was obtained at pH ¼ 2 (Tauanov et al., 2017).
Liu et al. (2013) studied the adsorption process of Hg(II) ions using a
hybrid mesoporous aluminosilicate (HMAS) synthesized from CFA.
The study reported that the adsorption of Hg(II) ions followed the
chemical ion-exchange mechanism, and the maximum adsorption
efficiency of 95% was obtained at pH ¼ 6. The hydroxysodalite
zeolite prepared from CFA was used to remove Pb(II) ions from
aqueous solutions. The maximum adsorption efficiency of 98.1% by
the synthetic zeolite indicated the favorable efficiency of the
adsorbent (Golbad et al., 2017). Additionally, Pb(II) ions were
removed from aqueous solutions by a type of CFA-based geo-
polymer. Under the optimum conditions of pH ¼ 5 and contact
time ¼ 2 h, the maximum removal efficiency reached 90.66% (Al-
Zboon et al., 2011). Yu et al. (2016) examined the adsorption ca-
pacity of a CFA-based zeolite to remove Ni(II) ions from aqueous
solutions. The study compared the adsorption capacity of the
synthetic zeolite and commercial zeolite (4A), concluding that CFA-
based zeolite had higher adsorption capacity (75.6 mg g
1) than
zeolite 4A (27.6 mg g
1). A highly valuable research was conducted
by Chen et al. (2016) to provide four types of CFA-based zeolites to
adsorb Ni(II) ions from aqueous solutions. The obtained removal
efficiencies were in the range of 92.5%e96.2%. Shukla et al. (2013)
utilized an artificial zeolite prepared from CFA to remove As(VI)
ions from aqueous solutions. At a low initial concentration of As(VI)
ions (C0 ¼ 60 mmol), the maximum capacity was reported to be
40.48 mmol g
1. The complete sequestration of Mn(II) ions from
aqueous solutions (100%) was achieved by 10 g of the synthetic
CFA-based zeolite (Belviso et al., 2014). A type of zeolite prepared
from CFA was used for multi-cation wastewater treatment con-
taining Pb(II), Zn(II), and Cd(II). In comparison with Cd(II) ions with
60% adsorption efficiency, Pb(II) and Zn(II) ions were efficiently and
selectively removed with 100% and 70% adsorption efficiencies,
respectively (Visa et al., 2012). Shyam et al. (2013) reduced the
concentration of Pb(II), Ni(II), and Cr(VI) ions from aqueous solu-
tions by means of a CFA adsorbent modified with CaCO3. The study
reported that under the optimum conditions, 1:10 CaCO3/CFA
removed Pb(II) up to 90%, 50% of Ni(II), and 30% of Cr(VI). In a
similar research, the Brazilian CFA was used for the production of
NaeP1 zeolite to cleanup contaminants from acid mine drainage.
The authors announced that most of the contaminants, like man-
ganese (99.8%), iron (>98%), copper (>96%), calcium (>98%), and
zinc (81%) were effectively removed during the first 30 min
(Cardoso et al., 2015a). The single and multiple systems of heavy
metal ions were adsorbed separately using a CFA-based zeolite.
Langmuir isotherm model well described the adsorption process,
and the maximum adsorption capacities for Pb(II), Cu(II), Cd(II),
Ni(II), and Mn(II) were 65.75, 56.06, 52.12, 34.40, and 30.89 mg g
1,
respectively, in the single system, and 45.28, 32.86, 26.93, 16.25,
and 14.63 mg g
1, respectively, in the multiple system (He et al.,
2016a). The multi heavy metal ions available in the wastewater
were removed by another type of CFA-based zeolite (MCM-41), and
approximately 90% of heavy metals were omitted from the waste-
water (Hui et al., 2009). In the same way, the adsorption of multi
heavy metal ions from aqueous solutions was investigated using
CFA coated with chitosan. The prepared adsorbent showed satis-
factory performance within 3 h. The adsorption capacities for Cr(III,
VI), Cu(II), Zn(II), and As(V) ions were reported to be 36.22, 28.65,
55.52, and 19.10 mg g
1, respectively (Adamczuk and Kolodynska,
2015). A CFA-based zeolite was applied to reduce ammonium
concentration in swine wastewater. Ammonium concentration was
reduced from 1205 mg g
1 to half (h ¼ 52%), and the maximum
adsorption capacity of 31 mg g
1 was obtained (Cardoso et al.,
2015b). Jiang et al. (2016) utilized a Na-A zeolite prepared from
CFA to remove ammonium contamination in aqueous solutions. At
1139
optimum conditions, the maximum removal efficiency was 60%
with the adsorption capacity of 60.6 mg g
1. Furthermore, a type of
CFA-based zeolite was chemically modified with hydrous
lanthanum oxide and used for phosphate removal from lake water.
The maximum adsorption capacity of 43.4 mg g
1 and the removal
efficiency of 60% showed the satisfactory performance of the
zeolitic composite (Wang et al., 2016c). The sequestration of nu-
trients (NHþ 3

4 (N) and PO4 (P)) from swine wastewater was con-
ducted using a CFA-based nano-zeolite. Under the optimum
conditions with the adsorbent dosage of 10 g L
1, the maximum
removal efficiencies for N and P were 51% and 91%, respectively. It is
worth noting that by increasing the adsorbent dosage to 80 g L
1,
removal efficiencies for N and P reached 95% and 99%, respectively
(Chen et al., 2012). He et al. (2017) studied the sequestration of
nutrients (N and P) from wastewater using a NaeP1 zeolite syn-
thesized from CFA. Magnesium as an ion exchange agent was added
to the adsorption process through two methods: adding directly to
the solution and adding to the zeolite. As a result, a rapid precipi-
tation occurred, and the concentration of N and P decreased. The
authors reported that under the optimum conditions of Z-P1
dosage ¼ 20 g L
1, mg2þ ¼ 4 mM, and t ¼ 30 min, adsorption effi-
ciencies for N and P were 65.2% and 92.3%, respectively, and any
increase in the amount of adsorbent dosage resulted in higher
adsorption efficiency. In addition, higher adsorption efficiencies
were obtained using the directly adding method. Information
regarding the adsorption of heavy metals and agricultural nutrients
by some CFA-based adsorbents is summarized in Table 3.
6.3. Removal of petroleum compounds
CFA-based adsorbents can effectively remove petroleum com-
pounds from wastewaters (Sasithorn et al., 2010). Asmaly et al.
(2016a,b) examined the adsorption capacity of aluminum oxide
impregnated CFA to remove phenol from aqueous solutions. The
investigation showed that phenol was completely removed with
the maximum adsorption capacity of 2.105 mg g
1 at pH ¼ 7 within
2 h. The experimental data had good compatibility with Langmuir
isotherm model. In another study, two types of CFA-based adsor-
bents were impregnated with aluminum (AFA) and iron (FFA), and
then applied for phenol removal from aqueous solutions
(Chaudhary et al., 2015). Higher adsorption capacities were ob-
tained by the modified adsorbents (AFA ¼ 14.07 mg g
1 and
FFA ¼ 12.63 mg g
1) compared with the raw CFA (7.99 mg g
1). The
maximum removal efficiencies of phenol were reported to be
85.6%, 82.1%, and 68% for AFA, FFA, and raw CFA, respectively.
Moreover, the authors reported that the Redlich-Peterson and Toth
isotherm models adapted well with equilibrium data.
The degradation of O-methyl phenol (OMP) was conducted us-
ing a type of CFA with high aluminum content chemically modified
by Fe(II)/Fe(III) (Meng et al., 2016). The fabricated catalyst (Fe-CFA)
efficiently removed OMP from aqueous solutions with 100%
removal efficiency during catalytic ozonation of OMP at pH ¼ 11.
The study claimed that the degradation process of OMP was
described well using pseudo-first-order kinetic model. Ma et al.
(2014) initially used CFA to adsorb Ni(II) ions, and then it was
directly applied in the ozonation degradation of 2-chlorophenol.
High adsorption efficiency (~100%) was observed by the CFA cata-
lyst, and the ozonation oxidation process followed pseudo-firs-
order kinetic model. A similar research was conducted for the
oxidation degradation of phenol by a CFA supported Co catalyst.
The degradation efficiency of phenol was reported to be almost
100% within 90 min at 45  C. Also, pseudo-first-order kinetic model
fitted well the experimental data, yielding the activation energy of
47 kJ mol
1 (Saputra et al., 2012). The CFA-cenospheres/Fe3O4
magnetic particles were used as a support to fabricate the magnetic
1140 S.M. Hosseini Asl et al. / Journal of Cleaner Production 208 (2019) 1131e1147

Table 3
Adsorption conditions of various heavy metals and agricultural nutrients by the CFA-based adsorbents.

Heavy metals & Adsorbent Preparation method pH Time Dosage C0 Sorption Removal Ref.
Nutrients (h) (ppm) capacity efficiency
(mg g
1)

As3þ Raw CFA 5 24 0.2 kg L
1 500 17.5 92% (Ulatowska et al., 2014)
As5þ Fe-AZ Modified with iron nitrite 6 24 50 mg 60 mM 40 mM g
1 (Shukla et al., 2013)
FAICS Coating technique 6 3 0.2 0.003 M 19.1 (Adamczuk and Kolodynska,
2015)
Cd2þ ZFA-600 Alkaline fusion treatment 5 5 0.1 g 53 26.246 84% (Javadian et al., 2015)
Zeolite X Alkaline fusion treatment 5.5 4 0.5 g 0.8 mM 1.18 mM g
1 100% (Wang et al., 2016a)
TiO2/FA Hydrothermal treatment 6.5 4 0.4 g 100 80% (Visa and Duta, 2013)
FA-Z Hydrothermal treatment 6.5 1.5 0.5 g 30.21 60% (Visa et al., 2012)
MG-Z & MT-Z Hydrothermal treatment 1.5 2 1g 1000 ~98% & 75% (Itskos et al., 2015)
Co2þ MCM-41 Alkaline activation 3 4 0.01 50 9.65 ~90% (Hui et al., 2009)
Cr3þ MCM-41 Alkaline activation 3 4 0.01 50 12.28 ~90% (Hui et al., 2009)
Cr6þ ZFA Alkaline fusion treatment 2 4 0.3 g 50 37.4 >80% (Hosseini Asl et al., 2013)
CFA-FeOOH Acidic and basic treatment 6 8 2 g L
1 53 33.3 84.9% (Hosseini Asl et al., 2017)
MSFA/PPy Chemical polymerization 2 40 10 mg 100 119.33 (Zhou et al., 2016)
ZFA-Na-A Fusion and hydrothermal 3.1 2 5 g L
1 50.26 8.7 (Xiao et al., 2015)
Zeolite X Mechano-chemical 2 1g 40 1.549 (Wang et al., 2017)
treatment
Chitosan/CFA Chemical activation 5 0.83 0.1 g 100 33.27 (Wen et al., 2011)
Cu2þ FA-MS Co-condensation with TEOS 7 2 3g 30 4.1 98% (Pizarro et al., 2015)
FA-IOT-Geo Alkaline activation 6 1.5 3 g L
1 100 113.41 98.3% (Duan et al., 2016)
CFA-Geo Alkaline ultrasonification 6 2 2 g L
1 100 152.3 93.9% (Al-Harahsheh et al., 2015)
MPF Hydrothermal treatment 4.4 0.5 0.01 g 200 221 (Wu et al., 2012)
TiO2/FA Hydrothermal treatment 6.5 4 0.4 100 90% (Visa and Duta, 2013)
MG-Z & MT-Z Hydrothermal treatment 1.5 2 1g 1000 100% (Itskos et al., 2015)
Fe 3þ
Zeolite NaeP1 Hydrothermal treatment 0.5 10 g L
1 5620 142 100% (Cardoso et al., 2015a)
Hg2þ Zeolite LTA Microwave irradiation 2.5 2 10 g L
1 10 0.7 94% (Attari et al., 2017)
ZFA Hydrothermal treatment 2 0.3 g 10 91.27% (Tauanov et al., 2017)
HMAS zeolite Hydrothermal treatment 6 1.66 1 g L
1 10 ~11 ~95% (Liu et al., 2013)
Mn2þ CFA Zeolite Alkaline fusion treatment >6 2 20 g 10 100% (Belviso et al., 2014)
Zeolite Alkaline fusion treatment 7 2 5 g L
1 100 30.89 100% (He et al., 2016a)
Ni2þ Zeolite Hydrothermal synthesis 3 24 1g 75.6 (Yu et al., 2016)
FA-Na-P/TEA Hydrothermal synthesis 2 0.1 g 50 96.2% (Chen et al., 2016)
FA-Na-X 95.5% (Chen et al., 2016)
FA-Na-P/NaeBr 95% (Chen et al., 2016)
FA-Na-P 92.5% (Chen et al., 2016)
Zeolite X Alkaline fusion treatment 5.5 1 0.5 g 0.8 mM 1.35 mM g
1 95% (Wang et al., 2016a)
MG-Z & MT-Z Hydrothermal treatment 1.5 2 1g 1000 ~50% & 52% (Itskos et al., 2015)
PB/FA - SA-FA Hydrothermal activation 2 50 g 1000 100% (Koukouzasa et al., 2010)
Pb2þ ZCFA Hydrothermal synthesis 5.5 12 3 g L
1 100 153.8 98.1% (Golbad et al., 2017)
Geopolymer Alkaline activation 5 2 0.07 g 100 174.34 90.66% (Al-Zboon et al., 2011)
FA-Z Hydrothermal treatment 6.5 1.5 0.5 g 2000 100% (Visa et al., 2012)
1:10 FA Chemical activation 5 1 100 mg 20 >90% (Shyam et al., 2013)
MG-Z & MT-Z Hydrothermal treatment 1.5 2 1g 1000 100% (Itskos et al., 2015)
PB/FA - SA-FA Hydrothermal activation 2 50 g 1000 100% (Koukouzasa et al., 2010)
Zn2þ FA-Z Hydrothermal treatment 6.5 1.5 0.5 g 18.87 70% (Visa et al., 2012)
FAICS Coating technique 2 3 0.2 g 0.003 M 55.52 (Adamczuk and Kolodynska,
2015)
PB/FA - SA-FA Hydrothermal activation 2 50 g 1000 100% (Koukouzasa et al., 2010)
NHþ
4 Zeolite NaeP1 Hydrothermal treatment 0.5 10 g L
1 9.6 2.7 ~61% (Cardoso et al., 2015a)
Zeolite NaeP1 Hydrothermal synthesis 7 0.5 20 g L
1 1205 31 52% (Cardoso et al., 2015b)
Zeolites Na-A Fusion & hydrothermal 7 1 0.1 50 60.6 60% (Jiang et al., 2016)
treat.
ZFA Hydrothermal synthesis 8.2 24 10 g L
1 652 51% (Chen et al., 2012)
Z-P1 Alkali hydrothermal 8.5 0.5 20 g L
1 500 65.2% (He et al., 2017)
reaction
PO3

4 ZHLO Chemical activation 9 24 0.01 g L
1 25 43.4 60% (Wang et al., 2016c)
ZFA Hydrothermal synthesis 8.2 24 10 g L
1 31.3 91% (Chen et al., 2012)
Z-P1 Alkali hydrothermal 8.5 0.5 20 g L
1 120 92.3% (He et al., 2017)
reaction

nanoparticles imprinted polymers (MNIPs) and magnetic molecu-
larly imprinted polymers (MMIPs) adsorbents. Both adsorbents
were surveyed for a competitive adsorption of nonylphenole (NP),
2e4 dichlorophenol (2e4 DCP), bisphenol A (BPA), 3e4 methyl-
enedioxy phenol (3e4 MDP), and p-(tert-octyl) phenol (PTOP). The
maximum NP, 2e4 DCD, BPA, 3e4 MDP, and PTOP adsorption ca-
pacities were ~90, 85, 80, 90, and 90 mg g
1, respectively, for the
MMIPs, and ~80, 80, 72, 73, and 75 mg g
1, respectively, for the
MNIPs. In addition, the authors asserted that the adsorption kinetic
followed pseudo-second-order model, and the equilibrium data
were fitted well with Langmuir isotherm model (Pan et al., 2013). A
modified CFA (impregnated with Al, Cd, Cu, Fe, and Ni) was
employed as an adsorbent for organic acids. The removal effi-
ciencies for b-napthaleneacetic acid, b-naphthoxyacetic acid, oxalic
acid, trichloroacetic acid, cinnamic acid, and indole-3-acetic acid
were 100%, 95.25%, 85.71%, 78.26%, 75%, and 63.63%, respectively
 S.M. Hosseini Asl et al. / Journal of Cleaner Production 208 (2019) 1131e1147 1141

(Li et al., 2012). In another research, CFA was modified through
acidic and microwave treatment, and then used to reduce sulfo-
nated humic acid (SHA) from aqueous media. SHA was completely
removed by only 3 g L
1 of the adsorbent at pH ¼ 3 within 8 min
(An et al., 2016). Evaluations illustrated that other organic com-
pounds, such as chrysoidine R (Matheswaran and Karunanithi,
2007), carbosyl group (Rao and Rao, 2006), and polychlorinated
biphenyls (Nollet et al., 2003) could also be removed from aqueous
media using CFA-based adsorbents. Recently, CFA-based zeolite
(NaeP1) was used to remove BTX from aqueous solutions. The
maximum removal efficiencies for benzene, toluene, o-xylene, and
p-xylene were 35%, 55%, 77%, and 99%, respectively. The kinetic and
isotherm studies demonstrated that the adsorption data were more
adaptable with pseudo-second-order kinetic and Langmuir
isotherm models (Bandura et al., 2017). Another new achievement
is related to the mixture of CFA and clay used in the purification of
crude oil contaminations from aqueous media. Maximum turbidity
and TDS removal efficiencies were reported to be 383.5 mg L
1 and
97.6%, respectively, at pH ¼ 8.78 within 20 min (Adams et al., 2017).
A similar research was performed by Bandura et al. (2015) for the
adsorption of oil products. NaeP1 and Na-X as CFA-based zeolites
were used to remove diesel fuels, yielding the adsorption capacities
of ~0.91 g g
1 and 0.79 g g
1, respectively. The authors stated that
CFA-based zeolites could be used as promising adsorbents for pe-
troleum spills cleanup. A summary of some organic pollutants
removed by the CFA-based adsorbents together with the prepara-
tion methods, adsorption conditions, and the performance of each
adsorbent is shown in Table 4.
6.4. Removal of radioactive pollutants
CFA-based adsorbents have shown good adsorption perfor-
mance towards radioactive pollutants available in wastewaters.
Fungaro et al. (2012) studied the adsorption capacity of CFA-based
zeolite-iron oxide magnetic nanocomposite to remove uranium
ions from aqueous solutions. The study reported that under opti-
mum conditions of C0 ¼ 100 ppm, pH ¼ 3, and t ¼ 2.5 h, U(VI) ions
were successfully removed (h ¼ 100%) from aqueous solutions, and
a monolayer adsorption with the maximum adsorption capacity of
22.4 mg g
1 was obtained due to the good compatibility of the
adsorption data with Langmuir isotherm model. In another
research, the mesoporous calcium-silicate material (MCSM) syn-
thesized from CFA was used to remove a variety of radionuclides
from wastewater. MCSM could remove up to 99.1% of 58Co, almost
100% of 60Co, and up to 98.7% of 51Cr, 54Mn, 59Fe, 95Nb, 95Zr, 99Mo,
and 137Cs. The authors reported that the adsorption efficiency of
iodine (132I and 133I) and noble gases (133Xe, 135Xe, and 41Ar) were
not satisfactory due to the negatively charged iodine ions and low
tendency of noble gases to enter in the reaction, consequently, they
did not participate well in the electrostatic interaction with the
negatively charged surface of the adsorbent (Qi et al., 2015). In
addition, the study proposed the adsorption mechanism of Co(II)
with four consecutive steps, including hydration, hydrolysis, sur-
face complexation, and ion exchange with Ca(II) as shown in Fig. 8.
Firstly, the hydrated cobalt ions diffused into the solution, reached
the boundary layer, and surrounded the MCSM particles. Secondly,
the hydrated cobalt ions diffused into the boundary layer, and the
hydrated cobalt cations were released among water molecules. In
the next step, i.e. complexation, the surface interactions and ion
exchange occurred between Co(II) cations and SiOH or CaOH of the
adsorbent, and the calcium ions were adsorbed onto the surface
and edge of the particles. Finally, in the hydration step, the diffusion
of Co(II) cations into the interlayer of CeSeH(I) took place and, as a
result, the cations were exchanged with calcium. Noli et al. (2016)
investigated the adsorption of barium (Ba) and europium (Eu) ra-
dionuclides from aqueous solutions using a type of CFA-based
zeolite containing NaeY and SOD. They reported the excellent
performance of the adsorbent in the adsorption process of both
radionuclides (h ¼ 100%), particularly at the optimum conditions of
T ¼ 308 K, pH ¼ 4, and t ¼ 2 h. The adsorption properties of two
kinds of modified CFA-based zeolites (A and B) to remove U(VI) ions
from aqueous solutions were examined, as well. U(VI) ions were
effectively removed within 1 h with the maximum removal effi-
ciencies of 90% and 99.5% for A and B, respectively (Xie and Zhou,
2017). Lieberman et al. (2015) conducted a series of experiments
for the stabilization of four radionuclides on the surfaces of two
types of CFAs. The study showed that Ce(III) and Ce(IV) ions were
completely removed from aqueous solutions, while the adsorption
efficiency of Cs(I) ions was not satisfactory (30%), and the fixation of
Sr(II) ions was not observed. Strontium ions were converted to

Table 4
Organic and petroleum reduction by the CFA-based adsorbents.

Organic & petroleum Adsorbent Preparation method pH Time Dosage C0 Sorption Removal Ref.
compounds (h) (ppm) capacity efficiency
(mg g
1)

Phenol FA-Al2O3 Impregnated with Al2O3 7 2 200 mg 2 2.105 100% (Asmaly et al., 2016)
AFA Impregnated with Al2O3 and 5 2 20 g L
1 200 14 85.6% (Chaudhary et al.,
Fe3O4 2015)
FFA 12.6 82.1% (Chaudhary et al.,
2015)

1
Co/FA Impregnation technique 0.5 0.4 g L 30 100% (Saputra et al., 2012)
O-methyl phenol (OMP) Fe-CFA Modified with Fe(II)/Fe(III) 11 0.2 5 g L
1 200 100% (Meng et al., 2016)
catalyst oxide
2-chlorophenol (2-CP) Ni-CFA Surface adsorption 8 0.2 2.775 ~100% (Ma et al., 2014)
Nonylphenol (NP) MMIPs Co-precipitation technique 6 2 100 434.8 ~90% (Pan et al., 2013)
MNIPs 6 2 100 357.1 ~80% (Pan et al., 2013)
BTX Zeolite NaeP1 Hydrothermal treatment 24 0.5 g 20 0.147 35% eB (Bandura et al., 2017)
0.129 55% -T (Bandura et al., 2017)
0.050 77% eO-x (Bandura et al., 2017)
0.038 99% eP-x (Bandura et al., 2017)
Sulfonated humic acid BD-FA Acid- and microwave assisted 3 8 3 g L
1 200 392.07 100% (An et al., 2016)
(SHA) treatments
Crude oil CFA/Clay Mix with clay 8 0.33 20 g 97.6% turbidity (Adams et al., 2017)
Diesel fuels Zeolite NaeP1 Hydrothermal treatment 24 5g 910 (Bandura et al., 2015)
Zeolite X 790 (Bandura et al., 2015)
1142 S.M. Hosseini Asl et al. / Journal of Cleaner Production 208 (2019) 1131e1147
Fig. 8. Proposed mechanism of Co(II) adsorption onto the surfaces of the MCSM
(Boundary layer between the solid surface and bulk solution, Ca(II) at the edge, CaeOH
sites in the Ca sheet and SieOH sites in the bulk silicate chains) (Qi et al., 2015).
SrCO3 (a carbonate salt), and then successfully trapped on the
surfaces or in the pores of the adsorbents. Furthermore, the authors
proposed the fixation mechanism of the radionuclides by CFA
adsorbent. The study remarked that Csþ interacted with CFA sur-
face through ion exchange mechanism (Fig. 9a), while in the case of
Ce3þ/4þ, the complexes of cesium and CFA were formed due to the
rapid equilibrium and precipitation. It was mentioned that the
main reason for this phenomenon could be the interaction between
cesium radionuclides and the functional groups available on the
surface of the adsorbent (Fig. 9b). The fixation mechanism of
strontium ions on the surface of CFA is shown in Fig. 9c.
6.5. Removal of COD and SS
Chemical oxygen demand (COD) and suspended solid (SS) are
considered as important factors in the quality evaluation of water
and wastewater. COD and SS are the indexes for the identification of
the amount of organic compounds and the presence of solids in
water and wastewaters. COD rate indicates the mass of oxygen
required for oxidation of organic compounds in water or
Fig. 9. Proposed mechanisms for fixation of radionuclides on the CFA surface: (a)
cation exchange between Csþ and CFA, (b) formation of Ce3þ/4þ complexes through
coordination sites and (c) SrCO3 precipitation on the surfaces of CFA at pH > 10.5
(Shukla et al., 2013).
wastewater. High concentrations of COD and SS in water and
wastewater are detrimental for human health, and particularly
aquatic organisms. One of the most effective adsorbents to remove
COD and SS is CFA. Hu et al. (2017) surveyed the adsorption of COD
and SS from soybean and dairy wastewaters by means of the
aluminum and iron-based coagulants prepared from CFA. It was
observed that the maximum removal efficiencies of COD and SS
achieved at pH ¼ 8 were around 20% and 80% for soybean waste-
water, and around 65% and 92% for dairy wastewater, respectively.
A series of experiments were conducted to remove COD from
aqueous solutions containing o-methyl phenol (OMP) using a CFA
catalyst modified by Fe(II)/Fe(III) oxides. The maximum removal
efficiency of COD was reported to be 44.5% at pH ¼ 11 (Meng et al.,
2016). Devi and Dahiya (2006) utilized CFA to eliminate COD from
domestic wastewater. They announced that the maximum removal
percentages of COD by the CFA, brick kiln, and commercial activated
carbon were 87.84, 83.22, and 99.35, respectively. The optimum
conditions were the adsorbent dosage of 180 g L
1 within 3 h,
60 g L
1 within 4 h, and 45 g L
1 within 5 h for the active carbon,
CFA, and brick kiln, respectively.
6.6. Capturing gaseous pollutants
The utilization of solid waste residual generated by industries as
an adsorbent to capture and store (CS) various gaseous pollutants
has attracted the attentions of many researchers. CFA as an abun-
dant waste is considered as a cheap source of aluminosilicate that is
able to capture gaseous contaminants (Wee, 2013). In a study, the
removal of CO2 was carried out using a raw CFA through surface
adsorption and carbonation process. Siriruang et al. (2016) studied
the capture of CO2 in a tubular reactor with the possibility of con-
trolling the gas flow temperature and pressure using a PID
controller (Fig. 10). As can be seen in Fig. 10, initially, nitrogen gas
was injected to carry all gas samples from the reactor to gas chro-
matography (GC). Then, CO2 was released to be captured by the
solid CFA, and the amount of CO2 in the outlet was measured by GC
equipped with a thermal conductivity detector (TCD). The
maximum capture rate of the CFA was 304.7 mmol g
1 of CFA con-
sisting of 2.9 and 301.8 mmol g
1 of CFA for adsorption and
carbonation, respectively. CO2 capture was also conducted by two
types of CFA adsorbents modified with NaOH and CaO (WNCF and
WNC). Both adsorbents showed excellent performance with CO2
adsorption efficiencies of 94.7% and 105.1% for WNCF and WNC,
respectively (Lee et al., 2014). Dananjayan et al. (2016) investigated
the capture and storage capacity of the CFA for sequestration of CO2.
The authors mentioned that the maximum capture and wet
Fig. 10. Schematic of dynamic experimental setup for CO2 sequestration by the CFA
adsorbent (Siriruang et al., 2016).
 S.M. Hosseini Asl et al. / Journal of Cleaner Production 208 (2019) 1131e1147 1143

The uptake capacity of a CFA to capture CO2 was surveyed by

Fig. 11. Schematic diagram of the setup for adsorption of H2SO4 mist by the CFA-based
adsorbents (Shu et al., 2015).
carbonation capacities of the CFA were 26.3 g kg
1 of CFA at 10 bar
within 1 h and 50.3 g kg
1 of CFA at 4 bar within 2 h, respectively.
Mazzella et al. (2016) at different pressures and temperatures. CO2
was completely captured by the CFA under the specific operational
conditions of P ¼ 15 bar, T ¼ 45  C, and t ¼ 134.8 min. A CFA modi-
fied by potassium (K-FA) was used to sequestrate CO2 at high
temperature. CO2 uptake rate reached 1.45 mmol g
1 at 700  C. In
addition, the authors reported that in the presence of Li2CO3, this
rate increased to 2.38 mmol g
1, and CO2 uptake of 90% was ach-
ieved within 5 min (Sanna and Maroto-Valer, 2016a). A similar
research was carried out using a CFA adsorbent modified by Na2CO3
(Na-FA). The maximum CO2 uptake rate of 9.24 wt% was achieved at

700 C in the presence of 12.5% CO2 and 12% H2O. This rate
increased to 11.2 wt% by the addition of 20% Li2CO3 (Sanna and
Maroto-Valer, 2016b). Yan et al. (2016) studied the adsorption
process of CO2 at different operational conditions using a high-

Table 5
Uptake of gaseous pollutants by the CFA-based adsorbents.

Gaseous Adsorbent Preparation method Operational conditions Capture capacity Capture Ref.
pollution efficiency

CO2 Raw CFA T: 30  C, t: 1 h, P: 1 atm 807.1 mmol g
1 >99% (Siriruang et al., 2016)
WNCF Mixing with NaOH and CaO T: 800  C, t: 1 h, d: 10 mg 94.7% (Lee et al., 2014)
WNC 105.1% (Lee et al., 2014)
Raw CFA T: 30  C, t: 1 h, P: 10 bar 26.3 g kg
1 67.87% (Dananjayan et al., 2016)
Raw CFA T: 45  C, t: 134.8 min, P: 181.76 g kg
1 100% (Mazzella et al., 2016)
15 bar
K-FA Mixing with K2CO3 T: 700  C, t: 1.5 h 1.45 mmol g
1 90% (Sanna and Maroto-Valer,
2016a)
Na-FA 0.5:1 Mixing with Na2CO3 T: 700  C, t: 45 min 9.24 wt.% (Sanna and Maroto-Valer,
2016b)
HACFA Alkaline activation T:323.15 K, t: 1 h, F: 8.67 mg g
1 (Yan et al., 2016)
95 mL min
1
Zeolite A Alkali fusion and hydrothermal T: 298 K, t: 20 min 145 mg g
1 (Soe et al., 2016)
Zeolite 13 treatment 220 mg g
1 (Soe et al., 2016)
Zeolite X Alkali fusion and hydrothermal T: 22  C, t: 1 h 60 mg g
1 (Kalvachev et al., 2016)
treatment
MCM-41-PFA Hydrothermal treatment T: 75  C t: 1 h, d: 20 mg, P: 13.31 wt.% 90% (Panek et al., 2017)
1 bar
Na-X-PEI-600 Alkaline fusion and hydrothermal T: 70  C, t: 2 h, F: 26 mg g
1 (Dindi et al., 2017)
treatment 0.5 ml min
1
Zeolite 13 Hydrothermal treatment T: 25  C, t: 1 h, F: 225 mg g
1 (Zhang et al., 2017)
100 ml min
1
SO2 Lignite CFA-AKP- T: 100  C, t: 90 min 46.6 g kg
1 (Kisiela et al., 2016)
5

H2SO4 NaOH/CFA Alkaline activation and chemical T: 120 C, t: 2 h 100% (Shu et al., 2015)
CaO/CFA treatment 100% (Shu et al., 2015)
H2O/CFA >60% (Shu et al., 2015)
H2S ACeNH4OHeOFA Physicochemical treatments T: 22  C, t: 15 min 0.3001 mg g
1 100% (Aslam et al., 2015)
MSWI-FA T: 25  C, t: 10 h 15.89 mg g
1 (Wu et al., 2018)
Hg HBr-CFA Chemical activation T: 150  C, t: 10 min 1500 mg kg
1 96.7% (Wang et al., 2016b)
CFA zeolite Hydrothermal treatment T: 100  C, t: 1 h 100% (Wang et al., 2015a)
CuCl2-MF Impregnation technique T: 200  C, t: 10 min 90.6% (Yang et al., 2016)
catalyst
NO LY-Cu Alkaline treatment and chemical T: 200  C, t: at initial times 100% (Izquierdo et al., 2016)
LU-Fe activation 100% (Izquierdo et al., 2016)
CFB Modified with gases T: 100, t: 30 min, Power: 80% (Nie et al., 2017)
60 W
BTX Zeolite Na-X Hydrothermal treatment T: 150  C 383.76 mmol g
1 B (Bandura et al., 2016)
T: 270  C 525.03 mmol g
1 T (Bandura et al., 2016)
T: 280  C 545.26 mmol g
1 (Bandura et al., 2016)
o-X
T: 280  C 563.82 mmol g
1 (Bandura et al., 2016)
m-X
T: 200  C 582.91 mmol g
1 (Bandura et al., 2016)
p-X
Zeolite NaeP Hydrothermal treatment T: 120 C 
1.44 mmol g
1 B (Bandura et al., 2016)
T: 100  C 10.52 mmol g
1 T (Bandura et al., 2016)
T: 100  C 26.22 mmol g
1 o- (Bandura et al., 2016)
X
T: 100  C 25.96 mmol g
1 m- (Bandura et al., 2016)
X
T: 100  C 20.50 mmol g
1 p- (Bandura et al., 2016)
X
1144 S.M. Hosseini Asl et al. / Journal of Cleaner Production 208 (2019) 1131e1147
alumina CFA. The study showed that at T ¼ 323.15 K and the flow
rate of 95 mL min
1, the maximum CO2 uptake rate reached
8.67 mg g
1. Zeolite A and 13 synthesized from CFA were
employed in the capture process of CO2, indicating that both zeo-
lites captured CO2 well (Zeolite A ¼ 145 mg g
1 and 13
X ¼ 220 mg g
1) (Soe et al., 2016). Kalvachev et al. (2016) examined
the adsorption of CO2 using Zeolite X synthesized from CFA. It was
observed that the uptake rate increased to 60 mg g
1 at 22  C
within 1 h. Recently, MCM-41 fabricated from CFA was used as a
cheap silica support for impregnating polyethyleneimine (PEI).
Thereafter, this novel adsorbent (MCM-41-PFA) was applied to
capture CO2. The CO2 equilibrium uptake efficiency of 90% was
obtained at 75  C within 1 h, and the uptake rate sharply increased
to more than 11 wt% in the first 5 min (Panek et al., 2017). Another
recent report is related to the capture of CO2 using the CFA-based
zeolite X modified with PEI by wet impregnation technique. The
synthesized adsorbent (Na-X-PEI-600) efficiently captured CO2
with the maximum adsorption capacity of 26 mg g
1 (Dindi et al.,
2017). The capture capacity of CO2 using zeolite 13  prepared
from CFA was studied by Zhang et al. (2017). CO2 was effectively
adsorbed with the adsorption capacity of 225 mg g
1. In an inter-
esting research, the adsorption and carbonation capacities of CO2
were examined using CFA to produce carbonated CFA to be later
applied in cement manufacturing. The maximum carbonation ef-
ficiency and CO2 uptake rate were reported to be 83.5% and
32 g kg
1 of the carbonated CFA, respectively (Ebrahimi et al., 2017).
Shu et al. (2015) investigated the adsorption capacities of CFA-
based adsorbents to remove sulfuric acid mist from lead-acid bat-
tery plants. The adsorption experiments were performed using a
fixed bed apparatus with the possibility of placing 300 g of the
adsorbents in a vertical organic glass reactor equipped with an inlet
for nitrogen as a sweeping gas (Fig. 11). As can be seen in Fig. 11, the
NaOH bath was placed after the reactor to ensure the complete
removal of H2SO4 mist. Consequently, H2SO4 mist was completely
removed (h ¼ 100%) by the NaOH/CFA and CaO/CFA, while the
maximum removal efficiency of H2O/CFA was only 60%. It was
asserted that the adsorption mechanism was the combination of
electrostatic interaction and chemical precipitation at the interface
of the adsorbent and H2SO4 mist (Shu et al., 2015). In a similar
study, oil fly ash (OFA) was activated by the adsorption of CO2 and
chemicals to remove H2S from a gas stream. It was reported that
during the first 15 min, H2S was effectively removed (h ¼ 100%)
using AC-NH4OH with the maximum uptake rate of 0.3001 mg g
1
(Aslam et al., 2015). A magnetic catalyst (CuCl2-MF) synthesized
from CFA was employed to eliminate mercury from the flue gases.
At the optimum conditions, the maximum uptake percentage of
Hg0 was reported to be 90.6 (Yang et al., 2016). In a creative
research, a modified CFA was used to remove the secondary release
of mercury from the flue gases of a coal-fired power plant. The
authors reported that by adding CaBr2 to CFA before coal com-
bustion process, the removal efficiency of Hg reached 94% (He et al.,
2016b). Furthermore, the removal of NO was conducted by two
types of zeolite Y catalysts (LY-Cu and LY-Fe) synthesized from CFA.
The denitration mechanism of CFA catalysts modified with various
gases (O2, N2, and Ar) was recently studied using the low-
temperature plasma technology. It was reported that at optimum
adsorption conditions, NO uptake efficiency reached 80% ((Nie
et al., 2017). The performance of various CFA-based adsorbents
for the adsorption of gaseous pollutants is summarized in Table 5.
7. Conclusions
The opportunities and challenges of CFA as a by-product of coal
factories and coal-fired power plant were investigated. According
to the published outlooks, CFA production rate will be increased
until 2040 due to the global growth in demand of energy. The
irregular disposal of CFA in landfills leads to irreparable damages to
the environment. The remarkable amount of aluminosilicate
available in CFA can be utilized as a source to produce valuable
advanced materials, such as zeolites, catalysts, photocatalysts, and
geopolymers all of which significantly improve the adsorption ca-
pacity of pollutants. As a result, the conversion of CFA to valuable
products seems to be indispensable. The adsorption capacity of
CFA-based adsorbents produced by various chemical syntheses and
modification methods were analyzed. In comparison with com-
mercial adsorbents, CFA-based adsorbents as efficient and
environmentally-friendly products can be used to clean up real
wastewaters containing dyes, petroleum compounds, heavy
metals, agricultural nutrients, radionuclides, COD, SS. Moreover, the
investigations confirmed that CFA-based adsorbents have good
performance in removing gaseous pollutants such as CO2, SO2,
H2SO4, H2S, Hg, NO, BTX. The findings during several years of
studies confirmed that this profitable by-product can benefit the
environment as well as being a source of income for producers.
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