Accepted Manuscript

Title: Fly ash zeolites for water treatment applications

Author: Nevin Koshy D.N. Singh

PII: S2213-3437(16)30046-X
DOI: http://dx.doi.org/doi:10.1016/j.jece.2016.02.002
Reference: JECE 969

To appear in:

Received date: 8-11-2015

Revised date: 8-1-2016
Accepted date: 1-2-2016

Please cite this article as: Nevin Koshy, D.N.Singh, Fly ash zeolites for
water treatment applications, Journal of Environmental Chemical Engineering
http://dx.doi.org/10.1016/j.jece.2016.02.002

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Fly ash zeolites for water treatment applications

Nevin Koshya and D. N. Singhb*

a
Research Scholar, Department of Civil Engineering, Indian Institute of Technology Bombay,
Powai, Mumbai-400076, India, nevinkoshy@gmail.com
b
Professor, Department of Civil Engineering, Indian Institute of Technology Bombay, Powai,
Mumbai-400076, India, dns@civil.iitb.ac.in
*Corresponding author. Tel.: +91-22-2576-7340; fax: +91-22-2576-7302

Highlights

1. Conventional and novel applications of fly ash zeolites for water treatment.
2. Fly ash zeolites have been used for removal of heavy metals and ionic species.
3. Treatment of industrial sludges, acid mine drainage and domestic wastewater.

Abstract
In the last few decades, fly ash, a coal combustion residue, has been used as a raw material

for synthesis of microporous aluminosiliceous minerals known as zeolites. Due to their

excellent ion exchange capacity, high surface area and unique pore characteristics, zeolites

have been used for removal of heavy metals (viz., As, Cd, Cr, Cs, Cu, Fe, Hg, Mn, Ni, Pb, Sr,

W and Zn) and ionic species (viz., ammonium, chloride, fluoride, nitrate, phosphate and

sulphate) from industrial sludges, acid mine drainage and wastewater from domestic and

industrial sources. In addition, fly ash zeolites find their application as sorbent medium in

permeable reactive barriers and contaminant barrier liners for immobilizing the contaminant
1
plume in soil. This paper reviews the applications of fly ash zeolites in various water

treatment studies and other related environmental cleanup projects, viz., depuration of

wastewater containing industrial dyes and hazardous ions and leachate treatment.

Furthermore, novel applications in the use of fly ash zeolites as permeable reactive barriers

and contaminant barrier liners as well as the future scope of research for environmental

cleanup are also discussed.

Keywords: Fly ash zeolite, applications, water treatment; heavy metal removal, effluent

treatment, permeable reactive barrier.

Notation

The following symbols are used in this paper:

AMD acid mine drainage

BOD biological oxygen demand
CEC cation exchange capacity (in meq/100g)
ce equilibrium concentration (in mg/l)
ci initial ion concentration (in mg/l)
COD chemical oxygen demand
HTAB hexadecyltrimethylammonium bromide
pHe pH after interaction
PRB permeable reactive barrier
PZC point of zero charge
q contaminant uptake (in mg/g)
SSA specific surface area (in m2/g)
t interaction time
T temperature (in º C)
VOC volatile organic compounds
η contaminant removal efficiency (in %)

2
1. Introduction

Fly ash is a coal combustion by-product generated in large quantities from coal thermal

power plants around the globe (Blissett and Rowson 2012). Hence, its utilization has gained

momentum in the past few decades and has been used as cement additive (due to its

pozzolanic property), in brick manufacturing (Koukouzas et al. 2011b), as backfill material

(Nhan et al. 1996; Shih and Chang 1996), for reinforcing filler in polymers (Kruger 1997;

Garde et al. 1999) and as a soil ameliorant (Jala and Goyal 2006). Furthermore, due to its

high silica and alumina content, fly ash has been perceived as an ideal precursor for synthesis

of zeolites (Holler and Wirsching 1985) and geopolymers (Silverstrim et al. 1988; Davidovits

1991).

Zeolites are three-dimensional tetrahedral aluminosilicate minerals, having their

negative charge (generated by isomorphous substitution of Si4+ by Al3+) counterbalanced by

native cations (Na+, K+, Ca2+ and Mg2+) and water molecules in their pores and channels. The

general formula for a zeolite is M2/nO.Al2O3.xSiO2.yH2O where M is any alkali or alkaline

earth element, n is the valence charge on that element, x varies from 2 to 10 and y varies from

2 to 7. The Al2O3 and SiO2 are the structural cations because they form the tetrahedral

framework with oxygen (Mumpton, 1985). Some common zeolites synthesized from fly ash

are presented in Table 1. Naturally occurring zeolites (natural zeolites) have restricted pore

sizes and channels, whereas fly ash-based synthetic zeolites possess a variety of pore

structures and are potential and probably economically viable sorbent minerals for trapping

various contaminants from air and water (Hollman et al. 1999, Franus et al. 2014). Though

raw fly ash has the potential for the removal of heavy metals, dyes and anions (Mohan et al.

2002; Weng and Huang 2004; Cho et al. 2005; Gitari et al. 2006; Alinnor 2007; Lu et al.
3
2009; Balsamo et al. 2011; Al-Khaldi et al. 2013), zeolites synthesized from it, augment its

immobilization characteristics to several folds (Lin et al. 1998; Woolard et al. 2002; Li et al.

2006;). Incidentally, zeolitized fly ash has been reported to have higher lead sorption capacity

than raw fly ash (6-7 times) and natural zeolites (3-5 times) (Lee et al. 2000; Itskos et al.

2010a).

Utilization of fly ash for synthesizing zeolites and determination of their heavy metal

uptake potential is important in consumption of ash currently dumped at disposal sites and

also for creating water treatment solutions for regions/countries facing limited water

resources. Based on the available literature, the locations of fly ashes, which have been

zeolitized for applications in depuration of contaminated water and wastewater, have been

illustrated in Fig. 1. In spite of India producing over 130 million tons/year and Russia having

1.5 billion tons of ash-slag waste stored in ash-disposal sites, very few studies have been

conducted in these countries with regard to environmental cleanup using fly ash zeolites that

would subsequently help in the bulk utilization of fly ash (Haque 2013; Kakaras et al. 2004;

Mir and Sridharan 2013; http://ksfenix.org/en; Putilov and Putilova 2010).

1.1. Synthesis and pretreatment of zeolites before their applications

Fly ash due to its activation using alkalis, such as NaOH, KOH, Ca(OH)2 and LiOH,

undergoes dissolution and subsequently crystallizes into zeolitic minerals (Steenbruggen and

Hollman 1998; Kolay et al. 2001; Moreno et al. 2001; Chen et al. 2006; Medina et al. 2010;

Jha and Singh 2014; Koshy et al., 2015a; Koshy et al., 2015b). The synthesis methods

include: (i) conventional hydrothermal treatment (Holler and Wirsching 1985; Murayama et

al. 2002; Adamczyk and Bialecka, 2005; Cundy and Cox, 2005; Moriyama et al. 2005;
4
Derkowski et al., 2006; Fansuri et al., 2008; Wdowin et al. 2014), (ii) alkali fusion-assisted

hydrothermal treatment (Shigemoto et al. 1993; Ojha et al., 2004; Terzano et al., 2005;

Mishra and Tiwari 2006; Wu et al., 2008; Kazemian et al. 2010; Jha and Singh, 2013), (iii)

microwave-assisted hydrothermal treatment (Inada et al. 2005; Querol et al. 1997; Tanaka et

al., 2008), (iv) ultrasonication-assisted hydrothermal (Feng et al., 2004; Andaç et al., 2005;

Kim et al., 2010; Belviso et al. 2011; 2013) and (v) molten salt method (Park et al., 2000;

Choi et al., 2001). In addition, pure zeolites can be synthesized from silica and alumina

extracts obtained by alkali leaching of fly ash (El-Naggar et al. 2008). Upon activation, the

particle size range of the original fly ash (generally, 0.5 µm to 400 µm) decreases, due to the

alkali etching on the surface of the fly ash particles and subsequent nucleation and

crystallization of small zeolitic minerals (Fig. 2), finally resulting in an increase in specific

surface area (Apiratikul and Pavasant 2008; Visa et al. 2012; Itskos et al. 2015).

Consequently, this augmentation in surface area facilitates better sorption characteristics in

the end product (read zeolites).

The presence of significant amount of fly ash residues after synthesis of zeolites limits

its contaminant sorption capacity (Zhang et al., 2011a). Hence, pretreatment of raw fly ash

can be employed to obtain purer zeolites as well as for synthesizing application-specific end

products. In larger particle size fractions of fly ash, i.e., >250 µm, unburnt carbon is also

present (generally, less than 20% depending on type of coal and coal-firing system), which

can be removed using sieves in order to increase its zeolitization potential, resulting in a

larger surface area (Jha et al. 2009; Itskos et al. 2010b; Visa and Chelaru 2014; Cardoso et

al., 2015a). Alternatively, calcination at elevated temperature (800 ºC) can remove unburned

carbon and other volatile compounds (Prasad et al. 2011). Furthermore, the removal of Fe2O3
5
and TiO2 using magnetic separation also enhances the zeolitic end products in terms of its

purity and structure (Lee et al. 2000; Cardoso et al., 2015a). A 6000 Gauss permanent magnet

coated with a low-porosity paper can be used to manually separate the magnetic and non-

magnetic fractions (Cardoso et al., 2015a). Interestingly, surface loading on zeolites with

species such as iron and titanium, has been reported to boost their cation exchange capacity

(Doula and Dimirkou 2008; Doula 2009; Visa et al. 2015). Washing of fly ash with water

reduces the concentration of soluble compounds such as Na2O, MgO, CaO and K2O (Wang et

al., 2009a; Visa and Chelaru 2014) and lowers the pH (which is initially >10) (Murayama et

al. 2003). In addition, acid treatment removes impurities, such as iron oxide, from raw fly

ash, yielding a higher concentration of aluminosilicates (Wang et al., 2009a; 2009b; Zhou et

al. 2014). Furthermore, the synthesized zeolites can be washed with NaCl solution to obtain

mono-cation saturated zeolite (i.e., sodium zeolite), which offers better ion exchange capacity

(Wei et al. 2013; Zhang et al., 2011b). In this context, although washing using

distilled/deionized water lowers the pH, the pH of synthesized zeolite is generally not

lowered below neutral (Jha et al. 2008). This is because drastic lowering of pH can cause

collapse of the zeolitic crystals, which is initially indicated by exfoliation of top layers of

crystals (at pH=4.2 for zeolite P), followed by entire breakdown of crystallinity (at pH=3.8

for zeolite P) and subsequent exposure of the underlying fly ash spherules (Murayama et al.

2003; Qiu and Zheng 2007). In addition, mild acid washing of the synthesized zeolite

converts calcite present in the sorbent into soluble gypsum and anhydrite, which aid

precipitation of calcium phosphate when utilized for phosphate removal (Zhang et al. 2007).

In this context, to ascertain their sustainability in acidic environment, acid resistance of the

zeolites is determined by mineralogical analysis of the acid-treated end product (Murayama et

6
al. 2003). Loading of alumina on zeolites through wet impregnation method using aluminium

chloride hexahydrate improves the adsorption characteristics (Qiu and Zheng 2007).

2. Conventional applications of fly ash zeolites

In order to reduce contaminant concentration in water to permissible limits, as demanded by

environmental regulations, several methods have been used viz., adsorption, precipitation,

coagulation, flocculation, ion exchange, reverse osmosis, biosorption and photocatalysis (Ali

and Gupta 2006; Blais et al. 2008; Ali 2010; Ali 2012; Ali et al. 2012; Ali 2014; Visa and

Chelaru 2014). Out of these, ion exchange is a popular technique, using sorbents such as

activated carbon, polymeric resins and zeolites (Ali and El‐Bishtawi 1997). In this context,

zeolites synthesized from fly ash appear to an economically viable and efficient choice as a

potential ion-exchanger. Due to the presence of innocuous exchangeable ions, zeolites have

been proven to be ideal for ion-exchange applications, such as removal of hazardous heavy

metals and radioactive ions (Hafez et al. 1978; Dyer and Keir 1984; Mimura et al. 2001;

Bosso and Enzweiler 2002; Borhade et al. 2012; Ogata et al. 2015). Furthermore, they are

excellent sorbents, owing to their highly porous microstructure containing a large number of

rigid cages and channels (Álvarez-Ayuso et al. 2003).

Generally, zeolites can be applied in various forms, viz., powder (Moreno et al. 2001),

slurry (García-Sánchez et al. 1999) and pellets (Ostroski et al. 2009) depending on the

requirement and situation. For large flowing water bodies, zeolite powder is feasible while

zeolite slurry is ideal for closed wastewater treatment system and for injection grouting for

the soil remediation. Pelletized zeolite has been applied in soil remediation and is suitable for

water treatment through a filter column and offers appropriate hydraulic conductivity along

7
with easy handling and replenishment in the reactor bed system (Gworek 1992).

2.1. Application for heavy metal removal

Heavy metals pose environmental concern due to their non-biodegradability and

bioaccumulation in humans, animals and plants, resulting in diseases and disorders (Shih and

Chang 1996; Al-Anber and Al-Anber 2008; Visa et al. 2012). Furthermore, they can kill the

bacteria responsible for decomposition of active sludge from secondary sewage treatment

plants (Visa et al. 2012). If not treated properly before discharge, effluents containing

ammonia and phosphorus can result in eutrophication of water bodies (Ji et al. 2015). Their

main sources include industries manufacturing paints, pigments, petrochemicals and battery

and effluents from metal extraction, fabrication and finishing (Ali and El‐Bishtawi 1997).

Furthermore, water from acid mine drainage contains high concentration of heavy metals

such as arsenic, chromium, copper, iron, lead, manganese, nickel and zinc in addition to

sulphate, ammonium and high total hardness and total dissolved solids with pH as low as 2

(Moreno et al. 2001; Ríos et al. 2008; Prasad and Mortimer 2011; Prasad et al. 2011). These

heavy metals reach water bodies through highway runoff (Laxen and Harrison 1977),

industrial effluents, contaminant spills (Liu et al. 2005) and water percolation through

contaminated soils (Mulligan et al. 2001) and consequently, they enter the food chain (Arora

et al. 2008).

Amongst the different sorbents, zeolites (fly ash-based zeolites, in particular) are

gaining popularity amidst researchers for heavy metal removal due to the low-cost and bulk

availability of raw material (i.e., fly ash) and also due to the presence of well-defined

molecular and porous structure, high thermal stability, ion selectivity, ion exchange capacity

8
and surface area (Petrus and Warchoł 2005; Nascimento et al. 2009). The heavy metal

removal efficiency of fly ash zeolites is much higher as compared to raw fly ash, which can

mainly be attributed to their mineralogical alteration (Kolay and Singh 2000; Kolay et al.

2001). For example, while, raw fly ash removes <8% Pb2+, its zeolitized counterpart shows

up to 98% removal (Lee et al. 2000).

From Table 2, it can be inferred that the metal uptake depends on several parameters

such as type and initial concentration of heavy metal, type of zeolite, dosage (liquid-to-solid

ratio), interaction time, temperature and pH of the system (Wang et al. 2006; Wu et al. 2008).

Different zeolites can selectively uptake heavy metals depending on their pore structures. For

example, the smaller pore size of hydroxysodalite aids Cr3+ sorption better than NaP1 due to

lack of competition from larger-sized innocuous cations such as Na+ and Ca2+ (Wu et al.

2008). Zeolites A and X, having high CEC and bigger pores (0.42 nm for A and 0.74 nm for

X), can allow heavy metals with hydrated radii less than their effective pore sizes to pass

through and can remove Cd2+, Co2+ and Zn2+ present in multi-contaminant systems (Chang

and Shih 2000; Wang et al., 2009a; Izidoro et al. 2013). Incidentally, the removal efficiency

is higher for ions with smaller hydrated radii (Visa et al., 2012). Zeolite W removes 99% of

As5+ in 5 min from a 740 ppb contaminated solution at pH=7 (Medina et al. 2010). As

observed from Table 2, the removal efficiency increases with increase in contact time due to

greater interaction between contaminant and sorbent (Wang et al. 2006). It has been reported

by few researchers that Pb2+ reached equilibrium in 25 min whereas Cr3+ required 4 h (Wu et

al. 2008; Visa et al. 2012). Increase in the initial concentration of the contaminant has been

observed to shift the equilibrium towards the higher sorption capacity region (Apiratikul and

Pavasant 2008). However, the systems with lower concentrations reached equilibrium faster
9
(i.e., equilibrium time gets reduced) and showed higher metal uptake (Wang et al. 2006;

Apiratikul and Pavasant 2008). This occurs due to the availability of more active exchange

sites on the surface for ion exchange with less number of adsorbate ions (Wang et al. 2006).

The increase in sorbent dosage decreases the equilibrium sorption capacities due to the

availability of more substrate for the sorbate (contaminant) to adhere on, thereby, decreasing

the sorbate population on it (Apiratikul and Pavasant 2008).

Incidentally, the sorbent characteristics and the sorption mechanism can be

understood using the kinetic models developed, which include pseudo-first order rate

equation (Lagergren 1898) and pseudo-second order rate equation (Blanchard et al. 1984; Ho

and McKay 1999; Rudzinski and Plazinski 2006). Generally, pseudo-second order kinetics is

followed in the case of sorption of most heavy metals and dye-heavy metal mixed pollutants

(Hui et al. 2005; Wang et al. 2006; El-Naggar et al. 2008; Fungaro et al. 2009; Visa and

Chelaru 2014). The rate-controlling mechanisms, which are essential for the design and

operation of full-scale batch processing plants, can be understood by analyzing the

experimental sorption data using Lagergren (Lagergren 1898), Ho and Mckay (Ho and

McKay 1999) and Morris-Weber (Weber and Morris 1962) models. For example, the rate

limiting steps for Cd2+ and Pb2+ are external mass transfer and intraparticle diffusion while

that of Cu2+ is governed by intraparticle diffusion (Apiratikul and Pavasant 2008).

Furthermore, determination of the sorption capacity of a sorbent per unit time is useful for

designing equipment and estimating the operating costs of effluent treatment facilities. In this

context, column study throws light on the transport phenomena, which takes place under

saturated conditions and is useful for determining optimum sorbent quantity and density of

packing (Hong et al. 2009; Rahman et al. 2009). Furthermore, it shows a breakthrough (i.e.,
10
excessive contaminant concentration beyond permissible limit after treatment through the

column bed) of heavy metals in the reverse order of the selectivity series (Table 3)

(Steenbruggen and Hollman 1998). However, when leachate containing suspended impurities

is passed through columns, clogging of pores can occur, resulting in large head losses (Otal et

al. 2005).

Along with the other parameters, the pH of the system also affects the performance of

contaminant-zeolite interaction and can be studied by considering a range of pH in the

sorption experiments which is generally adjusted by addition of appropriate concentration

and volume of acids (viz., HCl or HNO3) or alkalis (NaOH or Na-acetate) (Qiu and Zheng

2007; Apiratikul and Pavasant 2008). Some zeolites have negative surface charge at pH>3

(i.e., the point of zero charge (PZC) is less than 3), indicating its application as a potential

sorbent of cations (like heavy metals) for pH>3 (Apiratikul and Pavasant 2008). At higher

pH, lesser number of H+ ions competes for cation exchange sites thereby allowing cation

exchange of other ions, viz., heavy metals and ammonium (Juan et al. 2009). Generally, at

high pH (i.e., ~10), the uptake (immobilization) of heavy metals by zeolites is reported to be

higher than its CEC (Steenbruggen and Hollman 1998). This is due to the precipitation of

hydroxides from the solution in addition to the cation exchange taking place in zeolitic matrix

(Steenbruggen and Hollman 1998; Ríos et al. 2008; Sui et al. 2008; Deng and Ge 2015). The

preferential uptake (i.e., ion selectivity) of certain heavy metals, such as copper and iron, is

due to their lower precipitation pH (Dean et al. 1972, Jha et al. 2008). At pH>7, zinc

precipitates while it gets adsorbed on the zeolite at lower pH (Hong et al. 2009).

Nevertheless, precipitation reaction is not preferred at times, due to sludge generation (i.e.,

the undesirable precipitate formation), which further demands supplementary

11
treatment/removal (Visa et al. 2012). Generation of sludge with low settling and dewatering

characteristics will hinder large-scale treatment process (Zhang et al., 2011c). In order to

prevent precipitation, the pH of the solution can be lowered through acidification (Qiu and

Zheng 2009). However, for large scale treatment of effluents, addition of acid is dangerous,

difficult and costly and may even destroy the zeolite structure.

2.2. Application for textile effluent treatment (dye removal)

The effluents discharged from textile industries include dyes, hazardous and toxic metals,

suspended solids, pathogenic microorganisms and biodegradable organic compounds, which

are capable of harmfully affecting the ecosystem of water bodies (Wang et al., 2009b). These

colored textile effluents having varying pH, high chemical oxygen demand, temperature and

suspended oils, reduce light permeability, thereby, affecting photosynthesis (Visa and

Chelaru 2014). Table 4 shows the utilization of fly ash zeolites for dye removal. Fly ash

treated with NaOH and the surfactant hexadecyltrimethylammonium bromide (HTAB), when

interacted with bi-pollutant solutions having methylene blue along with either Cd2+ or Cu2+,

exhibited dye removal capacity of 1.6 mg/g and 1.7 mg/g, respectively (Visa and Chelaru

2014). Incidentally, pseudo second-order kinetics best fits the experimental data in

simultaneous sorption of dyes and heavy metals on surfactant modified zeolites (Wang et al.,

2009b; Visa et al. 2015). Both Langmuir and Freundlich isotherms have been opined to

describe methylene blue and on fly ash and its derived zeolites (Fungaro et al. 2009; Wang et

al., 2009b; Sun et al. 2010; Atun et al. 2011) while Langmuir best described indigo carmine

adsorption on hydroxysodalite (de Carvalho et al. 2011). The adsorption of methylene blue

on fly ash based NaP1 zeolite is an exothermic reaction and spontaneous in nature. It attains a

constant value for pH ranging from 5 to 10 due to ion exchange on pH independent sites and
12
reaches equilibrium in 10 min (Fungaro et al. 2009). The maximum adsorption of acid

fuchsin dye, on fly ash based zeolite LTA-Z has been reported at pH=5 and is endothermic in

nature (Xu et al. 2014). Interestingly, in dye sorption, there could be an initial competition in

adsorption between water and dye molecules, resulting in a two-step isotherm showing two

plateaus (Atun et al. 2011). In hydroxysodalite, methylene blue sorption takes place only on

the surface since these large dye molecules are unable to enter the small channels, thus

underutilizing the cation exchange capacity of the zeolite (Woolard et al. 2002). Similarly,

safranine, possessing larger size as compared to thionine molecule, shows lower adsorption

on the zeolitic porous surfaces (Atun et al. 2011). While it is evident that the metal uptake is

relatively high for fly ash zeolites with higher surface area, large-sized dye molecules cannot

enter the smaller pores of the zeolites, thus leaving the ion exchange sites underutilized.

2.3. Application for leachate and sewage effluent treatment

Municipal solid waste (MSW) landfill leachate, domestic wastewater, swinewater, dairy

soiled water and dairy cattle slurry have high biological and chemical oxygen demand (BOD

and COD) along with a large amount of ammonium and suspended solids (Chen et al. 2012;

Murnane et al. 2015). Ammonia remains as a long-term pollutant in the methanogenic phase

of decomposition and hence, its concentration has to be lowered (Otal et al. 2005).

Furthermore, due to unregulated disposal of hazardous and toxic waste, presence of heavy

metals has also been reported (Mohan and Gandhimathi 2009). Zeolites NaP1, analcime and

chabazite, synthesized from Spanish fly ash (60% zeolitic content, CEC=270 meq/100g),

have been employed as a decantation-assisting reagent in landfill leachate treatment. When

these are used along with a coagulant and a flocculant, reduction of 53% ammonium, 82%

13
suspended solids and 43% COD have been reported (Luna et al. 2007). Interestingly, when

MSW leachate was water-diluted to 10% and filtered, a decline has been observed in BOD,

COD and total kjeldahl nitrogen (TKN) by 18%, 12% and 38%, respectively. In some cases,

compared to synthetic zeolites, zeolitized fly ash exhibit better treatment efficiencies for

wastewater although insignificant reduction in COD has also been reported (Otal et al. 2005).

Fly ash zeolites have also been used for removal of ionic species such as ammonium,

phosphate and sulphates (Tables 5 and 6). In this context, in order to facilitate the removal of

negatively charged species, the polarity of zeolites can be modified using surfactant

compounds such as HTAB (Doula and Dimirkou 2008; Doula 2009; Visa et al. 2015; Visa

and Chelaru 2014). Different anionic species are present in water depending on its source,

i.e., acid mine drainage contains sulphate (Somerset et al. 2005) while sewage wastewater has

high concentrations of ammonium and phosphate (Chen et al. 2006; Zhang et al. 2007;

Cardoso et al., 2015b).

Domestic wastewater contains almost several folds more ammonium content as

compared to phosphate (N/P=5 in China) (Zhang et al. 2007). Ammonium is also present in

acid mine drainage along with other heavy metals (Ríos et al. 2008). Its taste threshold in

water is 35 mg/l while its odour limit is 1.5 mg/l (USEPA 2009). The presence of ammonia

gas in water, which is toxic for aquatic life, depends on the pH and temperature conditions. A

pH range of 5.5 to 10.5 has been reported to be optimum for ammonium removal (Zhang et

al. 2007). However, at high pH (pH>8), the ammonium ions in the solution get volatilized to

ammonia gas, resulting in possible overestimation of ammonium removal (Emerson et al.

2011; Zhang et al., 2011a; 2011b). Furthermore, the presence of other cations and anions

interfere with ammonium removal due to competitive sorption, with the order of influence of
14
cations: K+>Ca2+>Na+>Mg2+ and that of anions: CO32ˉ>Clˉ>SO42ˉ (Zhang et al., 2011a;

Cardoso et al., 2015b). Also, higher concentration and double charge of Ca2+, Mg2+ and Sr2+,

if present in wastewater, can lead to their preferential sorption, hence, reducing NH4+

retention. However, this does not pose much concern in fly ash zeolites since they inherently

contain oxides of Ca and Na, which tend to leach out (Juan et al. 2009; Cardoso et al.,

2015b). In swine wastewater treatment, the ammonium removal efficiency and the final pH

have been reported to decrease at higher concentrations due to the presence of multi-

contaminants in the system (Cardoso et al., 2015b). Incidentally, low-calcium fly ash based

zeolites show better ammonium removal capacities since high-calcium fly ash based zeolites

show Ca2+ leaching and have lower zeolitic content (Zhang et al., 2011a; 2011b).

Incidentally, the lower sorption capacity can be addressed, to some extent, by suitable

modification of the zeolite using mild acid (such as 0.01 mol/L H2SO4), which alters the

sparingly soluble calcite into soluble gypsum and anhydrite, thus favoring precipitation of

calcium phosphate (Chen et al. 2006). However, it should be noted that high concentration of

acid destroys the zeolitic structure, removes Al3+, Ca2+, Fe2+ and Mg2+ and lowers CEC

(Zhang et al. 2007). The adsorption kinetics has been reported to follow Langmuir,

Freundlich and Ho’s pseudo second-order models. However, best fit has been obtained using

Langmuir model for low-calcium fly ash zeolite and Freundlich for high-calcium fly ash

zeolite (Zhang et al., 2011b).

Phosphate immobilization capacity (PIC) of raw fly ash (around 52 mg/g) gets

augmented several folds upon alkali activation (Zhang et al., 2011c) and by saturation of Na-

zeolite with Ca2+ (Chen et al. 2006). PIC has been observed to be higher for zeolites

synthesized from high-calcium fly ashes where free CaO is the major contributor to
15
phosphate removal (Chen et al. 2006). Favorable pH for removal is 3.5 to 9 for zeolites from

fly ash having high calcium and 3.5 to 5.5 for fly ashes with low calcium (Chen et al. 2006)

and, in general, an optimum value of 7 is adopted (Zhang et al., 2011c; Ji et al. 2014).

Incidentally, iron modified zeolite (whose synthesis does not generate waste alkaline

solution) shows high PIC due to ligand exchange with Fe-based compounds (Chen et al.

2006; Xie et al. 2014). Ji et al. (2014) have used a 4:1 mixture of low- and high-calcium fly

ash based zeolites for removal of over 40% of both ammonia and phosphate (dosage=4g/l,

pH=7.5). The authors have opined that, in sewage treatment, these two types of fly ashes

should be applied one after the other for better efficiency (Ji et al. 2014). A zeolite with

CEC=279 meq/100g has shown PIC=12.98 mg/g while PIC=87.51 mg/g has been observed

for zeolite with CEC=69 meq/100g (Ji et al. 2014). Due to the presence of bivalent cations,

viz., Ca2+ and Mg2+, PIC is enhanced in seawater compared to pure water (Guan et al. 2009).

Langmuir model best fits the phosphate adsorption kinetics (Zhang et al., 2011c).

2.4. Other applications

Fly ash zeolites have been successfully used for treating lignite minewater (Itskos et al. 2015)

and for reducing hardness wherein 72% reduction has been reported for minewater treated

with 40 g/l (solid-to-liquid ratio) of fly ash zeolite (Prasad et al. 2011). In addition, soils with

heavy metal spillage when treated with zeolite (viz., NaP1 with CEC=200 meq/100g), along

with phytoremediation, have shown over 95% decrease in concentrations of Cd2+, Co2+, Cu2+,

Ni2+ and Zn2+ (dosage = 250 ton/ha) (Querol et al. 2006). Radionuclide, viz., 133Cs+, has

been immobilized by containment in a fly ash geopolymer through geopolymerization

reactions, forming a solid block with compressive strength of 30 MPa (Li et al. 2013). The
16
sulphuric acid mist generated in lead-battery manufacturing plants has been removed using

zeolites synthesized from fly ash activated using NaOH and CaO (Shu et al. 2015). Due to

their thermal stability, non-flammability, non-degradability and sorption characteristics,

zeolites can act as excellent sorbents of water in dehydration applications (Panitchakarn et al.

2014) and volatile organic compounds (VOCs) such as benzene, chlorofluorocarbons,

formaldehyde and methylene chloride, which pose health risks and harm the environment

(Rayalu et al. 2006; Zhou et al. 2014). Benzene vapor has been removed using NaP1 (69.2%

zeolite with SSA=22.08 m2/g) and Na-A (66.5% zeolite with SSA=39.28 m2/g) (Wei et al.

2013; Zhou et al. 2014).

2.5. Recovery of immobilized heavy metals from the spent zeolites

The recovery of contaminants and regeneration of spent sorbents (read zeolites) are useful to

make the water treatment processes economically viable and sustainable (Wang et al.,

2009a). NaCl solution can be used to recover heavy metals and ammonium adsorbed by

zeolites, to an extent (Steenbruggen and Hollman 1998; Wang et al., 2009a; Zhang et al.,

2011a). However, when leached with deionized or distilled water, fly ash zeolites have shown

negligible desorption of both dyes and heavy metals (Querol et al., 2006; Visa and Chelaru

2014). Similarly, leaching of manganese-sorbed zeolites using ammonium acetate followed

by acetic acid has shown negligible recovery of the heavy metal (Belviso et al. 2014). In this

context, it has been shown that regenerated zeolites show a decrease in its sorption capacity

due to the partial disintegration of its structure (Chunfeng et al., 2009).

3. Novel dimensions in zeolite applications

17
Apart from the conventional applications for water treatment, fly ash zeolites are now finding

applications for remediation of contaminated soils in the form of permeable reactive barriers

and liners and as backfill material in radioactive contaminant disposal sites (Ibrahim et al.

2008; Regmi et al. 2009; Indraratna et al. 2014; Du et al. 2015).

3.1. Application as permeable reactive barrier (PRB)

Spills or discharges of contaminants (leachates and hazardous compounds) in soil migrate

due to rainwater percolation, resulting in groundwater and surface water contamination (Erto

et al. 2011). In this context, permeable reactive barriers (PRBs) offer in-situ remediation at

low operating and maintenance costs (Regmi et al. 2009; Erto et al. 2011; Indraratna et al.

2014). Fig. 3 shows the conceptualization of PRB for treatment of a contaminant plume in the

soil. In a PRB, the reactive media (such as activated charcoal, exchange resin and zeolite)

should have hydraulic conductivity greater than the surrounding media, i.e., the soils, in order

to allow the flow of the contaminant plume through the barrier under natural hydraulic

gradient (Erto et al. 2011). Interestingly, a soil-natural zeolite layering technique has also

been used for treatment of polluted river water (Boonsook et al. 2003; Masunaga et al. 2003)

and this methodology has the potential to be augmented using fly ash based zeolites. Czurda

and Haus (2002) have suggested that in a fly ash zeolite PRB with funnel and gate

configuration (a system of walls which channelizes the contaminant plume towards the PRB),

a secondary electrokinetic treatment, which is provided after the treatment through the PRB

has been over, can be employed for ensuring complete contaminant removal.

3.2. Application as liner

In contaminant barrier liner systems (viz., radioactive waste disposal site and
18
municipal and industrial landfills), coarser particles (commonly, sand) are mixed with

bentonite in order to prevent desiccation cracking (Ruhl and Daniel 1997). However, such

materials added to compacted clays should ensure geotechnical stability and low hydraulic

conductivity (k≤10-9 m/s) (Hong et al. 2011). Hence, sorbents such as fly ash, natural zeolites

and fly ash zeolites have been investigated for their potential as additives in bentonite (Kaya

and Durukan 2004; Rahman et al. 2009; Çoruh and Ergun 2010; Ibrahim et al. 2008; Du et al.

2015). Practically, higher sorption capacity of the zeolites helps in reduction of liner

thickness in addition to lesser contaminant migration (Kaya and Durukan 2004).

4. Limitations

High pH (>10) in the zeolitic end product has to be lowered failing which the treated

effluent will have high pH and subsequently precipitate (Prasad et al., 2011). After zeolite

synthesis, removal of excess alkali (like NaOH or KOH) and lowering of pH, require huge

amount of water, hence adding to the production cost along with generation of highly alkaline

effluents (Moreno, 2001). Although deionized water can be used for removing excess alkali

(thereby lowering the pH), pH below 4 can lead to drastic disintegration of the zeolitic

crystals (Murayama et al., 2003). Furthermore, high pH and total dissolved solids and very

large concentrations of sodium and calcium in the treated water are current shortcomings in

using fly ash zeolites (Prasad et al., 2011).

Incidentally, leaching of hazardous elements such as Cr, Hg, Se and V from raw fly

ash has also been reported (Carlson and Adriano, 1993; Davidson and Bassett, 1993;

Steenbruggen and Hollman, 1998; Koukouzas et al. 2011a; Georgakopoulos et al. 2012).

While treating acid mine drainage water using zeolites synthesized from an Indian fly ash,

19
high leaching of chromium has been reported (Prasad and Mortimer, 2011). The type and

amount of leaching depends on the parent coal and combustion technique employed. Hence,

care should be taken to properly characterize the fly ash before applications in water

treatment (Hong et al., 2009).

5. Conclusions and future outlook

Fly ash based zeolites have been demonstrated extensively in literature to be an efficient

scavenger of hazardous and toxic cations and anions in water. Furthermore, they have the

potential in effluent treatment for removal of dyes and heavy metals and for applications such

as permeable reactive barriers and contaminant barrier liners. The contaminant removal using

zeolites takes place through sorption and/or precipitation and the removal efficiency depends

upon the pH, initial contaminant concentration and the solid to liquid ratio of the system.

Only few studies have been conducted on removal of arsenic and mercury using fly

ash zeolites and further studies using different types of zeolites would prove to be useful in

finding the ideal type of zeolite. Bacterial loading on fly ash based zeolites can be used for

heavy metal and phosphate removal, thus offering, an economically viable alternative to

existing methods. Although studies exist for landfill leachate treatment using raw fly ashes,

utilization of fly ash based zeolites could yield better results as indicated by few initial

studies. While a large number of studies have been conducted on heavy metal removal, very

few studies exist on other crucial applications such as soil remediation using permeable

reactive barriers (PRBs) and contaminant containment using zeolite-based liners. Despite

studies on PRBs using natural and commercial zeolites, utilization of fly ash based zeolites

has not been explored much. For containment of hazardous, toxic and radioactive waste,

20
feasibility of liner materials using bentonite-embedded fly ash zeolites can be investigated. In

addition, in situ remediation studies would be quite useful to understand the effectiveness of

this material in large-scale resource recovery technologies.

21
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45
List of Figures

Applications
AMD
Anions
Dye
Heavy metal
PRB and Liners
Wastewater
VOC

Fig. 1. Locations of fly ashes that have been zeolitized and characterized for water treatment
applications

46
Fig. 2. Scanning electron micrographs showing rod/needle shaped zeolites synthesized from
fly ash

47
Fig. 3. Conceptualization of a permeable reactive barrier (PRB)

48
 Table 1. Some common zeolites synthesized from fly ash
Zeolite Chemical formula References

Analcime NaAlSi2O6·H2O. Remy and Ferrell (1989)

Cancrinite Na6Ca2Al6Si6O24(CO3)2·2H2O Qiu and Zheng, 2009

Chabazite (Ca,Na2,K2,Mg)Al2Si4O12·6H2O Dêdêcêk et al. (2009)

Clinoptilolite (Na,K,Ca)2-3Al3(Al,Si)2Si13O36·12H2O Zabochnicka-Świątek and Malińska (2010)

Hydroxy-sodalite Na1.08Al2Si1.68O7.44·1.8H2O Ahmaruzzaman (2010)

Mordenite (Ca, Na2, K2)Al2Si10O24·7H2O Sasaki et al. (2003)

Na-A Na12Al12Si12O48·24H2O Qiu and Zheng, 2009

Na-P1 Na6Al4Si4O24·4H2O Qiu and Zheng, 2009

Na-Y Na58Al58Si134O384·260H2O Qiu and Zheng, 2009

Scolecite Ca2Al2Si3O10·3H2O Qiu and Zheng, 2009

Phillipsite (Ca,Na2,K2)3Al6Si10O32·12H2O Hay (1966)

Zeolite A NaAlSi1.1O4.2·2.25H2O Ahmaruzzaman (2010)

Zeolite X NaAlSi1.23O4.46·3.07H2O Ahmaruzzaman (2010)

Zeolite Y NaAlSi2.43O6.86·4.46H2O Ahmaruzzaman (2010)

49
 Table 2. Metal uptake characteristics of various fly ash based zeolites

Zeolite Operating conditions

Ionic Fly ash CEC η q
Zeolite a SiO2/ t T Ci Dosage Reference
species source (meq/100g) (%) (mg/g) pH
Al2O3 (min) (ºC) (mg/l) (g/ml)

Brazil 290 100 3.3 30 0.04 0.01 Cardoso et al. (2015a)

Na-P1
As5+ Spain 270 99.16 0.955 0.03 Querol et al. (2002)

W Mexico 99 7 5 25 0.74 0.01 Medina et al. (2010)

A South Africa 1.764 105 99.9 2h/24h 0.2

Koukouzas et al. (2010)
Erionite, Linde, ZSM-18 Poland 2.146 120 99.9 2h/24h 0.2

60 156.2 10.2 120 515 0.002

Na-al Romania Visa and Chelaru (2014)
Cd2+ 60 87.7 10.2 120 515 0.003

Brazil 290 94.09 3.3 30 0.22 0.01 Cardoso et al. (2015a)

Na-P1 Spain 270 100 0.186 0.03 Querol et al. (2002)

South Korea 1.22 85 117.5 25 0.0001 Lee et al. (2000)

50
 1.18 228.7 98.94 4.6 0.002 0.08
Na-P1, FAU, CHA UK Prasad and Mortimer (2011)
1.49 283.3 96.64 4.6 0.002 0.08

PHI Greece 2.47 98 1.55 60 20 1000 0.02 Itskos et al. (2015)

PHI, CLI Romania 30.2 90 0.013 Visa et al. (2012)

THO Greece 3.19 79 1.55 60 20 1000 0.02 Itskos et al. (2015)

Brazil 310 92.4 24h 1124.1 0.01 Izidoro et al. (2013)

X 140 97.8 120 21 1 Apiratikul and Pavasant

Thailand
140 90.9 120 21 1 (2008)

32.75 14.5 3 240 25 200 0.005

4A China Hui et al. (2005)
2+
Co 22.22 13.5 3 240 25 300 0.005

Na-P1 Spain 270 68.57 0.751 0.03 Querol et al. (2002)

China 1.2 560 38 3 25 200 Wang et al. (2009a)

A
South Africa 1.764 105 99.9 2h/24h 0.2 Koukouzas et al. (2010)
Cu2+
98.42 40.1 3 240 25 200 0.005
4A China Hui et al. (2005)
89.57 49.9 3 240 25 300 0.005

51
 Erionite, Linde, ZSM-18 Poland 2.146 120 100 2h/24h 0.2 Koukouzas et al. (2010)

71 119.1 10.2 120 350 0.002

Na-al Romania Visa and Chelaru (2014)
71 56.5 10.2 120 350 0.003

42 30 0.0005
Australia Wang et al. (2006)
80 64 40 0.0005

1.8 3.4 240 20

Na-P1 China Wu et al. (2008)
9 3.4 240 20

Spain 270 9.44 36 0.03 Querol et al. (2002)

South Korea 1.22 89 73.5 25 0 Lee et al. (2000)

1.18 228.7 84.24 4.6 0.053 0.08

Na-P1, FAU, CHA UK Prasad and Mortimer (2011)
1.49 283.3 84.95 4.6 0.053 0.08

PHI Greece 2.47 100 1.55 60 20 1000 0.02 Itskos et al. (2015)

THO Greece 3.19 98 1.55 60 20 1000 0.02 Itskos et al. (2015)

X China 1.31 500 28.9 3 25 200 Wang et al. (2009a)

Cr3+ A South Africa 1.764 105 100 2h/24h 0.2 Koukouzas et al. (2010)

52
 87.33 35.6 3 240 25 200 0.005
4A China Hui et al. (2005)
73.52 41.6 3 240 25 300 0.005

Erionite, Linde, ZSM-18 Poland 2.146 120 100 2h/24h 0.2 Koukouzas et al. (2010)

HS, Na-P1 China 32.2 3.4 240 20 Wu et al. (2008)

1.18 228.7 82.8 4.6 2.152 0.08

Na-P1, FAU, CHA UK Prasad and Mortimer (2011)
1.49 283.3 90.38 4.6 2.151 0.08

PHI Greece 2.47 100 1.55 60 20 1000 0.02 Itskos et al. (2015)

THO Greece 3.19 100 1.55 60 20 1000 0.02 Itskos et al. (2015)

290 97.47 3.3 30 5.62 0.01

Brazil Cardoso et al. (2015a)
2+
Fe Na-P1 290 99.87 3.3 30 4.64 0.01

Spain 270 99.25 444 0.03 Querol et al. (2002)

0.47
FAU, SOD, A South Africa 75.81 30 2.64 Somerset et al. (2008)
Hg2+ µg/kg

X, A, SOD Italy 125 99.65 5 10 0.1 Belviso et al. (2014)

Mn2+ Na-P1 Australia 28 30 0.0005 Wang et al. (2006)

53
 Brazil 290 93.33 3.3 30 0.06 0.01 Cardoso et al. (2015a)

Spain 270 63.63 11 0.03 Querol et al. (2002)

1.18 228.7 86.76 4.6 19.544 0.08

Na-P1, FAU, CHA UK Prasad and Mortimer (2011)
1.49 283.3 74.75 4.6 19.544 0.08

A South Africa 1.764 105 99.9 2h/24h 0.2 Koukouzas et al. (2010)

21.06 9.5 3 240 25 200 0.005

4A China Hui et al. (2005)
14.01 8.8 3 240 25 300 0.005

Erionite, Linde, ZSM-18 Poland 2.146 120 100 2h/24h 0.2 Koukouzas et al. (2010)

Australia 65.8 40 0.0005 Wang et al. (2006)

Na-P1
Ni2+ Spain 270 40.5 0.316 0.03 Querol et al. (2002)

1.18 228.7 48.28 4.6 0.52 0.08

Na-P1, FAU, CHA UK Prasad and Mortimer (2011)
1.49 283.3 25.59 4.6 0.52 0.08

PHI Greece 2.47 48 1.55 60 20 1000 0.02 Itskos et al. (2015)

PHI, CLI Romania 2000 25 0.005 Visa et al. (2012)

THO Greece 3.19 52 1.55 60 20 1000 0.02 Itskos et al. (2015)

54
 A South Africa 1.764 105 99.9 2h/24h 0.2
Koukouzas et al. (2010)
Erionite, Linde, ZSM-18 Poland 2.146 120 100 2h/24h 0.2

3.23
FAU, SOD, A South Africa 75.81 95 2.64 Somerset et al. (2008)
µg/kg

South Korea 1.22 98 266.4 25 0.41 0.0001 Lee et al. (2000)

Na-P1
Spain 270 100 240 0.03 Querol et al. (2002)
Pb2+
1.18 228.7 55.44 4.6 1.26 0.08
Na-P1, FAU, CHA UK Prasad and Mortimer (2011)
1.49 283.3 50.07 4.6 1.26 0.08

PHI Greece 2.47 100 1.55 60 20 1000 0.02 Itskos et al. (2015)

THO Greece 3.19 100 1.55 60 20 1000 0.02 Itskos et al. (2015)

Apiratikul and Pavasant

X Thailand 140 420.6 120 21 1
(2008)

Na-P1, FAU, CHA UK 1.18 228.7 98.77 4.6 0.647 0.08 Prasad and Mortimer (2011)
Sr2+
PHI, CLI Romania 18.9 90 0.013 Visa et al. (2012)

China 1.2 560 29.7 3 25 200 Wang et al. (2009a)

Zn2+ A
South Africa 1.764 105 100 2h/24h 0.2 Koukouzas et al. (2010)

55
 62.57 100
A, ANA, PHI, HC Brazil Nascimento et al. (2009)
57.2 100

66.42 30.6 3 240 25 200 0.005

4A China Hui et al. (2005)
42.17 27 3 240 25 300 0.005

Erionite, Linde, ZSM-18 Poland 2.146 120 100 2h/24h 0.2 Koukouzas et al. (2010)

Brazil 290 80.76 3.3 30 0.13 0.01 Cardoso et al. (2015a)

Na-P1 Spain 270 94.4 54 0.03 Querol et al. (2002)

South Korea 1.22 65 65.8 25 0.0001 Lee et al. (2000)

Na-P1, FAU, CHA UK 1.49 283.3 98.02 4.6 0.646 0.08 Prasad and Mortimer (2011)

PHI Greece 2.47 95 1.55 60 20 1000 0.02 Itskos et al. (2015)

THO Greece 3.19 60 1.55 60 20 1000 0.02 Itskos et al. (2015)

X China 1.31 500 22.4 3 25 200 Wang et al. (2009a)

a
ANA - analcime, CHA - chabazite, CLI - clinoptilolite, FAU - faujasite, HC - hydroxycancrinite, Na-al - Na-aluminosilicate, PHI - phillipsite, THO -
thomsonite

56
 Table 3. Heavy metal selectivity series of fly ash zeolites

CEC
a Fly ash
Zeolite (meq/100 Selectivity series Reference
source
g)
A, ANA, PHI, Brazil Pb2+>Cu2+>Zn2+≥Mn2+ Nascimento et al. (2009)
HC
4A China Cu2+>Cr3+>Zn2+>Co2+>Ni2+ Hui et al. (2005)
CAN Canada Pb2+>Cu2+>Ni2+> Qiu and Zheng (2009)
2+ 5+ 2+ 2+ 2+ 2+
FAU UK Fe >As >Pb >Zn >Cu >Ni > Ríos et al. (2008)
Cr2+
Brazil 290 As5+>Mn2+>Fe2+>Cu2+>Ni2+>Zn2+ Cardoso et al. (2015a)
Spain 270 Fe3+≥Cu2+≥Pb2+≥Cd2+>Zn2+>Mn2+ Moreno et al. (2001)
>Sr2+
Na-P1
South Korea Pb >Cu2+>Cd2+>Zn2+
2+
Lee et al. (2000)
The 240 Ba >Cu >Cd ≈Zn >Co>Ni Steenbruggen and Hollman
2+ 2+ 2+ 2+ 2+

Netherlands (1998)
PHI, CLI Romania Pb >Zn ≥Cd
2+ 2+ 2+
Visa et al. (2012)
SOD India Pb2+>Cd2+>Zn2+ Borhade et al. (2012)
2+ 2+ 2+
X Thailand 140 Pb >Cu >Cd Apiratikul and Pavasant
(2008)
2+ 2+ 2+ 2+
X, FAU Japan Pb >Cu >Cd >Ni Jha et al. (2008)
a
ANA - analcime, CAN - cancrinite, CLI - clinoptilolite, FAU - faujasite, HC -
hydroxycancrinite, PHI - phillipsite, SOD - sodalite

57
 Table 4. Dye removal using fly ash zeolites

SSA q t T Dosage
Fly ash
Dye Zeolite a pH Reference
source
(m2/g) (x10-5 mol/g) (h) (ºC) (g/ml)

Alizarin
HS South Africa 7.4 0.713 4 0.01 Woolard et al. (2002)
sulfonate

A China 25.98 30 Wang et al. (2009b)

HS South Africa 7.4 3.383 4 0.01 Woolard et al. (2002)

3
Methylene blue 24 4.46
d
Na-P1 Australia Wang et al. (2006)
3
25.7 5.32
d

X China 35.42 30 Wang et al. (2009b)

3
Rhodamine B Na-P1 Australia 25.7 0.398 Wang et al. (2006)
d

Na-P1, Y, X, SOD,
27.4 3 6.34 1 45 0.01
ANA

Safranine SOD, ANA Turkey 29.4 1.5 6.34 1 25 0.01

X, SOD 28.5 1.8 6.34 1 45 0.01

Atun et al. (2011)
Na-P1, Y, X, SOD,
27.4 3 6.39 1 45 0.01
ANA

Thionine SOD, ANA Turkey 29.4 4.25 6.39 1 25 0.01

X, SOD 28.5 3.6 6.39 1 25 0.01

a
ANA - analcime, HS - hydroxysodalite, SOD - sodalite

58
Table 5. Removal of ammonium using fly ash zeolites

Operating conditions
Fly ash SiO2/ SSA CEC η q
Zeolite a t T Ci Dosage pHe Reference
source Al2O3 (m2/g) (meq/100g) (%) (mg/g) pH
(min) (ºC) (mg/l) (g/ml)
2.54 8 25 100 0.004
GIS China 2.62 45.511 69 4.8 8 25 7.3 0.004 Zhang et al. (2011b)
8.5 25 10 0.004
137 76 2.52 7.7 30 25 52.2 0.02 9.2
K-F Spain Juan et al. (2009)
110 66 1.62 7.7 144 25 52.2 0.02
85 74 1.44 7.7 30 25 52.2 0.02 8.7
K-PHI, K-CHA Spain Juan et al. (2009)
115 71 1.8 7.7 144 25 52.2 0.02
290 28.1 3.3 30 9.6 0.010 Cardoso et al. (2015a)
52 31 5.7 30 25 1205 0.02 7.11
Brazil 59 17 30 25 578 0.02 8.05
280 Cardoso et al. (2015b)
81 14 30 25 340 0.02 9.3
70 4 30 25 125 0.02 10.7
Na-P1
131 76 2.34 7.7 30 25 52.2 0.02 8
Spain Juan et al. (2009)
99 71 1.8 7.7 144 25 52.2 0.02
1.82 213 24h 0.01
Zhang et al. (2007)
China 1.91 175 60 24h 10 0.01 10.08
1.56 161.5 154.3 70 4.5 7.5 25 25 0.005 Xie et al. (2014)
Na-P1, ANA, CHA Spain 56.7 5.24 30 245 0.03 8.11 Otal et al. (2005)
Na-P1, FAU, CHA India 1.49 283.3 19.57 1 485 0.01 Prasad et al. (2011)
47.7 17.77 8 75 25 152.6 0.004
48 23.89 8 75 25 50 0.004 Zhang et al. (2011a)
Zeolite X with small
15.7 8 35 0.004
amounts of A, P and China 3.34 27.015 279
18.19 8 25 100 0.004
HS
51.1 8 25 7.3 0.004 Zhang et al. (2011b)
74.6 25 10 0.004
a
ANA - analcime, CHA - chabazite, FAU - faujasite, GIS – gismondine, HS - hydroxysodalite, PHI – phillipsite

59
Table 6. Removal of anions using fly ash zeolites

Operating conditions
Fly ash SiO2/ SSA CEC η q
Anion Zeolite a t T Ci Dosage Reference
source Al2O3 (m2/g) (meq/100g) (%) (mg/g) pH
(min) (ºC) (mg/l) (g/ml)
Chloride Na-P1 Brazil 290 48.38 3.3 30 12.4 0.01 Cardoso et al. (2015a)
Fluoride Na-P1 Brazil 290 75 3.3 30 1.2 0.01 Cardoso et al. (2015a)
Nitrate Na-P1 Brazil 290 52.63 3.3 30 3.8 0.01 Cardoso et al. (2015a)
102.9 30 0.0125
56.28 94 7 28h 30 167.87 1
GIS China 2.62 45.511 69 Zhang et al. (2011c)
156.36 7 28h 40 1
184.17 7 28h 50 1
91.49 103 42.2 24h 1000 Chen et al. (2006)
HS China
90.84 101 47.17 24h 1000 0.0187
1.82 213 38.26 24h 0.01
Phosphate
62.77 5.31 24h 0.01 Zhang et al. (2007)
1.91 175
95 5.52 24h 12
Na-P1 China
1.56 161.5 154.3 18.2 24h 25 0.005 Xie et al. (2014)
213 34.68 Wu et al. (2006)
57.68 208.9 40.85 24h 1000 Chen et al. (2006)
Na-P1, ANA, CHA Spain 91 5.24 30 25000 0.03 Otal et al. (2005)
Na-P1, SOD Thailand 3.57 35.38 188 57.14 24h 15000 0.01 Pengthamkeerati et al. (2008)
Sulphate Na-P1 Brazil 290 84.97 3.3 30 406 0.01 Cardoso et al. (2015a)
a
ANA - analcime, CHA - chabazite, GIS - gismondine, SOD - sodalite

60