Chemical Engineering Journal 317 (2017) 821843

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Chemical Engineering Journal

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Review

Synthesis of nanoporous materials via recycling coal fly ash and other
solid wastes: A mini review
Yu-Ri Lee a, June Thet Soe a, Siqian Zhang a, Ji-Whan Ahn b, Min Bum Park c, Wha-Seung Ahn a,
a
Department of Chemistry and Chemical Engineering, Inha University, Incheon 22212, Republic of Korea
b
Korea Institute of Geoscience and Mineral Resources (KIGAM), 92 Gwahang-no, Yuseong-gu, Daejeon 305-350, Republic of Korea
c
Department of Energy and Chemical Engineering, Incheon National University, Incheon 22012, Republic of Korea

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Physicochemical pre-treatment of fly

ash for nanoporous materials
synthesis.

Synthesis of zeolites, mesoporous
silica, and silica aerogel/foam from fly
ash.

Synthesis of nanoporous materials
using solid wastes as silica and/or
alumina sources.

Applications of the synthesized
nanoporous materials via fly ash
recycling for sustainability.

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

Article history: Large quantities of fly ash are discharged as a by-product from coal power plants. Therefore, an effective
Received 18 December 2016 method to recycle this waste material is necessary. In this regard, the high silica content of fly ash makes
Received in revised form 21 February 2017 it a potential useful source for the synthesis of nanoporous materials, such as zeolites, mesoporous silica
Accepted 22 February 2017
or silica aerogels. In this mini review, zeolite synthesis from fly ash was examined by considering the ash
Available online 24 February 2017
composition, pretreatment procedures, and hydrothermal synthesis conditions (substrate composition
and synthesis temperature/time) to identify an optimal set of synthesis conditions. These zeolites can
Keywords:
be used as adsorbents and ion-exchangers for environmentally hazardous materials including those pre-
Fly ash
Recycling
sent in the fly ash itself. The synthesis of mesoporous silica materials with a high surface area and large
Zeolites pore volume derived from fly ash was next assessed for their use as a support and as a surface-
Mesoporous materials functionalized host for capturing the global warming CO2 and rare earth metal ions. Lastly, the utilization
Aerogel of fly ash for the preparation of silica aerogels or adiabatic foams, which are being considered as a poten-
Adiabatic foam tial building insulation materials, was briefly examined. Cases of synthesizing these nanoporous materi-
als using other solid wastes as silica and/or alumina sources were also examined. The synthesis of diverse
porous materials utilizing the waste sources would enable a high level of recycling for a sustainable soci-
ety with a low environmental burden.
2017 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 822
2. Characterization of fly ash and other solid waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 822

Corresponding author.
E-mail address: whasahn@inha.ac.kr (W.-S. Ahn).

http://dx.doi.org/10.1016/j.cej.2017.02.124
1385-8947/ 2017 Elsevier B.V. All rights reserved.
822 Y.-R. Lee et al. / Chemical Engineering Journal 317 (2017) 821843

3. Preconditioning of fly ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 823

3.1. Acid treatment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 823
3.2. Alkali-Fusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 823
4. Zeolites synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 825
4.1. Zeolite synthesis after alkali-fusion of fly ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 826
4.2. Zeolite synthesis after aqueous NaOH/KOH digestion of fly ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 830
4.3. Zeolite synthesis using other solid wastes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 833
5. Synthesis of mesoporous materials using fly ash. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 834
6. Synthesis of silica aerogel and adiabatic foam using fly ash or other solid wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 837
7. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 840
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 840
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 840

1. Introduction
With the rapidly growing demand for energy worldwide, large
quantities of coal ash are being discharged daily as a by-product
from coal power plants. Approximately 600 million tons of coal
ash are produced annually worldwide, of which fly ash accounts
for approximately 80% [1,2]. Only 20% of the fly ash is used as an
additive for cement and concrete-related applications [24]. The
remainder is disposed of in landfill and lagoons, which causes soil
and groundwater pollution. Because fly ash is highly contaminat-
ing owing to its heavy metal content (e.g., As, Pb, Sn, Cd, etc.), it
is important to recycle it after removing the contaminants rather
than by simple reclamation [2,5,6].
Fly ash is an agglomerate of spheres or hollow spheres with a
diameter of 1100 lm and is generally grey in color, abrasive,
and mostly alkaline [1,3,7]. The main components of fly ash
are amorphous aluminosilicate glasses, mullite (2SiO23Al2O3),
a-quartz (SiO2), hematite (a-Fe2O3), and magnetite (Fe3O4). Its
high silica content with some alumina present makes it a suit-
able starting material for the synthesis of zeolites [810]. The
main applications of these synthesized zeolites can be sorbents
and ion-exchangers for the removal of ions and hazardous mole-
cules from waste water and radioactive waste, as well as adsor-
bents for gases containing atmospheric pollutants [1113].
Recently, zeolites have also been studied extensively as a captur-
ing agent for the global warming CO2 [14]. Under these circum-
stances, zeolite synthesis by recycling hazardous power plant fly
ash can be a useful option for reducing the amount of solid
waste and offering valuable products for environmental applica-
tions [15]. Further applications of these zeolites have been sug-
gested for catalysis [16,17], detergent builder [18], mine-water
treatment [19], and oil spill treatment [20]. Many studies have
examined the synthesis of zeolites X (framework type FAU)
[2137], Y (FAU) [33,38], A (LTA) [21,22,27,29,30,3335,37,394
2], P (GIS) [27,29,4355], and some others, such as ZSM-5
(MFI) [56] and phillipsite (PHI) [57], using fly ash via hydrother-
mal treatments in an alkaline environment.
In addition to zeolites, the synthesis of mesoporous silica from
coal fly ash has also attracted attention owing to its high surface
area, large pore volume, and large pore size exceeding the limita-
tions of the microporous zeolites with pore sizes less than
1.3 nm [5865]. These mesoporous materials can be used for CO2
capture [14,66,67], adsorption [68,69], and catalysis [61,65,70].
Furthermore, fly ash can be converted to sodium silicate by a liquid
phase reaction with NaOH, which can be used as a silica source for
high surface area silica aerogels that can be used for building insu-
lation [71,72], catalyst [73], and adsorbent [74] through a route
involving the surface modification of wet gels and ambient pres-
sure drying [7577]. Sodium silicate can also be mixed with
acid-washed fly ash as an additive to produce adiabatic foams with
sufficient compression strength for use in insulation.
Several other solid wastes have also been considered as a silica
source for zeolite synthesis [71,7594]. A close inspection of the
data from the literature suggests that the chemical composition
of silica and alumina in fly ash and other solid wastes is signifi-
cantly different. In addition, the synthesis conditions, including
the pretreatment conditions, are often not specified clearly or there
are some inconsistencies among the literature sources.
This review systematically examines the synthesis of various
zeolites derived from fly ash by considering the fly ash/solid waste
properties, pretreatment protocols, and hydrothermal synthesis
conditions, including the synthesis temperature, time, and sub-
strate concentrations to identify an optimal set of synthesis condi-
tions. The cases of synthesizing mesoporous materials and lesser
known silica aerogels and adiabatic foam using fly ash are also
included to provide an overview for the diverse options available
for recycling silica-containing waste materials in preparing a range
of nanoporous materials.
2. Characterization of fly ash and other solid waste
The major chemical constituents and properties of coal fly ash
are influenced by the properties of coal burned (anthracite, bitu-
minuous, sub-bituminuous, and lignite), combustion method, and
heating and cooling regimes in the coal boiler [95]. Quartz and
mullite are the major crystalline compounds found in low calcium
fly ash, whereas high calcium-containing fly ash consists of quartz,
tricalcium aluminate, calcium silicate, and tetracalcium alumi-
nosilicate [1]. Steenari et al. reported that the chemical and leach-
ing characteristics of the fly ash must be known before ash residue
can be used or deposited [96]. Table 1 lists the chemical composi-
tion of the oxide forms of different fly ash sources reported in the
literature [14,25,26,28,29,3336,38,43,44,4749,52,53,61,62,64,65
,97,98]. X-ray fluorescence (XRF) has revealed the major compo-
nents of fly ash to be Si, Al, Fe, Ca, and K. Fig. 1 presents the powder
X-ray diffraction (XRD) patterns of representative raw fly ash sam-
ples [27,52,55,98]. The powder XRD patterns indicate that the
major crystalline phases in fly ash are aquartz and mullite along
with other amorphous aluminosilicates. Crystalline a quartz is
inactive and does not dissolve during zeolite synthesis. Fly ashes
usually have silica in amorphous aluminosilicate glass, quartz,
and mullite. Among them, the portion of amorphous aluminosili-
cate glass phase is the largest and most unstable under the
hydrothermal condition, which leads to the highest rate of dissolu-
tion and is the largest contributor to the synthesis of zeolites
[43,48]. Little to no reactivity was reported for quartz and mullite
[29,99]. Querol et al. [48] reported the highest synthesis yields up
to 80 wt% from fly ash with high concentration of amorphous silica,
and lower conversions attributed to both larger contents of non-
reactive phases (i.e., hematite and magnetite) and stable silica
phase of mullite and quartz in the fly ash. Therefore, raw fly ash
 Y.-R. Lee et al. / Chemical Engineering Journal 317 (2017) 821843 823

Table 1
Chemical compositions of diverse fly ash sources.

Fly ash no. Chemical composition (wt.%)a Ref.

SiO2 Al2O3 Fe2O3 TiO2 CaO MgO Na2O K2O Others
1 49.0 18.4 6.5 2.3 7.2 1.4 0.8 1.2 2.4 [14]
2 71.0 18.3 3.6 0.8 0.3 0.7 [25]
3 65.4 28.2 2.1 1.7 0.7 0.3 1.6 [26]
4 67.2 20.1 4.1 2.0 0.4 2.9 3.0
5 59.4 26.3 8.1 1.5 0.4 2.9 5.8
6 54.0 28.5 6.1 1.4 6.3 1.2 0.4 1.1 [27]
7 55.4 25.3 4.0 2.2 4.6 0.8 0.9 0.7 [28]
8 61.6 21.3 6.5 1.0 3.2 1.6 [29]
9 92.3 2.0 1.2 0.6 1.2 0.8 1.0 [33]
10 46.8 28.2 5.2 1.5 5.6 1.4 0.5 1.3 [34]
11 49.3 33.1 5.8 1.2 2.1 0.3 2.2 2.6 [35]
12 59.3 28.4 3.5 0.8 1.9 1.2 0.6 2.1 [36]
13 62.3 31.0 1.3 1.7 3.0 0.1 0.4 0.3 [38]
14 46.7 31.0 9.4 1.2 6.7 1.9 0.3 1.3 [43]
15 50.4 20.3 8.2 1.8 7.5 5.4 2.7 [44]
16 44.5 27.1 9.7 3.0 2.8 0.5 2.4 4.4 [47]
17 47.2 25.6 16.6 0.8 5.6 1.2 0.2 1.6 [48]
18 49.5 26.7 14.3 1.0 2.3 1.1 0.3 2.3
19 38.3 34.8 8.1 11.0 7.8 [49]
20 55.2 36.6 2.2 3.2 2.8
21 97.7 0.9 1.3 0.6 0.6 0.2 1.1 [52]
22 56.0 25.9 10.2 0.4 1.2 1.4 1.4 2.0 1.6 [53]
23 55.4 31.5 4.9 1.1 3.8 1.2 0.0 0.5 [55]
24 31.4 10.2 3.6 0.8 2.0 0.7 0.9 [58]
25 65.7 15.5 15.7 0.3 1.2 0.0 1.4 0.0 [62]
26 58.5 27.3 3.4 1.0 2.5 0.7 0.5 4.8 0.0 [64]
27 60.2 26.0 6.8 1.8 3.1 0.8 0.3 1.1 [65]
28 44.4 29.5 3.7 1.4 0.9 0.7 0.2 3.6 [97]
29 50.5 35.9 5.3 1.5 4.6 1.3 0.9 [98]
a
Determined by XRF.

needs to be preconditioned to a more suitable form of starting
material before the synthesis of zeolites and mesoporous materials
can be attempted. Direct alkali digestion without such pre-
conditioning usually results in lower zeolite yields (<50%) [12].
Table 2 lists the chemical composition of the oxide form of
other solid wastes for zeolite synthesis [7883,8994]. Similarly,
the major components are Si, Al, Fe, Ca, and Na. Fig. 2 shows the
powder XRD patterns of representative solid waste materials
[80,93]. In addition to amorphous aluminosilicates, quartz is the
major crystalline phase. These raw waste materials also require
an alkaline pretreatment prior to the synthesis of nanoporous
materials.
untreated fly ash [100,102,103]. According to Panitchakarn et al.
[104] (see Fig. 3), most of the impurities (Fe2O3, CaO and others)
in fly ash could be removed by acids (HCl, H2SO4, and HNO3) wash-
ing treatment (20% w/w) at the acid solution/solid ratio of 25 mL/g.
In addition, the peaks for calcite (CaCO3) present in the ash disap-
pear after the acid treatment, as shown in Fig. 4 [105]; an acid
treatment can remove the calcite phase directly. Alternatively, fly
ash calcined at 700 C for 2 h can result in the removal of some
unburned carbon and the decomposition of calcite. Acidification
may cause surface erosion and collapse. Moreover, some coarse
exterior and new cavities can appear during the acidification pro-
cess as calcium and some other acid-soluble salts are dissolved.

3. Preconditioning of fly ash 3.2. Alkali-Fusion

3.1. Acid treatment Alkali-fusion is a typical pretreatment necessary to extract silica

The preconditioning of fly ash with an acid treatment is a nec-
essary step to remove impurities, such as CaO and Fe2O3, from high
Ca- and Fe-containing fly ash. Their presence in the raw material
competes with the alumina for the formation of the zeolite frame-
work and accordingly, they can hinder the nucleation of zeolite
crystals during synthesis [32,90]. An acid treatment of fly ash can
also increase the activity, thermal stability, and acidity of the zeo-
lites for catalytic applications [100]. Typically, fly ash is treated
with 3 M HCl at a mass ratio of 1: 2 at 60 C for 1.5 h. Further
increases in the HCl concentration had shown no significant
changes, suggesting that 3 M HCl is sufficient for the removal of
impurities. After the acid treatment, the fly ash is washed thor-
oughly with distilled water until the pH reaches 67 to ensure that
no residual acid is present. The acid treated fly ash is then dried
and calcined at 700 C for 3 h to remove the incorporated organic
molecules [81,101]. A satisfactory acid treatment shows sharp
prominent peaks of quartz and mullite compared to those of
(mostly) and alumina (to a minor extent) from fly ash to prepare a
suitable silica and alumina precursors for zeolite synthesis
[28,37,38,47,94,106]. The fusion process helps generate active Si
and Al species in the synthesis mixture and increase the zeolite
yield. During the fusion process, inactive a-quartz and mullite in
fly ash are reacted with an alkaline reagent (usually NaOH powder)
according to the following reaction:
SiO2 s 2NaOHs ! Na2 SiO3 s H2 O
Al2 O3 s 2NaOHs ! 2NaAlO2 s H2 O
Elemental analysis of the aqueous solution containing the dis-
solved fused ash indicates that it is composed mostly of silicates
with a small amount of aluminates [52]. The resulting amorphous
sodium silicates and sodium aluminates dissolve readily in water
and participate in zeolite synthesis. If the alkali-fusion process is
not properly conducted, crystalline silicate impurities (quartz
phase) remain in the final product.
824 Y.-R. Lee et al. / Chemical Engineering Journal 317 (2017) 821843

Fig. 1. Powder XRD patterns of representative raw fly ash sources from different areas: fly ash No. of (a) 6, (b) 21, (c) 23, and (d) 29 listed in Table 1. Adapted from Refs.
[27,52,55,98].

Table 2
Chemical compositions of other waste sources.

Source Chemical composition (wt.%)a Ref.

SiO2 Al2O3 Fe2O3 TiO2 CaO MgO Na2O K2O Others
Oil shale ash 56.1 13.9 6.4 2.6 2.1 1.6 2.9 [78]
Oil shale ash 32.5 6.5 3.0 0.2 50.0 3.3 0.5 4.0 [79]
Lithium slag 71.7 25.2 0.6 0.0 0.2 0.1 0.4 1.6 [80]
Cupola slag 47.3 12.1 5.1 0.1 24.1 0.0 0.1 0.1 [81]
Cupola slag 70.1 18.9 3.2 1.2 3.3 1.3 2.4 0.8 [82]
Glass residue 70.5 1.2 0.4 19.7 3.4 0.4 4.4 [83]
Meta-kaolin 46.5 38.3 0.6 [89]
Steel slag 96.9 0.5 0.2 0.5 1.4 0.3 [90]
Rice husk ash 95.5 0.8 0.2 0.0 0.3 0.6 0.1 0.7 1.7 [91]
Rice husk ash 95.5 0.8 0.2 0.0 0.3 0.6 0.1 0.7 1.7 [92]
Laterite residue 83.8 2.3 4.6 2.8 6.5 [93]
Laterite residue 18.5 59.5 18.4 0.5 3.0 [94]
a
Determined by XRF.

A satisfactory fusion pretreatment can be confirmed by powder
XRD and scanning electron microscopy (SEM). Fig. 5 shows the
XRD peaks of sodium silicate as a major phase concurrent with
the removal of crystalline quartz and mullite phases after an
alkali-fusion treatment [26]. As shown in Fig. 6, although the orig-
inal fly ash has a spherical particle shape with a glassy and smooth
surface, the surface becomes rough after the alkali-fusion treat-
ment and larger cracks are eventually observed with increasing
treatment time, indicating the dissolution of a-quartz to the
sodium silicate form [97].
The conversion of fly ash to sodium silicate and sodium alumi-
nate by an alkali-fusion treatment depends on the amount of NaOH
 Y.-R. Lee et al. / Chemical Engineering Journal 317 (2017) 821843 825

Fig. 2. Powder XRD patterns of representative solid waste materials: (a) lithium slag, (b) laterite residue, and (c) bauxite. Adapted from Refs. [80] and [93].

Fig. 3. Chemical compositions of zeolite products synthesized from fly ash treated with various acids. Adapted from Ref. [104].

added to the fly ash, which influences the alkalinity of the zeolite
synthesis mixture directly [28,38]. No zeolite product was formed
with a 0.8 NaOH/fly ash mass ratio and zeolite formation was
observed only above 1.0 NaOH/fly ash. The crystallinity increased
abruptly to a maximum at a NaOH/fly ash ratio of 1.2. Further
increases in the NaOH concentration resulted in a decrease in crys-
tallinity. Therefore, 1.2 NaOH/fly ash is the optimum for the forma-
tion of sodium silicate and for the pH of the zeolite synthesis
mixture.
The effects of the fusion temperature from 100 to 800 C after
1 h at a NaOH/fly ash ratio of 1.2 on the crystallinity of the final
zeolite product were examined [28]. As shown in Fig. 7, no zeolite
formed in the samples fused at temperatures below 200 C. Quartz
still existed as a crystalline phase at these low temperatures and no
hydrothermal synthesis took place when the fused fly ash solution
was used for zeolite production. A higher zeolite yield was
observed at fusion temperatures above the melting point of NaOH
(318 C). The maximum crystallinity of the zeolites was achieved
when the fusion temperature was increased to 550 C. The crys-
tallinity decreased gradually at fusion temperatures higher than
800 C, and non-crystalline glass aggregates began to form. The
effects of the fusion time of fly ash (0.52 h) on zeolite formation
were also studied at 550 C [107]; a fusion time of 30 min was
insufficient and zeolite X peaks appeared after 1 h with a maxi-
mum crystallinity observed after 2 h.
4. Zeolites synthesis
A representative flow diagram for the zeolite synthesis proce-
dures from coal fly ash with acid washing pre-treatment is given
in Fig. 8. Fig. 9 shows some of the common zeolite framework
structures produced using fly ash as a silica source [108]. Two
types of zeolite synthesis methods have been reported. Typically,
the alkaline-fused fly ash discussed above was cooled to room tem-
perature and mixed with distilled water. The mixture was aged for
24 h with stirring at room temperature. Either the total solution
mixture of the fused fly ash or the supernatant solution after
removing the precipitate remaining at the bottom was introduced
to a polypropylene bottle. At this stage, an extra aluminum source
was added when necessary to prepare an appropriate synthesis
mixture composition for the particular zeolite phase. Further NaOH
addition may also be necessary to control the pH. The substrate
mixture was then treated hydrothermally at a fixed synthesis
temperature and time. Table 3 lists the reported zeolite synthesis
conditions after the alkali-fusion treatment of fly ash [14,21,22,2
6,28,3234,3638,52,53,6165,97].
826 Y.-R. Lee et al. / Chemical Engineering Journal 317 (2017) 821843
Fig. 4. XRD patterns of (a) fly ash treated with 0.25 mol/L HCl for 2 h (b) fly ash calcined at 700 C for 2 h, and (c) raw fly ash (q: quartz; c: calcite; m: mullite). Adapted from
Ref. [105].
As an alternative to the alkali-fusion treatment, digestion of fly
ash with 25 M of NaOH or KOH solution, was carried out for 2
12 h. When necessary, an extra aluminum source and water were
added to control the molar ratio of the synthesis mixture. Subse-
quently, hydrothermal synthesis was conducted at 100200 C
for 348 h in a Teflon-lined autoclave. Table 4 lists the reported
zeolite synthesis conditions after the NaOH digestion of fly ash
[35,40,43,50,51,54]. More detailed zeolite synthesis works using
the pre-treated fly ash are discussed in the following sections.
4.1. Zeolite synthesis after alkali-fusion of fly ash
June et al. [21] prepared zeolite A and 13X by a hydrothermal
treatment using fly ash after alkali fusion. Highly crystalline zeolite
A in cubic shape and 13X in octahedral morphology, both in ca.
2.5 mm size, were obtained at 100 C for 4 h and 90 C for 12 h,
respectively (see Fig. 10). Both products exhibited high Ca2+ ion-
exchange capacity (184 and 134 mg/g) and stable CO2 adsorption
capacities in cyclic performance (145 and 220 mg/g).
Chang and Shih [22] prepared zeolites A and X from three dif-
ferent fly ash sources. Aluminum hydroxide hydrate, as the alu-
minum source, was added to an aqueous solution of fused fly
ash. The results indicated that the amount of dissolved Al is critical
to what type of zeolite is formed from the fused fly ash solution.
Depending on the fly ash source, pure zeolite A or a mixture of zeo-
lites A and X were obtained after 3 to 7 days of heating at 60 C. A
decrease in the silica concentration of the synthesis mixture
favored the formation of zeolite A. Chang et al. [26] synthesized
different types of zeolites from a range of fly ash sources by varying
the synthesis temperatures. As shown in Fig. 11, zeolites X and P
were synthesized at 60 and 90 C, respectively, from the same syn-
thesis mixture and heating time (4 days). Zeolites A and X were
also synthesized from the supernatant solution of the fused mix-
ture with distilled water. Moreover, their purity and crystallinity
were higher than those synthesized using a total fused fly ash
solution.
Shigemoto et al. [28] selectively prepared zeolite X from fly ash
after alkali-fusion followed by hydrothermal synthesis. Zeolite X
with 62% crystallinity (compared to the standard sample) was
obtained at a fusion temperature of 550 C with a 1.2 NaOH/fly
ash mass ratio followed by a hydrothermal treatment at 100 C
for 6 h. When the NaOH/fly ash ratio was increased to 1.8 in this
 Y.-R. Lee et al. / Chemical Engineering Journal 317 (2017) 821843
Fig. 5. Powder XRD patterns of raw fly ash (bottom), fused fly ash (middle), and the sediment of fused fly ash solution after 1 day of aging at room temperature (top) (Q:
quartz, M: mullite, and S: sodium silicate). Adapted from Ref. [26].
mixture, hydroxysodalite (SOD) was obtained instead of zeolite X.
The addition of sodium aluminate to the above fused fly ash solu-
tion (NaAlO2/fly ash 0.41) led to the stabilization of zeolite A.
Fatovat et al. [33] also reported zeolite syntheses using high silica
fly ash as a raw material with varying its Si/Al ratios and heating
the synthesis mixture hydrothermally at 100 C for 12 h. The Si/
Al ratio was varied from 1.6 to 3.0 by adding NaAlO2 as an
aluminum source. Highly crystalline zeolite A was prepared at a
Si/Al ratio of 1.6, whereas zeolites X and Y were produced at ratios
of 2.4 and 2.8, respectively. In addition, the crystallinity of the
zeolites was improved by a systematic increase in the NaOH/fly
ash ratio from 1.2 to 2.0. The zeolites produced were tested for
Co2+ ion exchange. Of the zeolites tested, zeolite X exhibited the
highest capacity of 4.9 meq/g. Izidoro et al. [37] prepared zeolites
A and X using two different types of fly ash by alkali-fusion
followed by a hydrothermal method. Fully crystallized zeolite
A was obtained at 100 C after 7 h of heating, whereas zeolite
X was obtained at 100 C and 24 h. The cation exchange capacity
for the removal of Cd2+ and Zn2+ ions was also measured. Both
zeolites exhibited a better Zn2+ removal efficiency than Cd2+ with
a maximum uptake of 97.2 and 94.3%, respectively.
Rayalu et al. [38] examined the effects of the NaOH concentra-
tion, fusion temperature, and crystallization time on the synthesis
of zeolite Y. Fully crystallized zeolite Y was obtained under the
optimal conditions of 1.2 NaOH/fly ash and a fusion temperature
of 600 C, followed by a hydrothermal treatment at 100 C for
10 h. The surface area (600 m2/g) of the newly synthesized zeo-
lite Y was comparable to that of commercial zeolite Y and its
Ca2+ cation exchange capacity was 44.5 meq/g. El-Naggar et al.
[97] obtained a mixture of zeolites A and X with a maximum crys-
tallinity of 96% and surface area of 594 m2/g after hydrothermal
synthesis at 90 C for 8 h using fused fly ash as a synthesis mixture.
The resulting zeolite A and X mixture also exhibited a high Cs+
removal efficiency.
827
Chen et al. [36] proposed a new alkaline fusion route in the
presence of a composite alkali mixture (NaOH and Na2CO3). As a
major product, zeolite X was produced under the optimal condi-
tions of a 1.5 composite alkali mixture/fly ash mass ratio and a
fusion temperature of 800 C, followed by a hydrothermal treat-
ment at 110 C for 8 h. Park et al. [14] prepared zeolite X using a
solid precipitate extracted from a supernatant solution of fused
fly ash. The optimal synthesis conditions were determined by vary-
ing the hydrothermal reaction temperatures (7595 C) and reac-
tion time (1248 h). As shown in Fig. 12, zeolite X with the
maximum crystallinity was obtained at 85 C after 36 h of heating.
The surface area (465 vs 624 m2/g) of the resulting zeolite X was
comparable to that of commercial zeolite X and the material show-
ing a high CO2 capture capacity of 152 mg/g.
Interestingly, Belviso et al. [34] prepared magnetic zeolites
using a mixture of fly ash and red mud (RM) as precursors at low
temperatures (2540 C) for 4 days. The hydrothermal synthesis
was carried out by varying the RM to fly ash ratio (0.25, 1.0, and
4.0); a mixture of zeolites A, X, and ZK-5 (KFI) was obtained at
RM/fly ash ratio of 0.25, and zeolite A with trace amounts of soda-
lite was obtained at a RM/fly ash ratio of 1.0. Sodalite and Ti-Fe
oxide mixtures were produced at a RM/fly ash ratio of 4.0. Both
products obtained from 0.25 and 1.0 RM/fly ash ratios exhibited
good magnetic properties, but the former exhibited a higher
adsorption of Reactive Orange 16 (RO16), probably due to the pres-
ence of both A- and X-type zeolites. After hydrothermal synthesis,
the prepared zeolites could be separated easily using an external
magnet.
Molina and Poole [32] prepared zeolites from fly ash using both
alkali-fusion and alkali-digestion methods (see below). The
well-crystallized zeolite X was formed at 90 C after 6 h of heating
after the alkali-fusion of fly ash, whereas zeolite A was formed as
the main product at 60 C after 6 h of heating after the alkali-
digestion of fly ash. In addition, a mixture of zeolites A and X
828 Y.-R. Lee et al. / Chemical Engineering Journal 317 (2017) 821843
Fig. 6. SEM images of (a) raw fly ash and (bd) fused fly ash treated for 15, 30, and 60 min at 550 C respectively. Adapted from Ref. [97].
Fig. 7. Effects of the alkali-fusion temperature on zeolite formation in the condition
of 1.2 NaOH/fly ash, fusion for 1 h, and hydrothermal reaction for 6 h at 373 K (d:
Na-A; s: Na-X; h: hydroxysodalite; 4: acid-soluble component). Adapted from Ref.
[28].
was formed after a 24 h hydrothermal treatment at 90 C from the
alkali-digestion method, which was converted successively to zeo-
lite P after further heating for 96 h. From the overall results of this
study, it is clear that a highly crystalline product with a shorter
crystallization time can be achieved preferentially using the
alkali-fusion method. Regardless of the pretreatment methods,
fly ash was used successfully to form zeolites A and X, which were
converted to the more stable zeolite P at a longer crystallization
time.
Kazemian et al. [52] reported the synthesis of zeolite P using fly
ash and its ion exchange property. Zeolite P with a particle size of
23 lm was obtained at 120 C for 4 h of hydrothermal synthesis
under at a chemical composition of 2.2SiO2Al2O35.28Na2-
O106H2O. Thermogravimetric analysis showed that zeolite P
remained stable to heating up to 800 C with a maximum H2O
weight loss of 12%. Zeolite P also showed a high NH+4 ion exchange
capacity (3.23 meq/g). Deng et al. [53] synthesized zeolite P with a
70.5% yield under the optimal fusion conditions of 1.2 Na2CO3/fly
ash at 550 C, followed by a hydrothermal treatment at 80 C for
7 h with 2 M NaOH. The Cu2+ ion-exchange capacity of zeolite P
was 3.12 meq/g. The Cu2+ adsorption-desorption cycles showed
that zeolite P was stable for up to 3 recycles without showing a
decrease in its adsorption capacity.
Park et al. [109] reported the synthesis of sodalite and can-
crinite from fly ash in molten alkali salt mixtures by a thermal
treatment without addition of water. A mixture of fly ash, alkaline
hydroxide (KOH, NaOH, or NH4OH), and the salt (KNO3, NaNO3, or
NH4NO3) were heated to the molten state at 350 C for various
time intervals. The resulting lump was crushed and then washed
with distilled water to remove the external base and salt. When
a NaOH-NaNO3 molten mixture was used, cancrinite was obtained
as the major product at 350 C after 1 day of heating. Further
 Y.-R. Lee et al. / Chemical Engineering Journal 317 (2017) 821843 829

Fig. 8. Zeolite synthesis from coal fly ash comprised of (I) acid treatment followed by either (II) alkali-fusion and hydrothermal reaction or (III) alkali digestion (acid-
treatment is optional).

Fig. 9. Structure of some common zeolites frameworks (a) LTA, (b) FAU, (c) SOD, (d) GIS, (e) ANA, and (f) MER. Adapted from Ref. [108].

Table 3
Synthesis of ordered porous materials after alkali-fusion of fly ash.

Alkaline fusion Fused ash treatment Synthesis of materials Ref.

NaOH/fly ash (wt./wt.) Time (h) Temp. (C) H2O (wt.%) Aging time (h) Time (h) Temp. (C) Products
1.2 1.0 600 4 36 85 FAU [14]
1.2 1.0 600 4 72 100 MCM-41, SBA-15
1.2 1.0 500 5 24 4 100 LTA [21]
1.2 1.0 500 5 24 12 90 FAU
1.2 1.0 550 5 24 60 LTA, FAU [22]
1.2 1.0 550 5 24 96 60 LTA, FAU, GIS [26]
1.2 1.0 550 4 12 6 100 FAU [28]
1.2 1.0 550 4 24 6 90 LTA, FAU, GIS [32]
1.2 1.5 600 5 8 12 100 LTA, FAU [33]
1.2 600 98 40 LTA, FAU, KFI, SOD [34]
1.5 1.0 800 8 110 FAU [36]
1.2 1.0 550 16 100 FAU [37]
1.2 1.0 550 7 100 LTA
1.2 1.0 600 8 10 100 FAU [38]
1.2 1.0 550 4 120 GIS [52]
1.2 2.0 550 7 80 GIS [53]
1.2 1.0 550 4 24 98 97 MCM-41 [58]
1.2 1.0 550 24 90 72 SBA-15
1.2 1.0 577 120 100 MCM-41 [62]
1.2 1.0 550 4 24 24 25 MCM-41 [63]
1.2 1.0 550 4 24 16 25 MCM-41 [64]
1.2 4.0 577 48 100 MCM-41 [65]
1.2 1.5 550 10 12 14 25 Al-MCM-41 [70]
1.0 1.0 550 8 0.5 8 90 FAU-LTA [97]
1.2 1.0 550 0.2 24 150 115 MCM-41 [123]
1.2 1.0 550 4 24 72 100 SBA-16 [124]
830 Y.-R. Lee et al. / Chemical Engineering Journal 317 (2017) 821843

Table 4
Synthesis of ordered porous materials after NaOH digestion of fly ash.

NaOH digestion Synthesis of materials Ref.

NaOH/fly ash (mL/g) NaOH conc. (M) Time (h) Temp. (C) Products
13.3 1.7 190 100 LTA [35]
13.3 5.0 250 100 LTA
13.3 6.7 340 100 LTA
8.0 2.0 24 85 LTA, FAU [40]
18.2 0.5 48 150 GIS, GIS derivatives, GME [43]
18.2 1.0 24 200 ANA
18.2 0.5 8 150 GIS [50]
18.2 3.0 24 240 JBW, tobermorite, SOD, CAN, ANA
8.0 2.0 5 120 GIS, hydroxyl SOD [51]
8.0 2.0 24 100 GIS and composite material [54]

Fig. 10. SEM images of (a) commercial zeolite A, (b) zeolite A prepared from fly ash, (c) commercial zeolite 13X, and (d) zeolite 13X prepared from fly ash. Adapted from Refs.
[21].

increases to 3 days resulted in the formation of a mixture of soda-
lite and cancrinite. In the case of a NaOH-KNO3 molten mixture,
cancrinite with the maximum crystallinity was formed at 350 C
after 1 day of heating. The other waste materials, such as kaolinite,
montmorillonite, and natural zeolites, were also used as the raw
materials for the zeolite synthesis, and the results showed similar
zeolite formation to those from fly ash.
4.2. Zeolite synthesis after aqueous NaOH/KOH digestion of fly ash
Wang et al. [35] reported the effects of the NaOH digesting solu-
tion concentrations (1.7, 3.3, 5.0, and 6.7 M) for the preparation of
zeolite A using fly ash as the starting material together with an
additional aluminum source. Initially, the raw fly ash was treated
with an acid solution to remove the impurities and increase the
amount of silica available for zeolite synthesis. Pure zeolite A
was obtained after heating at 100 C for 340, 250, and 190 min,
respectively, when 1.7, 5.0, and 6.7 M NaOH solutions were used.
The NaOH concentration affected both the crystallization time
and particle size. A shorter crystallization time and smaller particle
size were achieved at higher NaOH concentrations. On the other
hand, a mixture of zeolites A and X was obtained from a 3.3 M
NaOH solution, and zeolite A transformed gradually to the more
stable hydroxysodalite as the crystallization time was increased
to 370 min at 6.7 M NaOH. Under a given alkali condition, increas-
ing NaOH concentration resulted in a greater increase in Si dissolu-
tion than Al from coal fly ash [110,111].
Tanaka et al. [40] conducted the digestion of fly ash accompa-
nied by dialysis. A semi-permeable membrane tube containing
fly ash and 5 mL of an aqueous NaOH solution was immersed into
a sealed polypropylene vessel containing a NaOH solution and pre-
treated at 85 C for 24 h under an air flow. After dialysis of the aged
solution, the membrane tube was removed and zeolite A was syn-
thesized at 85 C for 24 h with the addition of a NaOH-NaAlO2 mix-
ture at different concentrations to adjust the SiO2/Al2O3 ratio from
0.9 to 4.3. Pure zeolite A was obtained at 0.9 SiO2/Al2O3, as shown
in Fig. 13. Weak XRD peaks for zeolite X began to appear at SiO2/
Al2O3  1.7 and its intensity increased sharply at SiO2/Al2O3 = 4.3
with a concurrent decrease in the crystallinity of zeolite A.
Querol et al. [43] prepared zeolite P and its derivatives, sodalite,
analcime (ANA), gmelinite (GME), and hydrated nepheline (JBW)
after a pretreatment with different fly ash types by NaOH diges-
tion. Sufficiently high activation efficiencies were achieved with a
1.0 M NaOH solution. Zeolite P derivatives and gmelinite were
obtained at 150 C after 48 h heating, and analcime was observed
at 200 C after 24 h. Fly ash with a very close SiO2/Al2O3 ratio
 Y.-R. Lee et al. / Chemical Engineering Journal 317 (2017) 821843 831

Fig. 11. Powder XRD patterns of zeolites X and P synthesized using alkaline-fused fly ash at 60 and 90 C, respectively. Adapted from Ref. [26].

Fig. 12. Characterization of synthesized zeolite X: (an and b) powder XRD patterns of zeolite X synthesized at different temperatures and times, respectively, (c) N2 sorption
isotherms (j: pure chemicals; N: alkaline-fused ash precipitate; d alkaline-fused ash), and (d) CO2 adsorption isotherms (r: pure chemicals; s: alkaline-fused ash
precipitate; j: alkaline-fused ash). Adapted from Ref. [14].

produced different zeolite phases despite the same activation con- the original fly ash source. Querol et al. [50] also prepared zeolite P
ditions, which might be due to the unknown impurities present in by microwave-assisted synthesis. Although the zeolite yields
832 Y.-R. Lee et al. / Chemical Engineering Journal 317 (2017) 821843
Fig. 13. Powder XRD patterns of zeolites A and X and their mixtures formed at various SiO2/Al2O3 molar ratio: (a) 0.9, (b) 1.7, (c) 2.6, (d) 3.5, and (e) 4.3. Adapted from Ref.
[40].
obtained were similar to those of hydrothermal synthesis, the syn-
thesis time required was reduced substantially to approximately
30 min.
Inada et al. [51] reported that the formation of zeolites depends
greatly on the Si/Al ratio of the fly ash as well as the alkali digestion
conditions. Zeolite P was obtained with a 2.0 M NaOH solution and
the yield decreased with increasing NaOH concentration. Hydrox-
ysodalite was formed with 4.0 M NaOH. Silicon-lean fly ash tended
to form hydroxysodalite with a low Si/Al ratio, whereas silicon-rich
fly ash tended to form zeolite P with a higher Si/Al ratio. Aono et al.
[54] synthesized zeolite P using a direct hydrothermal synthesis
process. Fully crystallized zeolite P was produced from a 2.0 M
NaOH solution heated at 100 C for 24 h and it showed a maximum
K+ ion exchange capacity of 4.83 meq/g. In addition, a composite
magnetic zeolite P was prepared using fly ash together with differ-
ent weight percentages of nano-sized magnetite (1075 wt.%). A
30 wt.% magnetite loading at 100 C for 24 h of heating were the
optimal synthesis conditions. The resulting composite material
exhibited a Cs+ ion-exchange capacity of 2.5 meq/g.
Bukhari et al. reviewed zeolite synthesis from fly ash using
microwave (MW) or ultrasound (US) irradiation [112], and sug-
gested that MW and US energy can decrease the synthesis time sig-
nificantly [113,114]. Several representative synthesis studies can
be mentioned. Bukhari et al. [115] prepared zeolite Na-A from coal
fly ash utilizing MW heating and compared the two methods of
hydrothermal synthesis with or without the prior alkali fusion of
fly ash in the substrate composition range of 4.714 Na2O: 0.582
1.0 Al3: 1.780 SiO2: 192 H2O. The crystallinity of the product was
affected by the power, time, and aluminate concentration; the pro-
duct treated with alkali fusion had a higher BET surface area
(64 m2/g) because of the differences in the dissolution of alu-
minum and silicon in the fly ash into the reaction gel. Inada et al.
[116] prepared zeolite Na-P1 using MW irradiation. Fly ash with
a Si/Al ratio of 1.10 was mixed with a 2 M NaOH solution and trea-
ted with MW at 100 C. The early-stage heating for 015 min
enhanced zeolite formation due to the stimulated dissolution of
SiO2 and Al2O3 from the fly ash. On the other hand, MW irradiation
in the middle stage in 4560 min retarded zeolite formation
caused by the retarded nucleation in the intermediate aluminosil-
icate gel. The zeolite product treated with MW irradiation in the
first 15 min followed by conventional heating for a total synthesis
time of 2 h exhibited a high XRD peak intensity and the best NH+4
exchange capacity (2.00 meq/g). Belviso et al. [117] reported
the synthesis of zeolite X from fly ash by a hydrothermal process
after a NaOH pre-fusion treatment at 550 C for 1 h, followed by
1 h of a sonication treatment with a US treatment of 240 W for
1 h. The US-treated samples produced zeolite X at 25 C, while
the untreated samples did now show any zeolite crystallization
until the temperatures reached higher than 40 C. Park et al.
[118] reported the synthesis of zeolite 4A from kaolin using a US
treatment. The kaolin used had a Si/Al ratio of ca. 1.15 and a molar
batch composition of Al2O3:1.94SiO2:4Na2O:100H2O. A fully
crystalline product was obtained at 70 C after 4 h of US treatment
at a frequency of 47 kHz with 130 W power supplied. From these
results, it was claimed that the application of an ultrasonic treat-
ment facilitates the formation of zeolites at significantly low tem-
peratures owing to accelerated dissolution of the source ash
material, leading to Al-Si supersaturation, which produced a high
nucleation rate of crystalline phases.
Zeolites prepared by direct alkali digestion without acid pre-
treatment can contain large amounts of impurities and the zeolite
stability may be inferior and ion-exchange capacities of the mate-
rials reduced. According to Ojha et al. [100], the stability of the zeo-
lite can be improved if these impurities are removed prior to the
zeolite synthesis. Molina and Poople [32] reported that the pre-
treatment of fly ash can lead to increase its Si and Al contents
together with a huge decrease (up to 65%) in impurities. If the pro-
duct is alkali-fused and dissolved in water so that the mother
liquor is used for zeolite synthesis, impurity level becomes
insignificant and stability is not usually a problem. The differences
in Ca2+ ion-exchange capacity and CO2 capture capacity of the zeo-
lite A and X samples either prepared using chemicals or fly ash
were within 20% [79]. The effect of impurity on the physicochem-
ical properties of synthesized zeolite products has been reported
 Y.-R. Lee et al. / Chemical Engineering Journal 317 (2017) 821843 833

Table 5
Optimum synthesis conditions of zeolites from other waste sources.

Wastes Molar compositions Alkaline fusion Fused ash treatment Synthesis of materials Ref.
SiO2 Al2O3 Na2O H2O NaOH/waste Time (h) Temp. (C) H2O Aging time (h) Time (h) Temp. (C) Products
(wt./wt.) (wt.%)
Oil shale ash 3.0 1.0 5.7 228 2.0 2 350 5 1 2.5 100 FAU + LTA [78]
3.0 1.0 5.7 228 2.0 2 350 5 3 12 100 FAU + LTA
Lithium slag 1.5 4 600 10 12 8 95 FAU [80]
Cupola and Al slag 18.2 11.9 57.3 75.9 3.0 1 700 3 90 LTA [81]
18.2 11.9 57.3 75.9 9 90 SOD
Cupola slag 20.1 0.1 5.7 2.8 1.2 1 550 24 150 ANA [82]
20.1 0.2 21.0 9.7 1.2 1 550 4 150 MFI
Glass powder 3.0 1.0 5.7 228 2.0 2 250 0.5 24 100 LTA + SOD [83]
3.0 1.0 5.7 228 2.0 2 500 0.5 LTA + FAU
Meta-kaolin 2.0 1.0 1.5 31 4.0 5 1 96 200 JBW [89]
2.0 1.0 1.9 41 0.1 48 200 CAN
2.0 1.0 31 96 200 Li-ABW
2.0 1.0 1.9 41 48 200 SOD
Steel slag 2.5 1.0 2.0 5 24 24 100 FAU [90]
Rice husk ash 3.8 1.0 2.1 50 1.0 15 48 100 GIS [91]
18.2 1.0 4.2 213 0.3 20 72 100 ERI-OFF [92]
Laterite residue/bauxite 3.2 1.0 5.1 205 1.6 2 600 5 24 6 100 FAU [93]
bentonite 1.4 6 600 4 24 12 80 FAU [94]

by others. The synthesized zeolite with 1.74 SiO2/Al2O3 ratio from
fly ash was observed to lose its crystallinity beyond 973 K and the
crystalline structure was mostly collapsed above 1073 K [100]; The
commercial zeolites having high SiO2/Al2O3 ratio can resist higher
temperature. Belardi et al. [103] also reported that K-L and K-W
zeolites prepared form fly ash exhibited high thermal stability up
to 600 C by increasing the Si:Al ratio of the slurry.
According to Panitchakarn et al. [104], large-scale production of
zeolite could cost approximately US $20.65 per kilogram of zeolite
in 2014, whereas the global price of 4A zeolite was US $83.87 per
kg by UOP. Ojha et el. [100] also reported that the cost of the zeo-
lite 13X synthesized from fly ash was about one-fifth of commer-
cial 13X by taking into account the costs of chemicals and
utilities for all the steps in the process. It may be possible to utilize
waste heat from the process, which can reduce the cost of the pro-
duction further.
4.3. Zeolite synthesis using other solid wastes
Table 5 summarizes the zeolite synthesis conditions adopted
when other solid waste sources were used as the silica source.
Machado and Miotto [78] synthesized zeolites A and X from pre-
treated oil shale using two different preparation methods. Alkali-
fusion at 350 C for 2 h was carried out prior to either reflux or
hydrothermal synthesis at 100 C. Zeolite X with a maximum crys-
tallinity of 61% and 72% (after 2.5 and 12 h), and zeolite A with only
32% and 26% crystallinity (after 1.5 and 72 h) were obtained under
reflux and hydrothermal synthesis conditions, respectively. In both
cases, the zeolites converted to the more stable hydroxysodalite
after 96 h heating. On the other hand, Shawabkeh et al. [79] pre-
pared zeolite P using pretreated oil shale ash. The optimal
hydrothermal synthesis conditions were heated to 160 C for
24 h after digestion in a 8 M NaOH solution. The resulting zeolite
P showed a higher removal efficiency of Cd2+ (95.6 mg/g) than
Pd2+ (70.58 mg/g) when the initial concentration for both ions
was 100 mg/L. Chen et al. [80] synthesized zeolite X using lithium
slag as the raw material. Prior to the hydrothermal process, alkali-
fusion was carried out at 600 C for 4 h. The adsorption capacity
(0.32 kg/kg) of water vapor was comparable to that (0.33 kg/kg)
of commercial zeolite.
Anuwattana and Khummongkol [81] prepared zeolite A from
two industry wastes, cupola slag and aluminum sludge, using
two different preparation methods: alkali-fusion followed by a
hydrothermal synthesis and a direct hydrothermal method. Both
wastes were initially pretreated with HCl and H2SO4 at 60 C for
1.5 h to remove impurities. The alkali-fusion process was carried
out by mixing the acid treated cupola slag, purified aluminum
sludge, and NaOH at a 1:1:3 mass ratio and fused at 700 C for
1 h. No zeolite A formation occurred without the addition of alu-
minum sludge in the fusion step. The optimal conditions to obtain
zeolite A with a maximum yield of 64 % was 90 C for 3 h of heating
at H2O/SiO2 = 4.17. The crystallinity of zeolite A reached 100 % after
9 h. On the other hand, direct hydrothermal synthesis produced
gibbsite after 5 h of heating at 90 C, which was then converted
to hydroxysodalite after prolonged heating for 9 h. Anuwattana
et al. [82] prepared ZSM-5 from cupola slag using two different
methods: hydrothermal and microwave-assisted syntheses.
Although ZSM-5 with a maximum crystallinity of 76.2% was
obtained at 150 C after 24 h hydrothermal synthesis using acid-
treated cupola slag, highly crystalline ZSM-5 was also obtained at
the same temperature but for a much shorter time of 4 h employ-
ing the microwave-assisted synthesis method. This suggests that
the latter could enhance the ZSM-5 crystallization rate up to 6-
fold compared to the conventional method.
Alves et al. [83] synthesized zeolite A from a glass powder resi-
due by hydrothermal synthesis after alkali-fusion, and examined
the effects of a mineralizing agents (NaOH and Ca(OH)2), fusion
temperature (250500 C), and synthesis temperature (100
170 C). No zeolite formation was observed when Ca(OH)2 was
used as the mineralizing agent, while predominantly zeolite A with
a secondary phase of hydrated sodalite formed when NaOH was
used. Only hydrated sodalite was obtained after alkali-fusion at
250 C, but zeolite A and hydrated sodalite were obtained at 350
and 500 C of alkali-fusion, respectively. The use of pseu-
doboehmite as an alternative aluminum source led to the forma-
tion of zeolite A with the presence of zeolite X as a secondary
phase after alkali-fusion at 500 C. Zeolite A, hydrated sodalite,
and cancrinite were formed by hydrothermal synthesis at 100,
135 and 152 C, respectively. Zeolite A with minor secondary
phases could be readily obtained at 100 C of hydrothermal heating
after alkali-fusion at 350 C.
Lin et al. [89] synthesized several low-silica zeolites, i.e., nephe-
line, cancrinite, sodalite, and ABW-type zeolite using meta-kaolin
as a raw material. Highly crystalline nepheline was obtained at
200 C after heating it for 4 days in an aqueous NaOH solution.
The co-crystallization of cancrinite and sodalite was observed at
834 Y.-R. Lee et al. / Chemical Engineering Journal 317 (2017) 821843
200 C after 2 days when both Na2CO3 and K2CO3 were used as
additives in a NaOH solution, whereas highly crystalline cancrinite
was obtained at 200 C after 8 days when KNO3 was used as the
additive in a NaOH solution. Highly crystalline sodalite was pre-
pared at 200 C after 2 days heating in a NaOH aqueous solution
with additives (NaCl, KCl, and KBr). Highly crystalline Li-ABW
was also obtained in a LiOH solution at 200 C after heating for
4 days.
Kuwahara et al. [90] synthesized zeolites X and Y using steel
slag as the raw material. Prior to the hydrothermal process, the
steel slag was pretreated with HCl for 4 h to remove impurities,
such as CaO and Fe2O3. Powder XRD confirmed that no zeolite for-
mation had occurred without the acid pretreatment and zeolites
with maximum crystallinities were obtained at 100 C after 6 h
of heating. The resulting zeolites with varying SiO2/Al2O3 ratios
(2.540) were used as a support for the photocatalyst. The zeolites
loaded on TiO2 exhibited photocatalytic activity applicable to the
degradation of organic pollutants, and revealed enhanced photo-
catalytic activity after being loaded onto a zeolite with a higher
SiO2/Al2O3 ratio.
Bohra et al. [91] prepared cashew nut-like zeolite P via the in-
situ extraction of silica from rice husk ash, using aluminum foil
and NaOH as low cost synthesis precursors under hydrothermal
synthesis at 100 C for 48 h. Zeolite P was obtained predominantly
as a product with a small amount of zeolite A. Bohra et al. [92] also
prepared zeolite T, which is an intergrowth-type zeolite of the eri-
onite (ERI) and offretite (OFF) ERI-OFF structure, by the direct dis-
solution of rice husk ash as a raw material in the presence of NaOH,
KOH, and tetramethylammonium hydroxide (TMAOH). The XRD
peaks for zeolite T were observed after 24 h and the crystallinity
increased with increasing synthesis time to 72 h at 100 C.
Fig. 14. Characterization data for the synthesized zeolite X: (a and b) powder XRD patterns of zeolite X synthesized at different temperatures and bentonite/NaOH weight
ratios, respectively, (c) CO2 capture capacity at different adsorption temperatures, and (d) CO2 adsorption (200 C desorption (350 C) cycles. Adapted from Ref. [94].
Liu et al. [93] prepared zeolite X by alkali-fusion followed by a
hydrothermal treatment using laterite residue and bauxite as raw
materials and examined its CO2 capture properties. The optimal
synthesis conditions were a synthesis mixture of 205 H2O:5.1
Na2O:3.2 SiO2:1.0 Al2O3, fusion temperature of 600 C, and a
hydrothermal treatment at 100 C for 6 h. The synthesized zeolite
X showed selective CO2 adsorption against N2 at 30 C, suggesting
its potential use as an adsorbent for post-combustion carbon
capture.
Chen et al. [94] synthesized zeolite X from bentonite by alkali-
fusion followed by a hydrothermal treatment. As shown in Fig. 14,
zeolite X was obtained under the optimal conditions of 1.4 ben-
tonite/fly ash and a fusion temperature of 600 C, followed by a
hydrothermal treatment at 80 C for 12 h. The prepared zeolite X
had a high CO2 capture capacity (211 mg/g) and CO2/N2 selectivity
(37 at 25 C, 1 bar). The thermal analysis data showed that the pre-
pared zeolite X had stable adsorption capacity for up to 5 recycle
runs with a CO2 uptake of 32 mg/g at 200 C.
5. Synthesis of mesoporous materials using fly ash
In addition to the various zeolites, mesoporous silica materials
can be synthesized using the high silica content in fly ash. Meso-
porous silica synthesis from fly ash is anticipated to overcome
the limitations of the microporous zeolite materials in the adsorp-
tive removal of macromolecule pollutants [65]. The mesoporous
materials have high specific surface areas above 1000 m2/g,
well-defined mesopores with a controlled size (approximately
from 2 to 20 nm) and large amounts of internal silanol (SiAOH)
groups inside the pores that can be modified easily by functional-
ization with other useful organic groups for a range of industrial
 Y.-R. Lee et al. / Chemical Engineering Journal 317 (2017) 821843 835

Fig. 15. Structures of mesoporous materials of (a) MCM-41/SBA-15, (b) MCM-48, and (c) MCM-50. Adapted from Ref. [121].

Fig. 16. Schematic illustration of the synthesis procedure of mesoporous materials using structure-directing agents: a) true liquid-crystal template and b) cooperative liquid-
crystal template mechanism. Adapted from Ref. [121].

applications [119]. These materials are typically classified accord-
ing to the order of the pores possessing hexagonal, cubic or
meso-lamellar phases, respectively, as in MCM-41, MCM-48 or
MCM-50 (see Fig. 15) [120,121]. On the other hand, hexagonal
SBA-15 silica, which exhibits remarkable hydrothermal stability
with a wide range of pore sizes is employed more widely for appli-
cations in catalysis and adsorption [122]. Two general pathways
have been proposed for the formation of mesoporous silica (see
Fig. 16). In the liquid-crystal templating mechanism, true or
semi-liquid-crystal mesophase micelles are produced by the addi-
tion of silicate using high concentrations of surfactants, such as
cetyltrimethylammonium bromide (CTAB) as a template, and the
silica polymerize around the micelles (Fig. 16(a)). In the coopera-
tive liquid crystal template mechanism, the addition of silicate to
an aqueous CTAB solution induced the ordering of silicate-
encased surfactant micelles simultaneously (Fig. 16(b)) [121].
Chang et al. [123] prepared MCM-41 having 13.4 Si/Al ratio
from fly ash by alkali fusion of 1.2 NaOH/fly ash at 550 C for
150 h and hydrothermally treatment at 115 C for 150 h with CTAB
a structure-directing agent (SDA). Misran et al. [62] also reported
MCM-41 synthesis using CTAB over the ash supernatant solution.
They pretreated the ash mixture of 1.2 NaOH/fly ash at a fusion
temperature of 577 C followed by a hydrothermal treatment at
100 C for 5 days. As shown in Fig. 17, a sharp peak that was
assigned to the (100) plane of the hexagonal pore structure was
observed at 2.30 and 2.36 2h for as-synthesized and calcined
MCM-41 samples, respectively. Park et al. [14] synthesized meso-
porous silica, MCM-41 and SBA-15, from a supernatant solution
obtained from fused fly ash with CTAB and poly (alkylene oxide)-
based triblock copolymer Pluronic P123 (EO20PO70EO20, BASF) for
MCM-41 and SBA-15, respectively, as a SDA. In addition, the
pore-enlarged mesoporous silica materials were also prepared
using butanol and mesitylene as a pore swelling agent to improve
the textural properties. As shown in Fig. 18A, the N2 adsorption-
desorption isotherms of all SBA-15 type mesoporous silica materi-
als exhibited type IV isotherms in the IUPAC classification with
hysteresis loops. The corresponding pore size distribution curves
indicate a rather broad distribution of mesopores in the range of
10120 nm (Fig. 18B). A high efficiency of CO2 capture (218 mg/g)
was obtained when the prepared SBA-15 was used as a support
for polyethyeneimine (PEI) with a 70 wt.% loading of impregnation.
Five cyclic runs of CO2 adsorption-desorption at 75 C resulted in
only a 3% decrease in the CO2 capture capacity. Kumar et al. [58]
also prepared alumina-containing Al-MCM-41 and SBA-15 using
836 Y.-R. Lee et al. / Chemical Engineering Journal 317 (2017) 821843

Fig. 17. XRD patterns of MCM-41 products using different silica sources; (a) pure chemical and (b) alkali-fused fly ash supernatant. Adapted from Ref. [62].

Fig. 18. (A) N2 adsorptiondesorption isotherms at 77 K and (B) corresponding size distribution curves calculated by the BJH method of the SBA-15 type mesoporous silica
materials (MS) prepared using the swelling agent of (a) butanol, (b) mesitylene, and (c) as-synthesized MS sample. Adapted from Ref. [14].

Fig. 19. TEM images of (a) Al-MCM-41 and (b) SBA-15 prepared using fly ash as the starting material. Adapted from Ref. [58].

the supernatant solution obtained from fly ash. Fully crystallized
Al-MCM-41 and SBA-15 were obtained after 4 and 3 days of heat-
ing at 97 and 90 C, respectively, with a high surface area (842 and
483 m2/g) and pore volume (0.75 and 0.53 cm3/g). Transmission
electron microscopy (TEM) images of both products (Fig. 19) con-
firmed that the materials indeed possess well-ordered hexagonal
arrays of 1D mesoporous channels. The distance between the two
consecutive corners of the hexagonal pores of the SBA-15 product
was ca. 10 nm and the average thickness was approximately 6 nm,
which was larger than that for the MCM-41, and the pore diameter
was approximately 5 nm. The synthesized MCM-41 was applicable
in limited catalytic reactions such as in cumene cracking using its
 Y.-R. Lee et al. / Chemical Engineering Journal 317 (2017) 821843
weak Brnsted or Lewis acid sites. Zhang et al. [70] synthesized fly
ash-based mesoporous CdS/Al-MCM-41 nanocomposites via two-
step preparation of Al-MCM-41 using extracted silicon and alu-
minum from alkali-fused fly ash and subsequent assembly of CdS
inside the Al-MCM-4 with pore size of about 3.0 nm. The prepared
CdS/Al-MCM-41 was applied as a heterogeneous catalyst for
hydrogen production by photocatalytic water decomposition
under visible light irradiation.
Hui and Chao [63] examined the preparation of MCM-41 at
room temperature employing silica extraction carried out in an
oil bath at 100 C for 4.5 h by mixing fly ash with a 2.0 M NaOH
solution. The MCM-41 samples were prepared using CTAB as the
surfactant at 25 C for 24 h of heating by varying the pH of the syn-
thesis mixture from 11.9 to 1.16 with the addition of H2SO4. MCM-
41 with highly ordered hexagonal arrays and a uniform pore size
was obtained at pH 3.57. The samples obtained at high pH were
more hydrothermally stable than those obtained at low pH. Dhokte
et al. [65] reported MCM-41 synthesis from a supernatant solution
obtained from fly ash; a uniformly ordered hexagonal structure
was obtained after 48 h of heating at 100 C using CTAB as a surfac-
tant. The catalytic activity of synthesized MCM-41 was examined
in the Mannich reaction of acetophenone, benzaldehyde, and ani-
line, i.e., R1COCH3 + R2CHO + R3NH2 ? R1COCH2CH(NHR3)R2, and
a 90% yield was obtained when 0.2 g of MCM-41 was used in an
EtOH solvent. No reaction took place in the absence of a MCM-41
catalyst, which indicates that the catalyst is the key for the reaction
to proceed. The resulting MCM-41 catalyst could be reused 3 times
without any significant loss of catalytic activity and yield. Chan-
drasekar and Ahn [124] also synthesized SBA-16 using a super-
natant solution obtained from alkali-fused fly ash with a small
addition of sodium metasilicate and triblock copolymer of Pluronic
F127 (EO106PO70EO106) as a SDA. The obtained SBA-16 was used as
a template for the synthesis of a mesoporous carbon.
Recently, Yan et al. [66] reported the synthesis of mesoporous
nanosilica from coal fly ash via the alkali-dissolution and twice-
carbonation processes. Firstly, the coal fly ash calcined for 2 h at
800 C was mixed with 25 wt.% NaOH solution and reacted at
110 C for 0.5 h until the liquidsolid ratio was reduced to 1.5:1.
Subsequently, simulated flue gas containing 15 vol.% CO2 was
introduced to precipitate the nanosilica with the assistance of
CTAB as a surfactant through a twice-carbonation process. A series
of characterization techniques confirmed that the synthetic
nanosilica has high purity (99.35%), high surface area (1157 m2/g),
large pore volume (0.95 cm3/g), and a highly ordered hexagonal
mesostructure similar to the characteristics of the mesoporous
material prepared using silicon alkoxide.
6. Synthesis of silica aerogel and adiabatic foam using fly ash or
other solid wastes
Silica aerogels are useful for applications, such as in catalysis,
adsorption, thermal insulation, and drug delivery, because of their
Table 6
Modulus of the sodium silicate solution obtained from fly ash after different
treatments [135].
NaOH/fly ash NaOH conc. Reaction time (h) Modulus (R)
(wt./wt.) (wt%)
0.4 12 4 0.71
0.4 15 4.5 0.69
0.4 18 5 0.58
0.5 12 4 0.48
0.5 15 4.5 0.82
0.5 18 5 0.43
a
R: the mole ration of SiO2/Na2O in sodium silicate solution.
837
large surface area, large pore volume, low bulk density, and low
thermal conductivity [125128]. The raw materials used for
preparing silica aerogels are usually among the following types:
tetramethoxysilane (TMOS), tetraethyl orthosilicate (TEOS), and
polyethoxydisiloxanes [129], which are expensive and toxic. Silica
aerogels in small amounts using these precursors are usually pre-
pared by a supercritical drying process to avoid capillary stress and
drying shrinkage to achieve desirable textural properties. Recently,
water glass and various industrial wastes containing silica species,
such as fly ash acid sludge [130], bagasse ash [131], wheat husk ash
(RHA) [132], bottom ash of sugar industry [133], or kaolin [134]
have been used to produce aerogels for ecofriendly recycling. An
ambient pressure drying process is more economic and practical
for the large scale production of these silica aerogels starting from
these low quality silica sources and for the less demanding appli-
cations of an insulating material.
Shi et al. [135] prepared silica aerogels from fly ash via ambient
pressure drying. The pretreated fly ash was reacted with a 12
18 wt.% NaOH solution to obtain sodium silicate solution with dif-
ferent moduli (SiO2/Na2O molar ratio in sodium silicate). Table 6
lists the results of silica digestion with NaOH. Two different meth-
ods were adopted to prepare the silica aqueous gel: (1) vitriol-
catalysis method, in which the pH of the sodium silicate solution
was adjusted to approximately pH = 10 with a H2SO4 solution;
and (2) resin-exchange alkali-catalysis method, in which the
sodium silicate solution was first ion-exchanged using an strongly
acidic cation exchange resin to obtain silicic acid of pH = 23,
which was then controlled to approximately pH = 56 with a NaOH
solution. A trimethylchlorosilane (TMCS)/ethanol (EtOH)/hexane
mixed solution was then used for the surface modification/solvent
exchange of the silica aqueous gel obtained by both processes, and
finally the solution was dried under ambient pressure conditions.
The silica aerogels prepared by the resin-exchange-alkali-
catalysis method showed a more uniform mesoporous structure,
higher pore volume, and specific surface area than that by the vit-
riol catalysis method, whereas silica aerogels were obtained in
higher yield by the vitriol-catalysis method. As shown in Table 7,
the pore volume and pore diameter of the as-prepared silica aero-
gels were highest when the modulus was equal to 0.69. Overall, a
sodium silicate solution can be transformed to a silica gel by the
following reaction:
The elimination of capillary stress during drying is very impor-
tant for obtaining a porous silica aerogel structure. For this pur-
pose, elimination of capillary stress before ambient pressure
drying is usually carried out by removing water in the pores and
surface modification of the wet gel [136]. During the solvent
exchange/surface modification of a wet gel, the following five reac-
tions occurred [135].
(i) 2(CH3)3SiACl(TMCS) + H2O (pore water) ? (CH3)3ASiAOASiA
a
(CH3)3 + 2HCl
(ii) (CH3)3SiACl + CH3CH2OH (EtOH) ? (CH3)3SiAOACH2CH3 +
HCl
(iii) 2(CH3)3SiAOACH2CH3 + H2O (pore water) ? (CH3)3ASiAOA
SiA(CH3)3 + 2CH3CH2OH
(iv) (CH3)3SiACl + BSiAOH ? BSiAOASi(CH3)3 + HCl
(v) 2(CH3)3SiAOACH2CH3 + BSiAOH ? BSiAOASi(CH3)3 + CH3
CH2OH
838 Y.-R. Lee et al. / Chemical Engineering Journal 317 (2017) 821843

Table 7
BET specific surface area, pore volume, and average pore diameter of the as-prepared silica aerogels using a sodium silicate solution with different moduli obtained from fly ash
[135].
a
Silica gel forming process Modulus (R) BET surface area (m2/g) Pore volume (m3/g) Average pore diameter (nm)
Vitriol catalysis 0.82 578.5 1.74 12.06
0.71 535.8 2.14 15.95
0.69 530.6 3.20 24.09
0.58 454.9 0.91 7.98
0.48 384.1 0.74 7.69
0.43 362.2 0.95 10.45
Resin-exchange-alkali-catalysis 0.69 907.9 4.88 21.48
a
R: the mole ration of SiO2/Na2O in sodium silicate solution.

Fig. 20. FTIR spectra of SiO2 aerogel synthesized using the obtained sodium silicate
solution with a modulus of R = 0.69 from fly ash by (a) vitriol-catalysis and (b)
resin-exchange alkali catalysis method. Adapted from Ref. [135].

TMCS reacts with SiAOH on the surface of the gel and the
hydrophobic surface generated expels pore water rapidly. After
the reaction of TMCS with SiAOH, the formed HCl will be replaced
by hexane. Due to the low surface tension of hexane and
hydrophobic SiACH3, capillary stress and associated drying shrink-
age and cracking can be decreased, and porous silica aerogel with
low density can be obtained.
Fig. 20 shows the FT-IR spectra of the silica aerogel samples pro-
duced. The absorption bands at around 1250 cm1 and 840 cm1
were assigned to the deformation and stretching modes of SiAC Fig. 21. Schematic procedure for preparing silica aerogels from bagasse ash.
bonds, whereas those around 2960 cm1 correspond to CAH Adapted from Ref. [131].

bonds. These absorption bands of SiAC and CAH indicate that

hydrophobic SiACH3 formed as a result of surface modification
[137].
Cheng et al. [130] also synthesized silica aerogels with fly ash
acid sludge (FAAS). As shown in Table 8, the aerogel modified by
TMCS was porous and lightweight with a significantly larger pore
volume and mean pore diameter compared to its unmodified coun-
terpart because the gel modified by TMCS underwent reversible
shrinkage during ambient pressure drying. Nazriati et al. [131]
used bagasse ash as a silica source when preparing silica aerogels
via ambient pressure drying. The sodium silicate solution was
prepared from bagasse ash and underwent ion-exchange over an
acidic ion exchange resin (see Fig. 21). After adding TMCS and
hexamethyldisilazane (HMDS) successively for surface silylation,
the mixture was titrated with 1 N NH4OH to induce gel formation
in Method I or the hydrogel was dropped slowly into hexane and
pyridine was then added to induce gel formation in Method II.
The largest surface area (1114 m2/g) was obtained at a silicic acid
(SA): TMCS: HMDS ratio of 1:0.03:0.06. NH4OH or pyridine was
used to increase the condensation reaction rates in Methods I
and II, respectively. NH4OH generated a homogeneous aqueous
solution with silicic acid, and a condensation reaction took place
fast. On the other hand, the pyridine in Method II must initially dif-
fuse from the hexane into the aqueous phase containing the silicic
acid before catalyzing the condensation reaction. Therefore, the

Table 8
Bulk density, BET specific surface area, pore volume, and average pore diameter of the silica aerogels [126].

Sample Bulk density (g/cm3) BET surface area (m2/g) Pore volume (m3/g) Average pore diameter (nm)
Unmodified aerogel 0.691 668 0.37 2.24
Modified aerogel 0.085 700 3.29 18.86
 Y.-R. Lee et al. / Chemical Engineering Journal 317 (2017) 821843
Fig. 22. Schematic diagram of the procedure for preparing silica aerogel from kaolin
and dried at ambient pressure. Adapted from Ref. [134].
Table 9
Density of silica aerogel prepared with HCl solutions of different concentrations [134].
Concentration (mol/L) 2 3 4 5 6 tion of highly pure amorphous silica were 1.5 mol/L NaOH,
Density (g/cm )3
0.14 0.10 0.06 0.08 0.15
condensation reaction took place slowly, which allowed sufficient
silylation, and the decreased number of silanol groups on the silica
surface hindered the aggregation necessary to form the gel net-
works. Hence, the surface area of the silica aerogels aged in hexane
was lower than that of the aerogels aged in water.
Liu et al. [132] prepared silica aerogels from wheat husk ash
(WHA) via a solgel process by ambient pressure drying. The
SiO2/H2O weight ratio is a critical parameter for the preparation
of silica aerogels, and silica aerogels were synthesized at SiO2/
H2O weight ratios ranging from 0.065 to 0.167. When the SiO2/
H2O ratio was less than 0.065, silica particles achieved a low degree
of condensation and the sol failed to transform into a gel. When the
SiO2/H2O ratio was higher than 0.167, the transition from a sol to a
gel occurred early during ion exchange, and it was impossible to
separate the silica gels from the ion-exchange resin. In addition,
Fig. 23. SEM images of silica aerogel prepared with different concentration of HCl solution of (a) 2 mol/L, (b) 3 mol/L, (c) 4 mol/L, and (d) 6 mol/L. Adapted from Ref. [134].
839
a high SiO2/H2O weight ratio resulted in a high pH outside the
applicable scope of the ion-exchange resin. Silica aerogels usually
have low density (<0.1 g/cm3), high porosity (>75%), high specific
surface area (6001000 m2/g), and low thermal conductivity
(<0.02 W/mK). The aerogel synthesized from solid waste had a
density ranging from 0.056 to 0.158 g/cm3, surface area from 513
to 587 m2/g, pore volume from 2.3 to 4.0 cm3/g, pore size from 9
to 15 nm, and thermal conductivity from 0.009 to 0.012 W/mK,
which were almost the same with those of the aerogel synthesized
using chemicals. Amin et al. [133] used alkaline extraction
followed by acid precipitation to synthesize a silica aerogel from
the bottom ash of the sugar industry. The extracted silica was
96% pure, as determined by the HF acid test and X-ray fluores-
cence. Amorphous silica was obtained at 100 C under normal
pressure, and the optimized conditions for the maximum extrac-
2.5 mol/L HCl with a 90 min heating time after boiling.
Hu et al. [134] prepared a hydrophobic silica aerogel from kao-
lin dried at ambient pressure. Fig. 22 summarizes the preparation
process of the hydrophobic silica aerogel. The process for preparing
the aerogel consists of the following steps: activation of kaolin
with Na2CO3, preparation of wet silica sol with HCl addition,
subsequent gelation using NH4OH; hydrophobic modification,
and drying. The concentration of the HCl solution had a critical
influence on the structure and property of the silica aerogel.
Decreasing the HCl concentration from 5 to 2 mol/L resulted in
increased water content in the wet silica gel, which caused insta-
bility of the gel during drying and an increase in the density of
the dried aerogel (see Table 9). The density of the aerogel increased
when the HCl concentration was increased beyond 6 mol/L. A wet
gel formed rapidly when NH4OH was added to the silica sol with
the concomitant generation of air bubbles. The air bubbles broke
easily during the gelling process and increased the density of the
dry aerogel. Fig. 23 presents SEM images of the silica aerogel.
When the HCl concentration was increased to 4 mol/L (Fig. 23
840 Y.-R. Lee et al. / Chemical Engineering Journal 317 (2017) 821843
(c)), an aerogel with a more refined and uniform particle morphol-
ogy was obtained, whereas the particle size of the aerogel
increased and an uneven pore structure was observed when the
HCl concentration was increased further to 6 mol/L (Fig. 23(d)).
As a potential building insulation material, adiabatic foams with
macropores were synthesized from sodium silicate using fly ash as
an additive [138]. First, sodium hydroxide was added to a sodium
silicate solution to adjust the modulus of sodium silicate to ca. 1.8.
The acid-treated fly ash was then added to increase the strength of
the samples. The mixer was stirred vigorously using a direct driven
motor for 6 h to produce a stable suspension. Subsequently, the
suspension was sintered in a muffle furnace at 450 C for 30 min.
at a heating rate of 5 C/min. The structural and features of the adi-
abatic foam were examined by SEM, FT-IR spectroscopy, density,
and compression strength measurements. The pore size distribu-
tion of the adiabatic foam ranged from 0.25 to 600 mm. Adiabatic
foam could also be made from sodium silicate using boric acid or
glass fiber as additives [139,140].
7. Concluding remarks
Fly ash is a useful silica and alumina source for zeolite synthe-
sis. Prior to zeolite synthesis, the preconditioning of fly ash via acid
and subsequent alkaline treatments is essential for converting raw
fly ash to a suitable synthesis substrate material comprised mainly
of sodium silicates and sodium aluminates. An acid treatment
should be carried out to remove the impurities (e.g., CaO and
Fe2O3) from the raw fly ash because their presence hinders the
nucleation of zeolites. The acid treatment with 3 M HCl at a 1:2
mass ratio at 60 C for 1.5 h has been considered to be the opti-
mum. Acid-treated fly ash showed an increase in the silica and alu-
mina concentrations, resulting in an increase in the extraction of
sodium silicates and sodium aluminates. Alkaline fusion and diges-
tion in the liquid phase have been considered to be two alkaline
treatment procedures. In the alkali-fusion method, a mixture of
fly ash and NaOH powder at a 1:1.21.4 mass ratios and heating
at 500550 C for 1 h was found to be the optimum. The fused
powder was mixed with a sufficient amount of water and aged
for approximately 24 h. The supernatant solution is recommended
for the subsequent hydrothermal synthesis of zeolites to achieve
high product purity. On the other hand, the alkali-digestion is car-
ried out by mixing fly ash with a NaOH/KOH mixture with ade-
quate alkalinity in an autoclave and aging followed by the
hydrothermal synthesis of zeolites. Further adjustments of the
water amount and/or pH value can be carried out after digestion.
Zeolites A and X are usually synthesized after the alkali-fusion acti-
vation, whereas zeolite P was prepared by the alkali-digestion
method. According to the authors experience, higher quality zeo-
lite products are generally obtained reproducibly by the alkali-
fusion method rather than by the alkali-digestion method, even
though additional heating is required. Alkali-digestion may not
be sufficient to extract the active silica precursors necessary for
zeolite synthesis from a highly stable quartz phase.
Although the syntheses of zeolites A, X, and P via different acti-
vation protocols have been reported, the synthesis of high silica
zeolites, such as ZSM-5 is still a challenge, because of the low silica
content of the extracted solution. Considering the high cost of
structure-directing agents usually required for the formation of a
particular structure, synthesis efforts for ZSM-5 without employing
a template may be desirable. The low quality zeolites produced can
be used as adsorbents and ion-exchangers for transition metals or
alkali earth metals for water treatment. In addition, they may also
be applicable to the removal CO2 and even NOX from the power
plant effluent gases.
Limited studies to synthesize mesoporous silica materials, such
as MCM-41 and SBA-15, using fly ash have been reported. Their
potential applications, such as CO2 capture after introducing guest
amine species inside their pores, need to be optimized further.
SBA-15 can also be functionalized with various organic functional-
ities via condensation reactions with surface SiOH species, which
can be effective for capturing rare earth metal ions by coordination
bonding. Another alternative to the use of fused fly ash is the
preparation of a silica aerogel via a solgel process with ambient
drying after adding surface modifying additives, which can prove
useful as a building insulation material in the near future. The adi-
abatic foam prepared from the sodium silicate solution with acid-
treated ash additive can serve the same purpose.
Many other industrial waste products also have significant sil-
ica or alumina contents, which can be used for the synthesis of
ordered nanoporous materials. Mixing these sources together with
fly ash is also a viable approach. Only limited attempts have been
made in that direction, which can lead to interesting composite
materials and a high level of solid waste recycling.
The nanoporous materials prepared using fly ash can be used in
an integrated manner to achieve high sustainability and a clean
environment. The acid solution after an ash pretreatment would
contain a high level of Ca2+ ions that can be induced to react with
the CO2 generated from power plants and NH4OH (aided by the
alkaline ash-washed solution) to form CaCO3 [141143]. The efflu-
ent stream can be treated with the organic-functionalized meso-
porous materials to capture and recycle rare earth element (REE)
ions [144146]. Our preliminary investigation showed that REE
ions do not compete strongly with the transition metal ions for
the adsorption sites provided by the functionalized materials.
Finally, the liquid stream free from Ca2+ and REE ions can interact
with the zeolites prepared to capture transition metal ions by ion-
exchange. Although the entire process would require optimization,
making zeolites and mesoporous materials or even aerogels with
substantially reduced contaminants using fly ash is a desirable
way of recycling fly ash.
Acknowledgments
This study was supported by a grant from the Energy Technol-
ogy Development Program (20141010101840) funded by the Min-
istry of Trade, Industrial and Energy of the Korean government and
Basic Science Research Program through the National Research
Foundation of Korea (NRF) funded by the Ministry of Education
(NRF-2015R1A4A1042434).
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