Accepted Manuscript

Review

Synthesis of Nanoporous Materials via Recycling Coal Fly Ash and Other Solid
Wastes: A Mini Review

Yu-Ri Lee, June Thet Soe, Siqian Zhang, Ji-Whan Ahn, Min Bum Park, Wha-
Seung Ahn

PII: S1385-8947(17)30289-9
DOI: http://dx.doi.org/10.1016/j.cej.2017.02.124
Reference: CEJ 16563

To appear in: Chemical Engineering Journal

Received Date: 18 December 2016

Revised Date: 21 February 2017
Accepted Date: 22 February 2017

Please cite this article as: Y-R. Lee, J.T. Soe, S. Zhang, J-W. Ahn, M.B. Park, W-S. Ahn, Synthesis of Nanoporous
Materials via Recycling Coal Fly Ash and Other Solid Wastes: A Mini Review, Chemical Engineering Journal
(2017), doi: http://dx.doi.org/10.1016/j.cej.2017.02.124

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 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
Tel: +82-32-860-7466; Fax: +82-32-872-0959; E-mail: whasahn@inha.ac.kr
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

Abstract
Large quantities of fly ash are discharged as a by-product from coal power plants. Therefore,
an effective method to recycle this waste material is necessary. In this regard, the high silica
content of fly ash makes it a potential useful source for the synthesis of nanoporous materials,
such as zeolites, mesoporous silica or silica aerogels. In this mini review, zeolite synthesis from
fly ash was examined by considering the ash composition, pretreatment procedures, and
hydrothermal synthesis conditions (substrate composition and synthesis temperature/time) to
identify an optimal set of synthesis conditions. These zeolites can be used as adsorbents and ion-
exchangers for environmentally hazardous materials including those present in the fly ash itself.
The synthesis of mesoporous silica materials with a high surface area and large pore volume
derived from fly ash was next assessed for their use as a support and as a surface-functionalized
host for capturing the global warming CO2 and rare earth metal ions. Lastly, the utilization of fly
ash for the preparation of silica aerogels or adiabatic foams, which are being considered as a
potential building insulation materials, was briefly examined. Cases of synthesizing these
nanoporous materials 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 society with a low environmental burden.

Keywords: fly ash; recycling; zeolites; mesoporous materials; aerogel; adiabatic foam
Contents

1. Introduction

2. Characterization of Fly Ash and Other Solid Waste

3. Preconditioning of Fly Ash

3.1. Acid Treatment

3.2. Alkali-Fusion

4. Zeolites Synthesis

4.1. Zeolite Synthesis after Alkali-Fusion of Fly Ash

4.2. Zeolite Synthesis after Aqueous NaOH/KOH Digestion of Fly Ash

4.3. Zeolite Synthesis Using Other Solid Wastes

5. Synthesis of Mesoporous Materials Using Fly Ash

6. Synthesis of Silica Aerogel and Adiabatic Foam Using Fly Ash or Other Solid Wastes

7. Concluding Remarks
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 [2-4].
The remainder is disposed of in landfill and lagoons, which causes soil and groundwater
pollution. Because fly ash is highly contaminating 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 1 - 100 µm and is
generally grey in color, abrasive, and mostly alkaline [1,3,7]. The main components of fly ash are
amorphous aluminosilicate glasses, mullite (2SiO2 ·3Al2O3), α-quartz (SiO2), hematite (α-Fe2O3),
and magnetite (Fe3O4). Its high silica content with some alumina present makes it a suitable
starting material for the synthesis of zeolites [8-10]. The main applications of these synthesized
zeolites can be sorbents and ion-exchangers for the removal of ions and hazardous molecules
from waste water and radioactive waste, as well as adsorbents for gases containing atmospheric
pollutants [11-13]. Recently, zeolites have also been studied extensively as a capturing agent for
the global warming CO2 [14]. Under these circumstances, 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 applications [15]. Further applications of these
zeolites have been suggested 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) [21-37], Y (FAU) [33,38], A (LTA) [21,22,27,29,30,33-35,37,39-42], P
(GIS) [27,29,43-55], and some others, such as ZSM-5 (MFI) [56] and phillipsite (PHI) [57], using
fly ash via hydrothermal 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
limitations of the microporous zeolites with pore sizes less than 1.3 nm [58-65]. 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 insulation [71,72], catalyst [73], and adsorbent [74] through a route involving
the surface modification of wet gels and ambient pressure drying [75-77]. 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
[71,75-94]. 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 significantly 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 substrate concentrations to identify an
optimal set of synthesis conditions. 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, bituminuous, 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 aluminosilicate [1]. Steenari et al.
reported that the chemical and leaching characteristics of the fly ash must be known before ash
residue can be used or deposited [96]. Table 1 lists the chemical composition of the oxide forms
of different fly ash sources reported in the literature [14,25,26,28,29,33-36,38,43,44,47-
49,52,53,61,62,64,65,97,98]. X-ray fluorescence (XRF) has revealed the major components 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 samples [27,52,55,98]. The powder XRD patterns indicate that the
major crystalline phases in fly ash are α–quartz and mullite along with other amorphous
aluminosilicates. Crystalline α –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 aluminosilicate glass phase is the largest and most unstable under
the hydrothermal condition, which leads to the highest rate of dissolution 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 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 [78-83, 89-94]. 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.

3. Preconditioning of Fly Ash

3.1. Acid Treatment

The preconditioning of fly ash with an acid treatment is a necessary 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 framework 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 zeolites 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 thoroughly with distilled water until the pH reaches 6 - 7 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 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) washing 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
disappear 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 process as calcium and some other acid-soluble salts are dissolved.

3.2. Alkali-Fusion

Alkali-fusion is a typical pretreatment necessary to extract silica (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 α-quartz and mullite in
fly ash are reacted with an alkaline reagent (usually NaOH powder) according to the following
reaction:

SiO2 (s) + 2NaOH (s) → Na2SiO3 (s) + H2O

Al2O3 (s) + 2NaOH (s) → 2NaAlO2 (s) + H2O

Elemental analysis of the aqueous solution containing the dissolved 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.
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 original fly ash has a spherical particle shape with a glassy and
smooth surface, the surface becomes rough after the alkali-fusion treatment and larger cracks are
eventually observed with increasing treatment time, indicating the dissolution of α-quartz to the
sodium silicate form [97].
The conversion of fly ash to sodium silicate and sodium aluminate by an alkali-fusion
treatment depends on the amount of NaOH 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 crystallinity. Therefore, 1.2 NaOH/fly ash is the
optimum for the formation 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 crystallinity
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 (0.5 to 2 h) on zeolite
formation were also studied at 550 oC [107]; a fusion time of 30 min was insufficient and zeolite
X peaks appeared after 1 h with a maximum crystallinity observed after 2 h.

4. Zeolites Synthesis

A representative flow diagram for the zeolite synthesis procedures 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
temperature 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 [14,21,22,26,28,32-34,36-38,52,53,61-65,97].
As an alternative to the alkali-fusion treatment, digestion of fly ash with 2 – 5 M of NaOH or
KOH solution, was carried out for 2 to 12 h. When necessary, an extra aluminum source and
water were added to control the molar ratio of the synthesis mixture. Subsequently, hydrothermal
synthesis was conducted at 100 - 200 °C for 3 - 48 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 micron size, were obtained at 100 oC for 4 h and 90 oC 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 different fly ash sources.
Aluminum hydroxide hydrate, as the aluminum 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 zeolites 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 synthesis mixture and heating time (4 days). Zeolites A and X were
also synthesized from the supernatant solution of the fused mixture 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 mixture, hydroxysodalite (SOD) was obtained instead of zeolite X. The addition of sodium
aluminate to the above fused fly ash solution (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 ºC after 7 h of heating, whereas zeolite X was obtained at 100 ºC 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 concentration, 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 zeolite Y was comparable to that of commercial zeolite Y and its Ca2+ cation
exchange capacity was 4 - 4.5 meq/g. El-Naggar et al. [97] obtained a mixture of zeolites A and
X with a maximum crystallinity of ~96 % and surface area of 594 m2/g after hydrothermal
synthesis at 90 ºC 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.
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
conditions of a 1.5 composite alkali mixture/fly ash mass ratio and a fusion temperature of 800 ºC,
followed by a hydrothermal treatment at 110 ºC 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 varying the hydrothermal reaction temperatures (75 - 95 °C) and
reaction time (12 - 48 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 showing 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 (25 - 40 °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
sodalite 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 presence 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 was formed after a 24 h hydrothermal treatment at 90 °C from the alkali-digestion method,
which was converted successively to zeolite 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 2 - 3 µm was obtained at 120 °C for 4 h of
hydrothermal synthesis under at a chemical composition of 2.2SiO2·Al2O3·5.28Na2O·106H2O.
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 NH4+ 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 cancrinite 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 increases to 3 days resulted in the formation of a mixture of sodalite 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 solution 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, increasing NaOH concentration resulted in a greater increase in Si
dissolution than Al from coal fly ash [110,111].
Tanaka et al. [40] conducted the digestion of fly ash accompanied 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 pretreated 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 synthesized at 85 °C for 24 h with the addition of a NaOH-NaAlO2 mixture 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/Al2 O3 = 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
digestion. 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 produced different
zeolite phases despite the same activation conditions, which might be due to the unknown
impurities present in the original fly ash source. Querol et al. [50] also prepared zeolite P by
microwave-assisted synthesis. Although the zeolite yields obtained were similar to those of
hydrothermal synthesis, the synthesis 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. Hydroxysodalite 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 different weight percentages of nano-sized magnetite
(10 – 75 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 suggested that MW and US energy can decrease the synthesis time
significantly [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
product treated with alkali fusion had a higher BET surface area (64 m2/g) because of the
differences in the dissolution of aluminum 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 treated with MW at 100 oC. The early-stage heating for 0–
15 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 45-60 min retarded zeolite
formation caused by the retarded nucleation in the intermediate aluminosilicate 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 NH4+ 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 oC 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 oC. 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 Al2O3:1.94·SiO2:4·Na2O:100·H2O. A fully crystalline product was obtained at 70
o
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 treatment facilitates the formation of
zeolites at significantly low temperatures 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
materials reduced. According to Ojha et al. [100], the stability of the zeolite 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 product 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 zeolite A and X samples either prepared using chemicals or fly ash were within 20 % [79].
The effect of impurity on the physicochemical properties of synthesized zeolite products has been
reported 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 oC 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 zeolite 13X
synthesized from fly ash was about one-fifth of commercial 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 production 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
pretreated 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
crystallinity 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] prepared 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 aluminum 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 employing 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 residue by hydrothermal synthesis
after alkali-fusion, and examined the effects of a mineralizing agents (NaOH and Ca(OH)2),
fusion temperature (250 - 500 °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 pseudoboehmite as an
alternative aluminum source led to the formation 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., nepheline, 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 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 prepared 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 formation 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 (2.5 - 40) 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 photocatalytic 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 erionite (ERI) and offretite (OFF) ERI-OFF structure, by the
direct dissolution 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.
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 bentonite/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 ºC, 1 bar). The thermal analysis data
showed that the prepared 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. Mesoporous silica synthesis from fly ash is anticipated to overcome
the limitations of the microporous zeolite materials in the adsorptive 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 ~ 20 nm) and large
amounts of internal silanol (Si-OH) groups inside the pores that can be modified easily by
functionalization with other useful organic groups for a range of industrial applications [119].
These materials are typically classified according 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 applications 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 addition 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 cooperative 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 oC 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° 2θ for as-synthesized and calcined MCM-41 samples,
respectively. Park et al. [14] synthesized mesoporous 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 materials 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 10 – 120 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 the supernatant solution obtained from fly ash. Fully
crystallized Al-MCM-41 and SBA-15 were obtained after 4 and 3 days of heating 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) confirmed
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 weak Brönsted 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 aluminum
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 synthesis 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 surfactant. The catalytic activity of synthesized MCM-41 was examined
in the Mannich reaction of acetophenone, benzaldehyde, and aniline, 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. Chandrasekar
and Ahn [124] also synthesized SBA-16 using a supernatant 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 oC for 0.5 h until
the liquid−solid 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 (1,157 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 large surface area, large pore volume, low bulk
density, and low thermal conductivity [125–128]. 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 prepared 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
applications 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 different moduli (SiO2/Na2O molar ratio in sodium silicate). Table 6 lists the results
of silica digestion with NaOH. Two different methods 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=2–3, which was then controlled to approximately
pH=5–6 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
vitriol 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 aerogels 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:

Na2O∙nSiO2 (sodium silicate) + H+ → HxSiOy (silicic acid) + Na+

↓

SiO2 sol → SiO2 gel

The elimination of capillary stress during drying is very important for obtaining a porous
silica aerogel structure. For this purpose, 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
reactions occurred [135].

(i) 2(CH3) 3Si-Cl(TMCS) + H2O (pore water) → (CH3) 3-Si-O-Si-(CH3) 3 + 2HCl

(ii) (CH3) 3Si-Cl + CH3CH2OH (EtOH) → (CH3) 3Si-O-CH2CH3 + HCl
(iii) 2(CH3)3Si-O-CH2CH3 + H2O (pore water) → (CH3) 3-Si-O-Si-(CH3) 3 + 2CH3CH2OH
(iv) (CH3) 3Si-Cl + ≡Si-OH → ≡Si-O-Si(CH3)3 + HCl
(v) 2(CH3)3Si-O-CH2CH3 + ≡Si-OH → ≡Si-O-Si(CH3)3 + CH3CH2OH

TMCS reacts with Si-OH on the surface of the gel and the hydrophobic surface generated
expels pore water rapidly. After the reaction of TMCS with Si-OH, the formed HCl will be replaced
by hexane. Due to the low surface tension of hexane and hydrophobic Si-CH3, capillary stress
and associated drying shrinkage 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 produced. The absorption
bands at around 1250 cm−1 and 840 cm−1 were assigned to the deformation and stretching modes
of Si–C bonds, whereas those around 2960 cm−1 correspond to C–H bonds. These absorption
bands of Si–C and C–H indicate that hydrophobic Si–CH3 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 counterpart 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−1) 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 diffuse from the
hexane into the aqueous phase containing the silicic acid before catalyzing the condensation
reaction. Therefore, the 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 networks. 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 sol–gel
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, 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 (600 ~1000 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 fluorescence.
Amorphous silica was obtained at 100 оC under normal pressure, and the optimized conditions
for the maximum extraction of highly pure amorphous silica were 1.5 mol/L NaOH, 2.5 mol/L
HCl with a 90 min heating time after boiling.
Hu et al. [134] prepared a hydrophobic silica aerogel from kaolin 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
instability 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(c)), an aerogel with a more refined and uniform
particle morphology 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 adiabatic foam were examined by SEM, FT-IR spectroscopy,
density, and compression strength measurements. The pore size distribution 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 synthesis. 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 optimum. Acid-treated fly ash showed an increase in the silica and alumina
concentrations, resulting in an increase in the extraction of sodium silicates and sodium
aluminates. Alkaline fusion and digestion 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 : 1.2 - 1.4 mass ratios and heating at 500 - 550 °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
carried out by mixing fly ash with a NaOH/KOH mixture with adequate 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 activation, whereas zeolite P was prepared by the alkali-
digestion method. According to the authors’ experience, higher quality zeolite 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 activation 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 functionalities 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 sol-gel
process with ambient drying after adding surface modifying additives, which can prove useful as
a building insulation material in the near future. The adiabatic 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 silica 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 [141-143].
The effluent stream can be treated with the organic-functionalized mesoporous materials to
capture and recycle rare earth element (REE) ions [144-146]. 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 Technology Development Program
(20141010101840) funded by the Ministry 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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List of Figures

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], and
[98].

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].

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].

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].

Fig. 6. SEM images of (a) raw fly ash and (b – d) fused fly ash treated for 15, 30, and 60 min at
550 oC 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 (● : Na-A; ○: Na-X; □ :
hydroxysodalite; △ : acid-soluble component). Adapted from ref. [28].

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].

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].
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: (a and b) powder XRD patterns of zeolite X
synthesized at different temperatures and times, respectively, (c) N2 sorption isotherms (■: pure
chemicals; ▲: alkaline-fused ash precipitate; ● alkaline-fused ash), and (d) CO2 adsorption
isotherms (♦: pure chemicals; ○: alkaline-fused ash precipitate; ■: alkaline-fused ash). Adapted
from ref. [14].

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].

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].

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].

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 adsorption–desorption 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].
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].

Fig. 21. Schematic procedure for preparing silica aerogels from bagasse ash. Adapted from ref.
[131].

Fig. 22. Schematic diagram of the procedure for preparing silica aerogel from kaolin and dried at
ambient pressure. Adapted from ref. [134].

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].
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], and
[98].
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].
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 refs. [105].
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].
Fig. 6. SEM images of (a) raw fly ash and (b – d) fused fly ash treated for 15, 30, and 60 min at
550 oC 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 (● : Na-A; ○: Na-X; □ :
hydroxysodalite; △ : acid-soluble component). Adapted from ref. [28].
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 refs. [108].
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].
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: (a and b) powder XRD patterns of zeolite X
synthesized at different temperatures and times, respectively, (c) N2 sorption isotherms (■: pure
chemicals; ▲: alkaline-fused ash precipitate; ● alkaline-fused ash), and (d) CO¬2 adsorption
isotherms (♦: pure chemicals; ○: alkaline-fused ash precipitate; ■: alkaline-fused ash). Adapted
from ref. [14].
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].
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].
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].
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 adsorption–desorption 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].
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].
Fig. 21. Schematic procedure for preparing silica aerogels from bagasse ash. Adapted from ref.
[131].
Fig. 22. Schematic diagram of the procedure for preparing silica aerogel from kaolin and dried at
ambient pressure. Adapted from ref. [134].
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].
List of Tables
Table 1 Chemical compositions of diverse fly ash sources.

Table 2 Chemical compositions of other waste sources.

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

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

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

Table 6 Modulus of the sodium silicate solution obtained from fly ash after different treatments
[135].

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].

Table 8 Bulk density, BET specific surface area, pore volume, and average pore diameter of the
silica aerogels [126].
Table 9 Density of silica aerogel prepared with HCl solutions at different concentrations [134].
Table 1
Chemical compositions of diverse fly ash sources.
chemical composition (wt. %)a
fly ash no. SiO2 Al2O3 Fe2O3 TiO2 CaO MgO Na2O K2O others ref.
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.
Table 2
Chemical compositions of other waste sources.
chemical composition (wt. %)a
Source SiO2 Al2O3 Fe2O3 TiO2 CaO MgO Na2O K2O others ref.
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.
Table 3
Synthesis of ordered porous materials after alkali-fusion of fly ash.
alkaline fusion fused ash treatment synthesis of materials
NaOH/fly ash H2O aging
(wt./wt.) time (h) temp. (°C) (wt. % ) time (h) time (h) temp. (°C) products ref.
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]
Table 4
Synthesis of ordered porous materials after NaOH digestion of fly ash.
NaOH digestion synthesis of materials
NaOH/fly ash (mL/g) NaOH conc. (M) time (h) temp. (°C) products ref.
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 derivitives, 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]
Table 5
Optimum synthesis conditions of zeolites from other waste sources.
wastes molar compositions alkaline fusion fused ash treatment synthesis of materials
NaOH/waste time temp. H2O aging time time temp. products ref.
SiO2 Al2O3 Na2O H2O (wt./wt.) (h) (°C) (wt. %) (h) (h) (°C)
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 18.2 11.9 57.3 75.9 3.0 1 700 - - 3 90 LTA [81]
slage 18.2 11.9 57.3 75.9 - - - - - 9 90 SOD
cupola sladg 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 hsk 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/ 3.2 1.0 5.1 205 1.6 2 600 5 24 6 100 FAU [93]
bauxite
bentonite - - - - 1.4 6 600 4 24 12 80 FAU [94]
Table 6
Modulus of the sodium silicate solution obtained from fly ash after different treatments [135].
NaOH/fly ash (wt./wt.) NaOH conc. (wt%) Reaction time (h) Modulus (R) a
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.

71
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].
Silica gel forming Modulus BET surface area Pore volume Average pore
process (R) a (m2/g) (m3/g) 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- 0.69 907.9 4.88 21.48
alkali-catalysis
a
R : the mole ration of SiO2/Na2O in sodium silicate solution.

72
Table 8
Bulk density, BET specific surface area, pore volume, and average pore diameter of the silica
aerogels [126].
Bulk density BET surface area Pore volume Average pore
Sample
(g/cm3) (m2/g) (m3/g) diameter (nm)
Unmodified aerogel 0.691 668 0.37 2.24
Modified aerogel 0.085 700 3.29 18.86

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Table 9
Density of silica aerogel prepared with HCl solutions of different concentrations [134].
Concentration (mol/L) 2 3 4 5 6
3
Density (g/cm ) 0.14 0.10 0.06 0.08 0.15

74
 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, Daejeon 34132, Republic of Korea

c
Department of Energy and Chemical Engineering, Incheon National University, Incheon 22012,
Republic of Korea

Graphical abstract

___________________

75
Corresponding author: W.S. Ahn

Tel : +82-32-860-7466, Fax : +82-32-872-0959, E-mail : whasahn@inha.ac.kr

76
 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
Tel: +82-32-860-7466; Fax: +82-32-872-0959; E-mail: whasahn@inha.ac.kr
b
Korea Institute of Geoscience and Mineral Resources, Daejeon 34132, Republic of Korea
c
Department of Energy and Chemical Engineering, Incheon National University, Incheon 22012,
Republic of Korea

Research Highlights

► 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

77