Microporous and Mesoporous Materials 287 (2019) 183–191

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Microporous and Mesoporous Materials

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Zeolite synthesis from industrial wastes T

*
M. Yoldi, E.G. Fuentes-Ordoñez, S.A. Korili, A. Gil
INAMAT-Science Department, Los Acebos Building, Public University of Navarra, Campus of Arrosadia, 31006 Pamplona, Spain

A R T I C LE I N FO A B S T R A C T

Keywords: Conventional synthesis conditions for each type of zeolite are tabulated and reported by the International Zeolite
Industrial waste valorization Association Structure Commission (IZA) and most of them are synthesized from commercial reagents, but they
Zeolite synthesis from wastes can also be synthesized from industrial by-products rich in Si and/or Al. In zeolite synthesis from wastes,
Zeolite environmental applications concentration of alkali source, temperature, reaction time, liquid/solid ratio and type of waste determine the
textural properties, crystal structure, Si/Al ratio and ion exchange characteristics of the fabricated zeolite and its
applications. This work summarizes the main methods that have been developed to synthesize zeolites using
industrial wastes as Al and/or Si sources, the parameters of synthesis and the advantages and limitations of each
synthesis process. The main characteristics and the applications of these synthetic waste zeolites are also re-
ported.

1. Introduction studied in the 1920s and the commercial use of natural zeolites some
years later. It was determined that natural zeolites are contaminated by
Zeolites are microporous crystalline hydrated aluminosilicates of Fe2+, SO42−, SiO2, other zeolites or amorphous glass and they have
tetrahedral SiO4 and AlO4− units. Si or Al atoms are centrally placed, restricted pore sizes and channels. So, they are not suitable for com-
and O atoms in the corners, shared between SiO4 and AlO4−, and or- mercial applications if uniformity and purity are critical. To solve these
iented to generate pores and channels [1]. Al3+ produces a net negative limitations, researchers started to investigate the synthesis of zeolites.
charge that is compensated by extra cations such as Na+, K+, Ca2+ and Conventional synthesis conditions for each type of zeolite are generally
Mg2+ in the voids. Moreover, zeolite lattice is very stable and the bonds performed in closed reaction systems, where Al and Si sources are
of ions and molecules in the pores are weak and they can be removed mixed to generate a supersaturated solution and heated at temperatures
without destroying zeolitic framework. Due to its negatively charged from 30 to 180 °C for minutes to days, to develop nucleation and
surface and internal pores, chemical composition and their interesting crystallization processes [1]. The synthesis conditions for each type of
properties, zeolites present interesting applications in separation, fil- zeolite are tabulated and reported by the International Zeolite Asso-
tration, ion exchange, catalysis and adsorption processes [1,2]. ciation (IZA) [3].
The main properties of zeolites are chemical composition, cation Synthesis procedures from industrial wastes have two advantages
exchange capacity (CEC), channel or pore diameter and volume. Some comparing to commercial zeolites synthesized from pure chemicals:
properties, such as acid resistivity, thermal stability and hydrophobicity waste zeolites are cheaper than conventional and using industrial
increase with the Si/Al molar ratio but other ones, as hydrophilicity, wastes as Al and/or Si sources leads to by-products valorization.
acid site density and cation concentration decrease. Based on the Si/Al Zeolitization mechanism from a waste have four stages: Al and Si dis-
molar ratio, there are 3 types of zeolites [1]: solution, geopolymer formation, crystalline structure nucleation and
zeolite crystal growth. And the main parameters of synthesis are: the
• low silica zeolites: Si/Al < 2, such as analcime (ANA), cancrinite available contents of Si and Al, temperature, pressure, alkalinity and
(CAN), Na-X (FAU), natrolite (NAT), philipsite (PHI), sodalite (SOD) liquid/solid ratio [1,2].
• intermediate silica zeolites: 2 < Si/Al < 5 as chabazite (CHA), The first aim of the researchers was studying the characteristics of
faujasite (FAU), mordenite (MOR), Na–Y (FAU) the industrial wastes and the parameters of synthesis to produce pure
• high silica zeolites: Si/Al > 5 like ZSM-5 (MFI), zeolite-B (BEA). and stable zeolites, suitable for industrial applications. And a second
important challenge was removing the non-zeolitic phases and residual
Zeolites were identified by Cronsted in 1756, their properties were waste to increase the quantity of zeolite produced and making its

*
Corresponding author. Tel.: +34 948 169602.
E-mail address: andoni@unavarra.es (A. Gil).

https://doi.org/10.1016/j.micromeso.2019.06.009
Received 24 March 2019; Received in revised form 6 June 2019; Accepted 10 June 2019
Available online 12 June 2019
1387-1811/ © 2019 Elsevier Inc. All rights reserved.
M. Yoldi, et al. Microporous and Mesoporous Materials 287 (2019) 183–191

Fig. 1. Steps of the hydrothermal method (adapted from Ref. [7]).

synthesis more efficient and cheaper.

2. Zeolite synthesis with Si sources from industrial wastes

This point summarizes the studies of zeolite synthesis from coal and
biomass fly ashes that have been published since 1990. Coal ash is the
major solid residue produced by coal combustion in thermoelectric
power plants and biomass ash is the combustion residue of biomass,
that is a renewable energy. As they contain available Si and Al in their
composition, are suitable to zeolite synthesis [4].
Coal fly ash as Al and Si sources for zeolite synthesis was published
by Höller and Wirsching in 1985 [5]. Low silica zeolites analcime
(ANA), cancrinite (CAN), Na-X (FAU), natrolite (NAT), philipsite (PHI),
sodalite (SOD) and the intermediate silica zeolites chabazite (CHA), Fig. 2. Multi step: pre-fusion + hydrothermal treatment (adapted from Ref.
faujasite (FAU), mordenite (MOR) and Na–Y (FAU) was reported but [7]).
high silica zeolites not. Conventional or fusion-assisted hydrothermal
processes, multi-step treatment, microwave heating or ultrasonic pro-
the CFA is not emitted because power plants clean the flue gases by
cessing were used to synthesize zeolites from coal or biomass (see
particle removal, but it requires large areas to storage so is mixed with
Figs. 1 and 2) [1–4]. All methods have advantages and disadvantages
water to deposit in controlled dumps. The main problems of CFA
and researchers have investigated strategies to improve them: Höller
management are the large area required for disposal, its toxicity and the
and Wirsching [5] studied an alkaline activation of the coal fly ash as a
expensive costs of transportation [7–10]. With an expected 0.6 ha per
function of temperature, solution composition and concentration in
MW, the area required in 2020 will be 82200 ha. CFA disposal costs are
open and closed systems for long activation periods (from 8 to 40 days).
function of the type of ash, distance from the plant to the landfill,
A fusion with NaOH before hydrothermal reaction has been applied by
transportation, weather, legal requirements and potential for future
Shigemoto et al. [6] to synthesize Na-X zeolites. Jha et al. [1,2] ob-
uses. If the disposal site is near the power plant and the material can be
tained high Na and K zeolites with an alkaline activation and synthesis
easily handled the cost is low, from €3.00 to €5.00 per ton. It increases
times from 8 to 100 h and published that alkali activation determines
up to €40.00 per to when distance is far, or CFA must be manipulated
efficiency, type of zeolite and crystallinity. Few studies have been re-
several times. CFA management does not finish with transportation and
ported using biomass ash in zeolite synthesis and most of them with rice
placement in a dump, the need for future space is important too. If CFA
husk ash [7]. Rice rush ask is interesting biomass ash for zeolite
is valorized disposal is not required and the need to develop future sites
synthesis, but recent studies reveals that oil palm mill fly ash (POMFA)
either [11].
and bagasse fly ash (BFA) too [7].
According to the hazardous waste management of 1989, fly ash is a
non-hazardous waste and CFA is treated as a by-product. It is used in
2.1. Zeolite synthesis from coal fly ash construction, Portland cement and ceramic production, fabrication of
catalysts, zeolites or fibers, fillers in polymers and as adsorbents for air
Coal combustion products (CCPs) are produced in coal-fired power and water. These applications valorize the 20% of CFA and the rest is
plants, and coal fly ash (CFA) is the abundant component. Due to the deposited in controlled dumps [8,9]. Recycling CFA instead of disposal
high and increasing energy need, the 7000 coal-fired power plants is the best solution and US, EU and India reported to recycle 50%, 90%,
produce MT600 of CCPs annually and CFA is the 80% [7–10]. Most of

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Fig. 3. XRD patterns of representative raw fly ash sources from various areas (adapted from Ref. [10]).

and 60% CFA, respectively [7]. According to the regulation, new plants mixture of K+ and Na+ [10]. The Si/Al ratio determine the CEC, sta-
will mandatory use the 100% of CFA in 9 years and the old ones in 15 bility and applications of the waste zeolite.
years [9]. So, valorization of CFA as residual resource to synthesize According to the published articles [7–25], zeolites Na-X (FAU),
value products is being studied. Zeolites are interesting as adsorbents, Na–Y (FAU), Na-A (LTA), Na–P (GIS), ZSM-5 (MFI) and phillipsite (PHI)
molecular sieves or catalysts because they have large specific surface have been synthesized by hydrothermal treatment in alkaline medium.
area, specific pore sizes, molecular sieving ability and acidity. More- Alkali activation is suitable to extract the Si and Al from the CFA waste.
over, zeolite X has high and selectivity adsorption for CO2 and good The characterization of the waste zeolites synthesized by alkali acti-
desorption properties. So, the synthesis of zeolites is very interesting for vation and hydrothermal method shows that the amount of Si and Al
researchers. CFA is a potential Si and Al source for zeolite synthesis but, dissolved from glass, quartz and mullite are 50%, 2% and 2%, respec-
as the Si content in CFA is low to synthesis high silica zeolites, only low tively. Studies also reveal that quartz and mullite dissolve completely
and medium silica waste zeolites are summarized in this point. applying fusion and hydrothermal activation [7,21].
XRD patterns of CFA show that 1/3 are crystalline phases quartz Zeolite X and Y are synthesized from CFA by fusion and hydro-
(SiO2), mullite (3Al2O3·2SiO2), hematite (Fe2O3) and magnetite (Fe3O4) thermal processes. The SiO2/Al2O3 ratio in the CFA is from 3.3 to 3.5,
and 2/3 are amorphous aluminosilicate. Si and Al of quartz, mullite and what is better for zeolite Y than for zeolite X, but not selective. So, it
aluminosilicate are solved in alkaline medium at hydrothermal tem- must be increased adding Na2SiO3 or decreased with NaAlO2 to have a
perature (see Fig. 3), reducing the amount of CFA as waste and gen- specific synthesis of zeolite Y or X. Crystallinity also depends on the
erating a Si and Al source to synthesize zeolites, that are high value amount of Na+ because it balances the Al3+ that went into the zeolite.
products [10]. As zeolite Y transforms to hydroxysodalite at high pH, NaOH is not
Alkaline-fusion and alkali-digestion activation have been studied to adequate neither as alkaline medium either to increase Na+. Na2SiO3
synthesize high pure zeolites from CFA. Zeolites A and X are synthe- and NaAlO2 are proper reagents to adjust Si/Al ratio and add Na+
sized by alkali-fusion activation while zeolite P by alkali-digestion. without increasing the pH [10]. Zeolite A, X or P, are synthesized ap-
According to Lee at al [10], alkali-fusion leads to obtain better zeolites plying longer crystallization times respectively [10,22]. As CaO and
alkali-digestion activation, but it requires heating. Fe2O3 difficult zeolite nucleation, acid activation is better than alkaline
Fig. 4 (SEM micrograph) show that CFA are made of glass particles one if CFA has these oxides as impurities, because it extracts Si and Al
with smooth boundaries that become irregular or disappear as being and also removes the oxides [10].
solved, and new crystalline particles appear, that are the precipitated Zhan et al. [21] reported an interesting procedure to synthetize
zeolites. Na–P1, hydroxysodalite, Na-X, Na–Y, Na-A, Na-4A, Na-4A-X, zeolite 13X by hydrothermal treatment using CFA as the only sources
philipsite, faujasite and analcime, as individual phases or mixtures, are for Si and Al (see Fig. 5). The zeolite 13X obtained has highly crystalline
obtained if the alkali source contain Na+. Hydroxycancrinite, Na–P structure and uniform octahedra particles (see Fig. 6), high BET surface
and/or chabazite are synthesized if the alkali source has K+ or a area (643 m2/g) and CO2 capture capacity (225 mg CO2/g zeolite) and

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Fig. 4. SEM images of (a) raw fly ash and (b–d) fused fly ash treated for 15, 30, and 60 min at 550 °C (adapted from Ref. [10]).

digestion and hydrothermal treatment with NaOH and microwave ir-

radiation improves this synthesis [10]. Ozdemir and Piskin [25] also
found that the aging time for the synthesis of zeolite X can be reduced
with the usage of ultrasonic energy. Recently, a green procedure to the
synthesis of zeolite 4A is reported by Yang et al. [23]. An alkaline
mixture of NaOH/Na2CO3 is proposed by the authors.

2.2. Zeolite synthesis from biomass ashes

Biomass is all material based in C, H and O that is produced by

plants, animals or humans. The estimated biomass production in the
world is 104.9·109 ton and wood are the largest biomass source [26,27].
Biomass is used as clean energy and as source to synthesize some
chemicals. Biomass stores energy from the sun because plants absorb it
from the photosynthesis processes, and it is released as heat by a simple
combustion, co-firing with other fuels or through gasification. Despite
its CO2 emissions, biomass energy is classified as renewable in the EU
and US because plant stocks are renovated with new growth and re-
duces the dependence on fossil fuels. The annual production of biomass
is 1·1011 ton and the stored energy is 25 TW per ton of biomass, so
biomass energy is 16.7–33.4 TW h. As annual world energy consump-
tion is 17.7 TW h, biomass could supply 1.4 times the demand [27].
Although biomass energy is interesting, the reports summarized in this
review only includes zeolite synthesis.

Fig. 5. Schematic diagram of one step acid leach process (adapted from Ref.
2.2.1. Palm oil mill fly ash (POMFA)
[21]). POMFA is used as source for concrete or solid additives but it can
also be used as Si source to synthesize zeolites. As it has been com-
mented, zeolites have good CO2 adsorption and desorption properties
fast adsorption kinetics [21].
and zeolite X, especially zeolite 13X, has higher absorption capacity and
Regarding alkali-digestion, NaOH/KOH is the better medium and
better selectivity for CO2 than other types of zeolite. Kognoo et al. [22]
alkalinity must be adjusted for each type of zeolite, but it does not
published an interesting and low-cost method to synthesize zeolite 13X
extract Si from quartz phase. Zeolite NaP1 is synthesized by alkali-
from POMFA by alkaline fusion and hydrothermal treatment. They

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Fig. 6. XRD patterns and SEM images of synthesized zeolite 13-X (adapted from Ref. [21]).

capacity than inactivated and 11% higher commercial zeolite 13X (see
Fig. 7). However, the crystallinity of the zeolite 13X decreases 17% in
acid activation although FAU structure is stable [22].

2.2.2. Bagasse fly ash (BFA)

Bagasse fly ash (BFA) is a solid residue from bagasse combustion
system in sugar industries and contain various types of particles with
different size, morphology and chemical composition. Fine particles
contain Si and are a suitable source for zeolite synthesis. As it has been
commented in the previous point, CFA is low cost Si and Al sources but
the alkali extract from CFA also contains other compounds that are
incorporated in the zeolite structure contaminating it [28]. BFA contain
fewer components than CFA and alkaline treatment extracts only Si and
Al, what is a purer source and leads to synthesized zeolite with higher
quality and reproducibility.
Hydrothermal treatments can be applied in one or in two steps [28].
The single step method used all the extracted Si without any separation,
so a residual waste is not generated, but the synthesized zeolite has
Fig. 7. CO2 adsorption isotherms at 32 °C on POMFA-zeolite 13X, acid-acti- particles irregularities and crystal differences. The two steps method
vated POMFA-zeolite 13X and commercial zeolite 13X (adapted from Ref.
separates the alkaline aqueous solution and the residual waste, and the
[28]).
obtained zeolite is purer and more regular. Purnomo et al. [28] pub-
lished the synthesis of high pure and regular zeolites using BFA as Si
studied the effects of mass ratio of NaOH/(SiO2 and Al2O3 precursors), and Al sources with low residual waste. Extraction is performed with
fusion temperature and fusion time, and the acid activation to increase NaOH fusion and residual waste is separated to remove impurities that
the CO2 adsorption capacity. The prepared zeolite 13X was character- reduce zeolite formation. The Si/Al ratio of the alkaline aqueous solu-
ized by XRD, XRF, SEM, N2 adsorption-desorption measurements and tion is adjusted according to the zeolite pursue and synthesis is made by
CO2 adsorption by thermogravimetric analysis. The higher efficiency, hydrothermal method. Adjusting the pH is also important because
zeolite 13 × 85%, was obtained with NaOH/(SiO2 and Al2O3 pre- zeolites dissolves in high alkaline medium. Low temperature leads to
cursors) ratio of 1.6, 600 °C, 1 h. Inactivated POMFA zeolite 13X has a synthesize zeolite with higher purity and smaller particle size, but
BET surface area of 643 m2/g and a CO2 adsorption capacity of 223 mg/ longer time is needed. BFA zeolites have higher porosity and ion ex-
g. Acid-activated POMFA zeolite 13X has 22% higher CO2 adsorption change capacity than the commercial ones because SOD, an impurity of

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low porosity and ion exchange capability, is not synthesized [28].

3. Zeolite synthesis with Al sources from industrial wastes

Aluminum saline slags are produced by the secondary aluminum

industry in the Al scrap/dross melting processes. The amount salt slags
generated ranges from 30 to 60% of the Al produced. This waste con-
tains 3–9 wt% metallic Al, 20–50 wt% oxides (non-metallic products) as
Al2O3, Na2O, K2O, SiO2, and MgO, 50–75 wt% flux brines as NaCl and
KCl and other components as NaI, Al4C3, Al2S3, Si3P4, Na2SO4, Na2S and
cryolite in small percentages. In contact with water, some of these
components generates NH3, H2, N2, CH4 that are emitted to the atmo-
sphere, aluminum saline slags are hazardous wastes and must be de-
posited in controlled dumps. Mton of aluminum saline slags are pro-
duced annually and the 95% is landfilled, what cost M€80 [29].
Fig. 9. XRD patterns of zeolite-X synthesized from Si sludge and precipitated Al
However, is a hazardous waste that can be valorized as inert filling (OH)3 from Al dross, 8 h at 90 °C (adapted from Ref. [34]).
for construction or polymer composites, adsorbents and mineral wood.
Moreover, is a suitable Al source to synthesize alumina, salts, hydro-
xides and hydrotalcites [29–32]. prepared with fresh alkaline solutions. Zeolite ANA has trapezohedral
Sánchez-Hernández et [33] al have studied the synthesis of zeolites morphology and can be used in heterogeneous catalysis and selective
NaP1, SOD and ANA by single step hydrothermal process, using a ha- adsorption. SOD structure is cubic with small pores, high stability in
zardous aluminum waste as main Al source. 2.5 kg of zeolite per kg of basic solution and high zeta potential and suitable as membrane to
waste is obtained and no residual wastes are generated. Samples were separation small molecules, as He and H2, from gas or liquid [33].
characterized by XRD, SEM-EDS, FTIR, TG-DTA and BET specific sur-
face area, zeta potential, granulometry and CEC were determined. 4. Zeolite synthesis with Si and Al sources from industrial wastes
Stirring, time, temperature and alkaline concentration were studied,
and the results show that the formation of type of zeolite is determined As Gil and Korili [29] commented in their review article about the
mainly by temperature and alkali concentration and the best synthesis studies of aluminum dross valorization, interesting results have been
conditions to obtain each of them are: NaOH 1 M, 120 °C, 6 h for NaP1, published about the synthesis of zeolite X from aluminum and silicon
NaOH 1 M, 200 °C, 6 h for ANA, NaOH 5 M, 120 °C, 6 h for SOD. These wastes. The strategy reported recently by Hiraki et al. [34] to synthesize
waste zeolites have similar properties as commercial and good thermal zeolite X is based on silicon sludge and aluminum black dross. Silicon
stability (see Fig. 8). NaP1 has GIS structure and the highest CEC, so sludge is hydrolyzed with aqueous NaOH to obtain Na2SiO3, H2 is also
potential applications in water purification. The mother liquor of NaP1 generated. The available Al of the aluminum black dross is precipitated
synthesis can be recycled twice and the NaP1 obtained is similar to the as Al(OH)3 with aqueous NaOH and hydrolyzed to NaAlO2, generating

Fig. 8. SEM images at various magnifications of zeolites obtained from the aluminum waste: (a,b,c) NaP1, (d,e,f) SOD, and (g,h,i) ANA (adapted from Ref. [33]).

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H2 but not CO2. Si and Al sources are mixed in the proper Si/Al ratio to volume (0.140 cm3/g). CO2 capture capacity is 3.9 mmol/g [39].
synthesize zeolite X and the residual liquid is save to other synthesis.
The waste zeolites X prepared were characterized by XRD, Si/Al molar 6. Hierarchical zeolites
ratio and BET surface area (see Fig. 9). They have Si/Al ratio from 1.0
to 1.5 and BET from 500 to 600 m2/g, that are similar as the reported As it has been previously explained, zeolite are crystalline alumi-
for the commercial zeolites X. Results also reveal that K+, Ca2+ and nosilicates of monovalent or multivalent metals. Zeolite lattice is very
Zn2+ from the wastes replace Na+ in the zeolite X structure. stable negatively, has a negatively charged surface and internal pores
The selective synthesis of zeolites A and X from crushed stone and channels, what makes them microporous materials [41–43]. Zeo-
powder and aluminum ash is reported by Kuroki et al. [35]. The pro- lites are applied in catalysis due to strong acidic centers, large specific
cedures used by the authors include a step of extraction of Si and Al surface area, high ion-exchange capacity and high thermal stability.
components by HCl treatment, followed by a hydrothermal treatment Moreover, zeolites are suitable as catalysts for shape-selective reactions
with NaOH at 80–120 °C. because the size of internal micropores and channels allows to differ-
Ma et al. [36] reported the synthesis of a magnetic zeolite, with a entiate molecules by their sizes [41,44–47]. The size of the zeolite
structure of cancrinite, from fly ash, red mud and steel slag, also con- micropores is named configuration diffusion and it is an advantage,
sidering an hydrothermal procedure at 374 °C in presence of NaOH. because the size of zeolite internal voids makes them selective, but also
a disadvantage, because molecules with size similar to the size of the
5. Zeolite synthesis from natural clays micropores are limited. Studies of zeolites as catalysts reveal that
configuration diffusion limits the reaction if molecules have similar to
As it has been explained before, one of the most interesting appli- the size of the pores in the zeolite. It has been reported that diffusion
cations of zeolites, fundamentally of zeolite X, is CO2 adsorption and in limitations reduce reactants and products movement to and from active
the last years, interesting studies about zeolite synthesis as CO2 ad- sites. This generates unwanted by-products that can block the micro-
sorbents have been published. There are reported various sources of Si pores reducing or even deactivating the zeolite as catalyst because only
and Al but, in order to reduce the cost of synthesis, natural clays as the external part of zeolite works if the interior is catalytically inactive.
bentonite, kaolinite and feldspars were studied [37–40]. Garshasbi Diffusion limitations is solved if the zeolite present pores at various and
et al. [37] reported a procedure to obtain zeolite 13X from kaolinite different sizes, what is a hierarchical structure. Zeolites with hier-
(13X–K), bentonite (13X–B) and feldspar (13X–F) by hydrothermal archical porous structure has secondary meso- or macroporosity that
treatment, comparing their properties with commercial zeolite 13X allows large molecules access to the active centers but maintain the
(13X–C). The parameters that determine the type, purity and crystal- acidity and crystallinity of convectional microporous zeolites. The
linity of the zeolite were NaOH concentration, crystallization tem- secondary meso- or macroporosity decreases the crystal size making the
perature and crystallization time. To synthesize zeolite X from natural diffusion path shorter, reduces dissolution of the active phase into the
clays NaOH 4 M, 65 °C, 72 h. The natural clays kaolinite, bentonite and medium, increases catalytic activity, decreases catalyst deactivation
feldspar, the synthesized zeolites 13X–K, 13X–B and 13X–F, and the and promotes multiple regeneration of the catalyst. The results of re-
commercial zeolite 13X–C were characterized by XRD, FTIR, SEM and actions catalyzed with conventional zeolites and hierarchical zeolites
N2 adsorption-desorption curves (see Fig. 10) [37]. are similar if the molecules are smaller than the micropores, but hier-
archical zeolites are better catalysts in reactions with large molecules
5.1. Kaolinite (K) (i.e. Friedel Crafts-alkylation of aromatics and conversion of methanol
to hydrocarbons) [41–45].
Kaolinite is a mineral clay that contains Si and Al, but Al amount Although the central theme of this review is the synthesis of zeolites
must be decreased, and Si amount increased to adjust the Si/Al ratio to from wastes, it is interesting to include the investigations in hier-
1.5, suitable to synthesis zeolite X [38]. XRD spectrum confirmed that archical zeolites because they improve the characteristics and applica-
obtained product is zeolite X. The synthesized zeolite 13X–K has a BET tions of all types of zeolites, the ones synthesized from commercial
surface area of 591 m2/g with micropore volume of 0.250 cm3/g. Si- reagents and the ones obtained from industrial wastes. This final section
milar values as the BET surface area and micropore volume of zeolite reviews the synthesis, characterization and applications of hierarchical
13X–C, that are 588 m2/g and 0.240 cm3/g, respectively. CO2 adsorp- zeolites with a secondary meso- and macroporosity imposed on the
tion capacity of zeolite 13-K is 6.9 mmol/g, higher than zeolite 13X–C primary microporous structure that optimizes molecular sieving prop-
value (6.2 mmol/g) and also higher than the reported values for many erties and improves molecule transport, having the catalytic properties
of the CO2 adsorbents [39]. of conventional zeolites and solving their diffusion limitations [41].
Pereira et al. [40] obtain zeolite A after alkali treatment of meta- There are two types of hierarchical zeolites:
kaolins with NaOH at 80 °C for 24 h. The metakaolins were prepared by
calcination of kaolins at 600 °C. The obtained zeolites were also applied • Pure zeolite phases (genuine hierarchical zeolites): the secondary
as adsorbents to remove emergent pollutants. meso- or macroporosity is placed either in the zeolite crystals or in
the intercrystalline voids.
5.2. Bentonite (B) • Composites: these materials have a zeolite phase and a non-zeolite
phase, and the meso-macroporosity is placed in additional phases. If
Zeolite 13X–B was prepared by alkaline fusion and hydrothermal the additional phase is a medium, secondary porosity comes from
treatment using bentonite as Si and Al sources, and no extra reactants the medium.
are needed [39]. The synthesized zeolite 13X–B has high BET surface
area (505 m2/g) with a high micropore volume (0.160 cm3/g). CO2 Synthesis of hierarchical zeolites consists of aggregation, extraction
capture capacity is 4.9 mmol/g [39]. and crystallization, that can be applied one synthesis process, in two or
more different syntheses. There are two types of hierarchical zeolites
5.3. Feldspar (F) synthesis:

As commented for kaolinite and bentonite, feldspar is a suitable • Bottom-up method: the secondary porosity is made during zeolite
source of Si and Al to synthesize zeolite 13X by alkaline fusion and synthesis by using templates or changing synthesis conditions (non-
hydrothermal and no extra sources are needed. The synthesized zeolite templating methods). Hard templating, soft templating, assembly of
13X–F has high BET surface area (472 m2/g) with a high micropore nanosized zeolite and zeolitization of materials are bottom-up

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Fig. 10. SEM images (a) kaolin, (b) bentonite, (c) feldspath, (d) 13X–F, (e) 13X–B and (f) 13X–K. XRD patterns of kaolin, bentonite, feldspath and zeolite 13X
commercial. CO2 adsorption isotherms of zeolites 13X commercial (13X–C), 13X–K, 13X–B, 13X–F (adapted from Ref. [37]).

methods [40]. 7. Conclusions

• Top-down methods: the secondary porosity is made after zeolite
synthesis. Dealumination, desilication, irradiation and recrystaliza- Researchers have been published different synthesis procedures to
tion are top-down methods [45,48,49]. obtain zeolites from industrial wastes as coal and biomass ashes, silicon
sludge, aluminum saline slags and aluminum dross. Zeolite synthesis
The main methods to synthesize hierarchical zeolites are: strategies using natural clays as kaolinite, bentonite and feldspars as Si
and Al sources have been also reported. The results of these studies
• Removal of framework atoms: demetallation, dealumination, desi- prove that industrial wastes rich in Si and/or Al are suitable materials
lication, irradiation to synthesize zeolites and the properties and applications of waste
• Template-assisted: hard-templating, carbonaceous templates, poly- zeolites are similar as the synthesized with commercial sources. The
meric templates, solid templates, soft-templating methods. main methods employed in waste zeolites synthesis are conventional
• Surfactant-assisted recrystallization hydrothermal method, microwave assisted hydrothermal method, fu-
• Dual templating with surfactants sion and hydrothermal method, digestion and hydrothermal method,
• Zeolitization of materials molten salt method. Zeolization mechanism from a waste is based on Al
• Nanoparticle assembly and Si dissolution, geopolymer formation, crystalline structure

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