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Zeolites: Properties, Applications, Modification and Selectivity

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Chapter

ZEOLITES: PROPERTIES, APPLICATIONS,

MODIFICATION AND SELECTIVITY

Ehsan Kianfar*
1
Department of Chemical Engineering,
Arak Branch, Islamic Azad University, Arak, Iran
Young Researchers and Elite Club,
Gachsaran Branch, Islamic Azad University, Gachsaran, Iran

ABSTRACT

Zeolite is a mineral that consists mainly of aluminosilicate, and its

major commercial use in the industry is as a surfactant. The word zeolite
was originally invented in 1756 by the Swedish mineralist Axel Fredrik
Cronstedt. The name of zeolite is composed of the combination of two
Greek words (zéo, meaning “boiling” and lithos (meaning “stone”).
Zeolites are widely used in the water purification industry as a catalyst for
the preparation of advanced materials. The most important use of zeolite
in the manufacture of clothing cleaners is also used in medicine and
agriculture and methanol to gasoline and methanol to dimethyl ether. For
natural zeolites, only 9 species are found to be abundant in nature. The

*
Corresponding author E-mail: e-kianfar94@iau-arak.ac.ir and ehsan_kianfar2010@yahoo.com.
2 Ehsan Kianfar

physical and chemical properties of natural zeolites are different and

different types of specimens Zeolite also has differences in physical
properties (pore size, crystalline size, capacity) Iodine ion and absorption
capacity) and chemical composition. The uses of synthetic and natural
zeolites originate from their physical and chemical properties, which in
turn is a function of crystalline structure and chemical composition of
zeolites. This review book studies the properties, applications and
modification and Selectivity yield.

Keywords: ZSM, catalyst, chemical properties, crystalline, modification,

selectivity

INTRODUCTION

In 1756, Swedish mineralogist Axel Fredrik Cronstedt discovered

naturally occurring zeolite. Since then, about 40 types of natural zeolites
have been discovered in which most of them have low Si/Al ratio. This is
due to the absence of organic structure–directing agents which is necessary
for formation of siliceous zeolites. Sometimes natural zeolites are found as
large single crystals in nature, however it is very difficult to make such
large crystals in the laboratory. Zeolites with high porosity such as
Faujasite (FAU), whose laboratory synthesised examples are zeolites X/Y,
are scarce in nature. Two natural zeolites used extensively in industry are
Mordenite (MOR) and Clinoptilolite (HEU). These materials have been
used for agronomy, horticulture and soil remediation to improve the soil
chemical and physical properties, treatment of effluents containing
radioactive contaminants or other heavy metals, or as molecular sieve to
trap or separate gases in agriculture (e.g., ammonia). Natural zeolites can
be used as a catalyst but their catalytic activity is limited by their
impurities and low surface areas. Figure 1 shows Clinoptilolite and
Mordenite, two naturally occurring zeolites.
 Zeolites 3

Figure 1. Left: Clinoptilolite-Na from Andalusia, Spain. Right: Mordenite from San
Juan, Argentina.

ZEOLITES STRUCTURE

Zeolites are microporous crystalline aluminosilicates with pore sizes

ranging from 3 to 7Å. About 176 framework structures have been listed in
the most recent Atlas of Zeolite Framework Types. The most important
characteristic properties of these solid materials are well-defined structure,
high surface area, selective sorption of small molecules (molecular sieves)
and ion exchange. Zeolite are composed of TO4 tetrahedra (T = Si, Al)
which are interlinked through oxygen atoms to have a 3D network. The
zeolite composition can follow this formula:

Mm+ Si1-nAlnO2 nH2O

Extra framework cation Framework Sorbed phase

The extra framework cations can be ion-exchanged with other cations

(e.g., alkali metals, alkaline earth metals and transition metals). Depending
on the synthesis conditions, the amount of Al within the framework can
vary from Si/Al≈1 to ∞. Moreover, post-synthesis modifications of zeolite
can insert Al or Si into the framework. Increasing the Si/Al ratio of the
framework can improve the hydrophobicity as well as the hydrothermal
stability. Zeolite frameworks contain cages of spherical or other shapes
which are interconnected by channels. The diameter of the channels is
4 Ehsan Kianfar

determined by the number of T atoms surrounding the opening of the

channels as n-member rings. Large pore zeolites are constructed of 12-
member rings (d > 7Å), medium pore zeolites contain 10-member rings
(5Å < d < 6Å) and small-pore zeolites contain 6- or 8-member rings
(diameter d: 2.8Å < d < 4Å). Figure 2 illustrates different zeolite
frameworks and some examples of synthesised zeolites with same
framework structure but different composition.

(a)

(b)
 Zeolites 5

(c)

Figure 2. Different framework of zeolites (a) Faujasite type 12-ring, examples: Linde
X, Linde Y, SAPO-37, ZSM-20, (b) Ferrierite type 10-ring, examples: NU-23, ZSM-
35 (c) Chabazite type 8-ring, examples: AlPO-34, Linde D, SAPO-34 (Baerlocher et
al., 2007).

The Structure Commission of the International Zeolite Association

(IZA-SC) identifies each framework type with a three-letter code. Table 1
lists some of the important zeolites with three-letter codes based on Si/Al
ratio or phosphate content.

Table 1. Nomenclature and specifications of important zeolites

Low Silica Intermediate Silica High Silica Other elements

Si Si Si
≤2 2< ≤5 5<
Al Al Al
IUPAC Example IUPAC Example IUPAC Example IUPAC Example
name name name name
ANA Analcime BHP Linde Q BEA Zeolite β AEI AlPO4-18
BIK Bikitaite FAU NaY FER Ferrierite AEL AlPO4-11
CAN Cancrinite FER Ferrierite MEL ZSM-11 AFN AlPO4-14
EDI Edingtonite LTL Linde L MFI ZSM-5 AFR SAPO-40
FAU NaX MAZ Mazzite MFS ZSM-57 AFX SAPO-56
FRA Franzinite MEI ZSM-18 MSO MCM-61 CAN Tiptopite
LTA Linde A MER Merlinoite MTF MCM-35 CHA SAPO-47
PHI Phillipsite MOR Mordenite MTT ZSM-23 FAU SAPO-37
SOD Sodalite OFF Offretite MWW MCM-22 OSI UiO-6
THO Thomsonite STI Stilbite ZSM ZSM-48 SAV Mg-STA-
7
6 Ehsan Kianfar

LOW-SILICA ZEOLITES

Low-Silica zeolites or aluminium-rich zeolites are nearly saturated in

aluminium with a molar ratio of Si/Al≈1 with maximum possible
aluminium content in the tetrahedral framework (e.g., zeolite A and X) and
as a result they contain the maximum number of cation exchange sites.
This characteristic gives them a strong hydrophilic surface selectivity.
Their pore volumes are the highest among other known zeolites and give
them a distinct economic advantage in bulk separation and purifications
where high capacity is required.

INTERMEDIATE-SILICA ZEOLITES

Intermediate-Silica zeolites were invented for the first time by

scientists at Union Carbide Laboratories in the early 1950's with improved
thermal, hydrothermal, and acid stability. They found significant
commercial market as both an adsorbent and hydrocarbon conversion
catalyst when they were introduced for the first time. The surface of these
zeolites is still heterogeneous and exhibits high selectivity for water and
other polar molecules. The intermediate zeolites with 2 < Si/Al < 5 consist
of the natural zeolites such as mordenite, erionite, clinoptilolite, Chabazite
and the synthetic zeolites such as omega, mordenite, Y, and L. These
materials still have hydrophilic property in this Si/Al range.

HIGH-SILICA ZEOLITES

High-silica zeolites with Si/Al > 5 or higher are more hydrophobic and
organophilic in nature, with more diluted numbers of strong Brønsted
acidic sites and also higher thermal and hydrothermal stability. High silica
zeolites can be obtained directly during the synthesis procedure by addition
of organic component to aluminosilicate and silicate gels or by post-
 Zeolites 7

synthesis or modification such as hydrothermal steaming, use of aqueous

(NH4)2SiF6, SiCl4 or F2 gases. Removal of framework aluminium by
dealumination results in better catalytic properties and enhanced thermal
stability.

OTHER ELEMENTS

Many elements now have been incorporated into zeolite framework.

Substitution of P in zeolite framework by Si leads to silica-alumina-
phosphates (SAPOs), with cation-exchange abilities. Aluminophosphates
(AlPOs) have alternating AlO2- and PO2+ units. The framework is neutral,
organophilic, and non-acidic. Incorporation of elements such as Si, Mg, Fe,
Ti, Co, Zn, Mn, Ga, Ge, Be, Li, As, and B into the tetrahedral sites of
AlPOs gives a vast number of element-substituted molecular sieves
(MeAPO, MeAPSO, SAPO) which are important heterogeneous catalysts.

APPLICATION OF ZEOLITES

Zeolites have a wide use in industries such as detergents, gas

separation, desiccants and catalysts. Natural zeolites are mainly used in
bulk mineral applications due to their lower cost. Figure 3 shows the
application of zeolites in different industries. In 2008, a total of 1.27×10 6t
was estimated to be consumed in those applications. The second largest use
of zeolites is as catalysts (17%) which accounts for more than 55% of the
market on a cash basis owing to the greater expense of zeolites used as
catalysts compared with other uses. More than 95% of the total zeolite
catalyst consumption is zeolite Y which is used for Fluid Catalytic
Cracking (FCC) process. Smaller volumes are used for petrochemical
synthesis or in hydrocracking process. In 2008 it was estimated that the
catalyst consumption has been around 0.3 × 106 t. Zeolites are used as
adsorbents for drying and purification of petrochemical streams (e.g.,
8 Ehsan Kianfar

ethylene, propylene) and natural gas, bulk separations of chemicals (e.g.,

normal paraffins or xylenes) and in air separation industries to produce
oxygen by pressure swing adsorption (PSA) or vacuum pressure swing
adsorption (VPSA). In 2008, about 0.18 × 106 t (10%) of zeolite was used
as adsorbent. Zeolites are also used in transformation of photochemical
organics, sensor industries, removal of odour, filler in paper, conversion of
solar energy, plastic additives, soil conditioner and fertiliser, pozzolanic
cement and concrete, lightweight aggregate, and dietary supplement in
animal nutrition.
In 2008, it was estimated that the world production of natural zeolites
is about 3.0 × 106 t. The biggest consumers of natural zeolites are China
and Cuba to mainly enhance the cement strength. The price of zeolites
significantly depends on the application. For example, in United States, the
price of natural zeolite for bulk applications is about 0.04-0.25 USD/kg
and 1.5-3.5 USD/kg for industrial adsorbent applications. The typical price
of zeolite for catalyst applications varies from 3-4 USD/kg for FCC to
about 20 USD/kg for specialty catalysts. This price is 5-9 USD/kg for
adsorbents and about 2 USD/kg for detergents.

Figure 3. Application of zeolites in different industries in 2008.

 Zeolites 9

ZEOLITES AS CATALYST

Table 2 lists the main applications of zeolites as catalyst. The catalysis

over zeolites can be categorised to three different classes: 1) Inorganic
reactions, 2) Organic reactions, and 3) Hydrocarbon conversion. Zeolites
as catalysts have many unique properties such as acidity, shape-selectivity,
high surface area and structural stability which will be discussed further in
the following sections.

Table 2. Application of zeolites as catalyst

Inorganic Organic reactions Hydrocarbon conversion

reactions
H2S oxidation Aromatisation (C4 hydrocarbons) Alkylation
NO reduction Alkylation (naphthalene, benzene Cracking
of NH3 ethylbenzene, aniline, biphenyl, Dehydration
CO oxidation, polyaromatics, etc.) Fischer-Tropsch
reduction Aromatics (hydrogenation, synthesis
Decomposition oxidation, nitration, Friedel-Crafts alkylation
of H2O disproportionation, Hydrocracking
hydroalkylation, hydroxylation, Hydrogenation,
oxyhalogenation, etc.) Dehydrogenation
Chiral (enantioselective) Hydrodealkylation
hydrogenation Isomerisation
Cyclohexane (oxidation, Methanol to gasoline
isomerisation, aromatisation, ring Methanation
opening) Shape-selective
reforming

ACIDITY AND BASICITY

A basic definition is that a Lewis acid is an electron pair acceptor and a

Lewis base is a species with an available (reactive) pair of electrons or an
electron donor. Brønsted argued that all acid-base reactions involve the
10 Ehsan Kianfar

transfer of a proton (H+ ion). According to this theory, an acid is a “proton

donor” and a base is a “proton acceptor.” Therefore, in solid surfaces, the
Brønsted acid site is able to transfer a proton from the solid to the absorbed
molecule while the Lewis acid sites are able to accept electron pair from
the adsorbed molecule.
The acidic nature of zeolites is due to the metal cations or hydroxyl
protons on their extra-framework. In aluminosilicate-type zeolites, the 4+
charges on framework silicon atoms at tetrahedral positions (T position)
and the 2− charges on the coordinating oxygen atoms lead to neutral SiO4
tetrahedra. Substitution of silicon atoms in the framework by aluminium
atoms can change the corresponding tetrahedra charges from neutral to 1−.
These negative framework charges are balanced by extra-framework metal
cations or hydroxyl protons forming weak Lewis acids site or strong
Brønsted acid sites, respectively, responsible for the catalytic activity of
the zeolite materials.
The first type of hydroxyl protons on zeolites are those located on
oxygen bridges connecting silicon and aluminium atoms of the framework.
These hydroxyl groups are commonly donated structural or bridging OH
groups or Si-OH-Al (Figure 4a). The second important type of hydroxyl
groups in zeolites are the silanol groups or Si-OH, also called terminal OH
groups, which are located on the external surface of crystal particles
(Figure 4.b). Dealumination of the zeolite framework by calcination,
hydrothermal treatment, or treatment with strong acids, is the most
important reason for the formation of these silanol groups. Depending on
the treatment conditions, silicon migration, formation of silanol groups,
formation of hydroxyl groups at extra-framework aluminium may occur
(Figure 4.c). Sometimes, dealumination of the zeolite framework is
accompanied by the formation of Lewis acid sites at extra-framework
aluminium species and framework defects (Figure 4.d). If these Lewis acid
sites are located in the area close to bridging OH groups, super-acidic
Brønsted sites are formed.
 Zeolites 11

Figure 4. Different types of hydroxyl group and acid sites in zeolites.

Although, acidic zeolites as solid catalysts have a wide range of

application in chemical industries, less attention has been paid in the
literature to use these microporous and mesoporous materials as a basic
catalyst. These solid catalysts with basic properties have a considerable
potential for a number of important industrially processes (e.g., Claus
reaction). The nature of basic sites in zeolites is less well-defined than that
of acid sites. This is probably due to the fact that the basic framework
oxygen atoms or alkali metal cations on the zeolite framework act as weak
Lewis acid sites as well. The basicity of zeolites can be enhanced by
changing the electronegative charge of the framework or by introduction of
a basic component to their structure. Alkali-exchange of zeolites in
aqueous solution or by solid-state ion exchange leads to materials which
possess basic framework oxygen atoms of relatively low base strength.
Different techniques such as IR Spectroscopy, Alkane Cracking, UV-
Visible Spectroscopy, Temperature-Programmed Desorption of Amines,
Microcalorimetry and Solid-state NMR Spectroscopy have been used to
quantify the Brønsted and Lewis sites in a solid acid system, however,
most of these techniques cannot easily discriminate between Lewis and
Brønsted sites. In other words, no single characterisation can provide all
the information unambiguously, so a combination of two or more
techniques is required.

Zeolite Selection for Processes

Catalytic sites associated with a zeolite often affect reaction selectivity.

A number of classical concepts are useful to the catalyst designer for their
rationalizing and even predicting power. Molecules can be excluded from
12 Ehsan Kianfar

chemical activation at intracrystalline active sites, depending on the size,

shape of the pores, and the reactant. To all such phenomena the concept of
reactant shape selectivity (RSS) was coined. From a mixture of product
molecules desorbing from the intracrystalline active sites the faster-
diffusing “slimmer” molecules will be abundantly present, generating a
pseudothermodynamic equilibrium in the bulk. The phenomena are
described as product diffusion shape selectivity (PDSS). Geometric
restrictions near the active site can inhibit formation of some transition
states and affect product selectivity.
The phenomena are known as transition-state shape selectivity (TSSS).
Whereas for RSS and PDSS crystallite encapsulated sites are needed,
TSSS may occur in half-open cages at crystal terminating locations as well.
Although such effects were mainly reported for hydrocarbons and
alkylaromatics in medium-pore zeolites with 10-membered rings (10-MRs)
of lattice atoms, viz.
MFI, MEL, TON, the concepts are applicable to functionalized
organics and other topologies as well. The nature of the sites is also not
limited to Brønsted acid sites, but also applies to metal and redox sites. The
area has been reviewed thoroughly. The use of the concepts implies
compositional homogeneity across the crystals and the existence of only
intracrystalline sites that all show identical selectivity.
Initially, it was proposed that pore size and tortuosity, as well as pore
architecture determined by the zeolite topology, were influencing
intrazeolitic fields and field gradients, thus affecting differently the relative
rates of primary and secondary reactions and overall selectivity. Recently,
effects of confinement on various kinetic and even thermodynamic effects
were shown that provide an understanding of the confinement effect on
adsorption and diffusion. Configurational-bias Monte Carlo techniques
allowed simulation of slowly diffusing molecules, trapped in cages or at
adsorption sites in zeolite topologies. This approach consisting of mapping
the free-energy landscape in the intracrystalline space, ignores effects of
local differences in site architecture, or concentration on reaction
selectivity.
 Zeolites 13

Figure 5. (a) Details of the T - atom connectivity comprising the LTL 12 - ring channel
system. (b) Diagram of the resulting channels.

To a number of unexpected shape-selectivity phenomena with long

alkane hydroconversion the term inverse shape selectivity was coined. In
zeolite pore widths of 0.65–0.74 nm, the opposite was encountered, as
expected from mere geometric effects, that is, preferential formation of
branched over linear hydrocarbons, viz. the formation of high yields of
dibranched from n-alkanes over 10-MR zeolites like AFI (SAPO-5), the
phenomenon being confirmed by adsorption experiments. The molecular
basis of such effects has been attributed to a purely entropic effect in
monodimensional pores at high pressures expelling larger molecules by
smaller ones.
Several shape-selective phenomena were attributed to topology-
dependent structural sites. Such nest effects were the result of tuning of the
curved catalyst surface to the configuration of adsorbed species, entropic
effects governing the fitting. A distinction between two types of extra-
framework catalysis mainly in ZSM-22 (TON), was made using the terms
of pore mouth and keylock selective catalysis (Figure 5). Apparently, it is
possible for alkanes via hydroconversion to be transformed in a selective
14 Ehsan Kianfar

way into products that are unable to be formed in or desorb from the
zeolite. The abundant formation of some molecules, viz. 2-methylbranched
alkanes from n-alkanes, was assigned to transformation in a single pore
mouth. Others, viz. 2,4-dimethyloctane from n-decane, happened to be
formed at neighboring pore mouths, as their selectivity was chain length as
well as topology dependent.

Shape Selectivity Zeolites

Shape selective catalysis is based on the difference between the

dimensions of reactants, products, or intermediate molecules and size of
the pores. Only molecules with dimensions less than a critical size can
enter the pores and react on the internal catalytic sites. Moreover, in the
final product, only molecules that can leave the pores appear. Thus, shape
selective catalysis can be used to improve the yield of desired products
and/or to prevent production of undesired products. Three types of shape
selectivity can be distinguished depending on whether pore size limits the
entrance of the reactant’s molecules, removal of the produced molecule
from the pores, or the formation of certain transition states.
These three variants, which can however, overlap are:

 Reactant selectivity
 Product selectivity
 Restricted transition state selectivity

Reactant selectivity means that starting material molecules that are

larger than the pore size cannot enter the pores, in other words, only
starting materials with a certain size and shape can penetrate into the
zeolite pores (Figure 6.a). The term “molecular sieve” applies to this class
of zeolites. Table 3 compares the kinetic molecular diameters of some
reagents with the pore opening of some zeolites. These data are useful to
choose a suitable zeolite for a particular starting material. However, it
 Zeolites 15

should be noted that the kinetic diameter is only a rough estimate of the
molecular size since molecules are not rigid objects.
Dehydration of butanol over CaA zeolite is an example of reactant
selectivity in zeolites. The straight-chain alcohol is dehydrated much faster
than iso-butanol which has a larger molecular diameter.
Product selectivity in zeolite occurs when the size of the molecule
formed inside the pores is too large to diffuse out of the pores. Methylation
of toluene and the disproportionation of toluene over ZSM-5 are the well-
known examples of product selectivity in the zeolites. In both cases all
three isomers o-, m-, and p-xylene are formed inside the pores and
although the thermodynamic equilibrium corresponds to p-xylene fraction
(as desired product) is only 24%, it can be obtained with selectivity of
more than 90 %. This is due to the fact that p-xylene has smaller
dimensions with a diffusion rate of 104 faster than other two isomers. In
other words, although all the isomers are produced relatively rapidly in the
zeolite cavity, the diffusion of p-xylene out of the cavity is much faster.

Table 3. Pore sizes of zeolites and molecule diameters

Zeolite Pore size (Å) Molecule Kinetic diameter (Å)

KA 3.0 He 2.5
SAPO-34 3.8 NH3 2.6
NaA 4.1 H2O 2.8
CaA 5.0 N2, SO2 3.6
Erionite 3.8×5.2 Propane 4.3
ZSM-5 5.1×5.5 n-Hexane 4.9
5.3×5.6
Beta 5.6 Isobutane 5.0
CaX 6.9 Benzene 5.3
Mordenite 6.7-7.0 p-Xylene 5.7
NaX 7.4 CCL4 5.9
AlPO-5 7.3 Cyclohexane 6.2
VPI-5 12.7 o-,m-Xylene 6.3
16 Ehsan Kianfar

(
a)

(
b)

(
c)

Figure 6. Shape selectivity of zeolites with examples of reactions: a) Reactant

selectivity: cleavage of hydrocarbons, b) Product selectivity: methylation of toluene, c)
Restricted transition state selectivity: disproportionation of m-xylene.

Restricted transition state selectivity depends on the available space in

the cavities or pores of the zeolite. In this case, the chemical reaction
pathway is altered because certain reactions are prevented due to the
required space for corresponding transition state. Only those intermediates
that have a geometrical fit to the zeolite cavities can be formed during
catalysis and reactions that require smaller transition states can be proceed
with no hindrance.
In practice, it is often difficult to distinguish between product
selectivity and restricted transition state selectivity. Alkylation of benzene
with ethylene over ZSM-5 zeolite to produce ethylbenzene is an example
 Zeolites 17

of restricted transition state selectivity. By suppression of other side

reactions it is possible to achieve high ethylbenzene selectivity.

MODIFICATION OF ZEOLITES

The structure and framework composition of zeolites can be tailored

and utilised for specific applications. There are two routes to achieve this
goal: (1) direct synthesis and (2) post-synthetic treatment and modification.
The direct synthesis is the main route of the synthesis of zeolites.
Many parameters such as composition of synthesis mixture, synthesis
temperature, and time, solution pH, aging and seeding, directing agent or
template have influence on the zeolite structure. However, in most cases,
the direct synthesis route does not lead to the formation of zeolites with
desirable properties for the final applications.
In addition to the direct synthesis method, post synthetic treatment
such as ion exchange, preparation of metal-supported zeolites,
dealumination, reinsertion of heteroatoms (e.g., B, Ga, Ge, or Al) into
zeolite framework, and other modification methods provides a more
practical route to modify the zeolites to acquire desirable framework
compositions and other properties. For example, for catalytic cracking
process over HY zeolite, strong acid activity and high thermal and
hydrothermal stability is required. It is well known that the higher the
SiO2/A12O3 ratio, the more stable the zeolite structure. Unfortunately, few
zeolites can be prepared with the desired SiO2/A12O3 ratio through direct
synthesis and this ratio is limited to a maximum value around six.
Dealumination, in this case is a useful way to increase the SiO2/A12O3
ratio. Three dealumination methods have been used to produce the desired
properties:

1) Hydrothermal treatment (e.g., steaming).

2) Chemical treatment (e.g., reaction with EDTA, (NH4)2SiF6, SiCl4,
F2 gas).
18 Ehsan Kianfar

3) Combination of hydrothermal and chemical treatment (e.g.,

treatment with HCl, HNO3, NaOH, KF).

The Si/Al ratio plays a significant role, since the catalytic activity of a
zeolite depends on the number of acidic OH groups on the aluminium in
the framework, and it is directly related to the formation of carbonium or
carbenium ions inside the zeolite. Dealumination can improve the porous
structure and enhance some important zeolite properties (e.g., zeolite
acidity, catalytic activity, thermal and hydrothermal stability, resistance to
aging and coking). However, severe dealumination can decrease the zeolite
crystallinity. Dealumination might be expected to reduce the catalytic
activity of zeolites; however, if the effect of increase in the acid strength
surpasses the effect of the decrease in the acidic centres, dealumination can
sometimes result in enhancement of catalytic activity. The enhancement of
the acid strength of OH groups is caused by their interaction with
aluminium species dislodged from the framework and left in the cavities.
The aluminosilicate structure of the zeolites is ionic and contain Si 4+,
Al3 and O2- ions. Replacing some of the Si4+ ions by Al3+ ions in the SiO4
+

tetrahedra of zeolite framework is led to generation of an excess negative

charge. In this case, a compensating source of positive charge (cations)
must be added to neutralise the framework charge. These non-framework
cations play an important role in determining the catalytic properties of the
zeolite. An aqueous salt solution may be used to incorporate the cations
from the salt into the zeolite.
Solid-state reactions between zeolites and compounds of cations,
which are desired to enter the porous structure of the zeolite, is another
method of preparation. Advantages over conventional ion-exchange in
liquid phase are:

1) Prevention of handling large volume of salt solutions

2) Less generation of waste salt solution
3) Introducing metal cations into narrow pore cavities where the ion-
exchange in aqueous solutions is not efficient.
 Zeolites 19

In this method, first, an intimate mixture of the two components (e.g.,

zeolite and compound with cation) is prepared. The mixture is
subsequently heated in an inert gas stream or high vacuum to release
volatile products such as hydrogen halides, ammonia, water, etc. Typically
reaction temperature of 250-350°C and reaction time of a few hours are
required.

CONCLUSION

The most effective and most widely used methods for the synthesis of
zeolite are the use of initial clear solutions and colloidal suspensions.
These colloidal suspensions are stable and dispersed zeolites do not settle
for a long time longer than the moon. Colloidal crystals give unique purity
to the production structures, and by increasing the level of zeolite contact,
they increase their applications in pharmaceutical, chemical, and
optoelectronic applications. With the appropriate pore size distribution in
the inert matrix, the size of the crystal zeolite can be controlled without gel
dependence. Synthesis like making zeolite by the composition of the gel is
theoretical, which is difficult and impossible with the usual methods, and
A, X is possible by synthesis with limiting telemeters. In summary,
advances in zeolite science require multidisciplinary skills (materials
synthesis and processing, detailed understanding of their chemical,
physical, thermal, and optical properties). The engineering of devices and
systems based on zeolite will continue to involve ever-greater interactions
and collaborations between chemists, physicists, materials scientists, and
engineers.

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