Zeolites

ROBERT W. BROACH, UOP LLC, A Honeywell Company, Des Plaines, Illinois,

United States 60017
DENG-YANG JAN, UOP LLC, A Honeywell Company, Des Plaines, Illinois,
United States 60017
DAVID A. LESCH, UOP LLC, A Honeywell Company, Des Plaines, Illinois,
United States 60017
SANTI KULPRATHIPANJA, UOP LLC, A Honeywell Company, Des Plaines, Illinois,
United States 60017
ECKEHART ROLAND, Degussa AG, ZN Wolfgang, Hanau, Germany
PETER KLEINSCHMIT, Degussa AG, ZN Wolfgang, Hanau, Germany

1. Introduction. . . . . . . . . . . . . . . . . . . 2 7.3. Raw Materials . . . . . . . . . . . . . . . . . 12

2. Nomenclature . . . . . . . . . . . . . . . . . 2 7.3.1. Synthesis Conditions . . . . . . . . . . . . . 13
3. History. . . . . . . . . . . . . . . . . . . . . . . 2 7.3.2. Examples of Industrial Zeolite
4. Structure, Composition, and Syntheses . . . . . . . . . . . . . . . . . . . . . 13
Properties . . . . . . . . . . . . . . . . . . . . 4 7.3.3. Post Synthesis Treatments . . . . . . . . . 16
4.1. Framework Structure . . . . . . . . . . . 4 7.3.4. Environmental Aspects . . . . . . . . . . . 17
4.2. Nonframework Cations . . . . . . . . . . 6 8. Commercial Applications and
4.3. Chemical and Physical Properties . . 7 Importance . . . . . . . . . . . . . . . . . . 17
4.3.1. Physical Properties . . . . . . . . . . . . . . 8 8.1. Natural Zeolites . . . . . . . . . . . . . . . . 18
4.3.2. Chemical Properties. . . . . . . . . . . . . . 8 8.2. Synthetic Zeolites. . . . . . . . . . . . . . . 18
5. Characterization . . . . . . . . . . . . . . . 9 8.2.1. Adsorption . . . . . . . . . . . . . . . . . . . . 19
6. Occurrence, Mining, and Processing 8.2.2. Membranes . . . . . . . . . . . . . . . . . . . . 22
of Natural Zeolites . . . . . . . . . . . . . 10 8.2.3. Catalysis . . . . . . . . . . . . . . . . . . . . . . 23
7. Production of Synthetic Zeolites . . 11 8.2.4. Other Uses . . . . . . . . . . . . . . . . . . . . 28
7.1. Chemistry of Zeolite Synthesis. . . . . 11 9. Toxicology . . . . . . . . . . . . . . . . . . . 28
7.2. Composition of Reaction Mixtures. . 12

Abbreviations and symbols used in this RON: research octane number

article SBUs: secondary building units
AA: atomic absorption SPA: solid phosphoric acid
CBUs: composite building units TIP: total isomerization process
EB: ethylbenzene TPABr: tetrapropylammonium bromide
FCC: fluid catalytic cracking TPD: temperature-programmed
ICP: inductively coupled plasma desorption
MAS: magic angle spinning TSA: temperature swing adsorption
MOGD: mobile ofefin to gasoline/destillate XPS: X-ray photoelectron spectroscopy
MON: motor octane number XRD: X-ray diffraction
MTG: methanol-to-gasoline XRF: X-ray fluorescence
MTP: methanol-to-propylene VPSA: vacuum pressure swing
PSA: pressure swing adsorption adsorption

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a28_475.pub2
2 Zeolites
1. Introduction
The exact definition of the term ‘‘zeolite’’ is still
the subject of discussion. Zeolites are generally
described as crystalline, hydrated aluminosili-
cates with a three-dimensional framework
structure [1–5] constructed of SiO4 and AlO4
tetrahedra linked through oxygen atoms. De-
pending on the structure type, they contain
regular channels or interlinked voids whose
aperture diameters are in the micropore range.
These pores contain water molecules and the
cations necessary to balance the negative charge
of the framework. The cations, which are mobile
and can be exchanged, are mainly alkali metal or
alkaline-earth metal ions.
The regular nature of the channels and aper-
tures, whose dimensions are of the same order of
magnitude as molecular diameters, enables the
zeolites to function as molecular sieves. This
outstanding property of zeolites gives them
value as selective adsorbents for separating
substances and as shape-selective catalysts.
2. Nomenclature
The naming of zeolites in the literature seldom
follows a scientific system. If natural analogs
exist, the synthetic zeolites are often named
after the minerals (e.g., faujasite, mordenite,
ferrierite, and offretite). Sometimes, the names
given by the discoverers are used. In the 1950s
and early 1960s, new synthetic zeolites were
named using the letters of the Latin and Greek
alphabets. Examples include the Linde molecu-
lar sieves A, L, X, and Y of Union Carbide and
the zeolites beta, rho, theta-1, and omega. Ac-
ronyms that indicate the industrial or university
laboratory that first synthesized a given material
were then increasingly used, supplemented by a
consecutive numbering system. Names, such as
ZSM-5 (Mobil Oil), Nu-13 (ICI), LZ-210 and
UZM-5 (Union Carbide/UOP), CSZ-3 (Grace),
and ECR-1 (Exxon) have gradually become
generally accepted. Zeolites with identical
framework structures can therefore appear in
literature under different names.
Some order was imposed with the establish-
ment of the Structure Commission at the 4th
International Conference on Molecular Sieves
in 1977 with the goals to evaluate zeolite
structural data in the literature and to prepare
compilations of those data for the benefit of the
zeolite community. The Structure Commission
of the International Zeolite Association [6] as-
signs framework type codes (given the authority
by IUPAC) consisting of three capital letters to
all unique and confirmed framework topologies.
For example, the framework type LTA is com-
mon to all of the materials commonly referred to
in the literature as Alpha, ITQ-29, Linde Type
A, 3A, 4A, 5A, LZ-215, N-A, SAPO-42, ZK-21,
ZK-22, ZK-4, and UZM-9. The information
from the Structure Commission is disseminated
in a series of publications that are updated on a
regular basis and a set of zeolite structure da-
tabases can be accessed via the internet [7, 8].
IUPAC provides guidelines [9] for specify-
ing the chemical formula for zeolites. In the
simplest form, a general formula can be given
as
jMx/n ðH2 OÞy j½Alx Siðt
xÞ O2t 
IZA
The guest species are listed between the
braces, ||, and the host framework is listed
between the brackets, []. M represents a
charge-balancing cation, x is the number of
framework Al atoms in the unit cell, n is the
cation charge, y is the number of adsorbed water
molecules, t is the total number of framework
tetrahedral atoms in the unit cell (Al þ Si), and
IZA is the code for the framework type assigned
by the Structure Commission of the Internation-
al Zeolite Association [8].
Formula 1 occurs frequently in the literature
and simply represents the overall chemical
composition.
M2/n OAl2 O3 ySiO2 wH2 O ð1Þ
3. History
The history of zeolites began in 1756 when the
Swedish mineralogist CRONSTEDT discovered
the first zeolite mineral, stilbite [10]. He recog-
nized zeolites as a new class of minerals con-
sisting of hydrated aluminosilicates of the alkali
and alkaline earths. Because the crystals exhib-
ited intumescence when heated in a blowpipe
flame, CRONSTEDT called the mineral a ‘‘zeolite’’
derived from two Greek words, ‘‘zeo’’ and
‘‘lithos’’ meaning ‘‘to boil’’ and ‘‘a stone’’. From

1777 through about the 1800s, various authors
described the properties of zeolite minerals,
including reversible cation exchange, dehydra-
tion, and adsorption properties. ST. CLAIRE
DEVILLE reported the first hydrothermal synthe-
sis of a zeolite, namely levynite, in 1862 [11]. In
1896 FRIEDEL developed the idea that the struc-
ture of dehydrated zeolites consists of open
spongy frameworks after observing that various
liquids, such as alcohol, benzene, and chloro-
form were occluded by dehydrated zeolites [12,
13]. In 1909 GRANDJEAN observed that dehy-
drated chabazite adsorbs ammonia, air, hydro-
gen, and other molecules [14], and in 1925
WEIGEL and STEINHOFF reported the first molec-
ular sieve effect [15]. They noted that dehy-
drated chabazite crystals rapidly adsorbed
water, methyl alcohol, ethyl alcohol, and formic
acid but essentially excluded acetone, ether, or
benzene. In 1927 LEONARD described the first
use of X-ray diffraction for identification in
mineral synthesis [16]. TAYLOR and PAULING
described the first single crystal structures of
zeolite minerals in 1930 [17–19]. In 1932
MCBAIN established the term ‘‘molecular sieve’’
to define porous solid materials that act as sieves
on a molecular scale [20].
By the mid 1930s, the literature described the
ion exchange, adsorption, molecular sieving,
and structural properties of zeolite minerals as
well as a number of reported syntheses of
zeolites. The early synthetic work remains
unsubstantiated because of incomplete
characterization and the difficulty of experi-
mental reproducibility.
BARRER began his pioneering work in zeolite
adsorption and synthesis in the mid 1930s to
1940s. He presented the first classification of
the then known zeolites based on molecular
size considerations in 1945 [21]. In 1948 he
reported the first definitive synthesis of zeolites
including the synthetic analogue of the zeolite
mineral mordenite [22] and a novel synthetic
zeolite [23, 24], which was much later identified
as the KFI framework. BARRER’s work in the mid
to late 1940s inspired MILTON of the Linde
Division of Union Carbide Corporation to initi-
ate studies in zeolite synthesis in search of new
approaches for separation and purification of
air. Between 1949 and 1954 MILTON and co-
worker BRECK discovered a number of commer-
cially significant zeolites, types A, X, and Y.
Zeolites 3
Zeolites only became of industrial impor-
tance in the 1950s, when synthetic examples
became available on an industrial scale [25]. In
1954 Union Carbide commercialized synthetic
zeolites as a new class of industrial materials for
separation and purification. The earliest appli-
cations were the drying of refrigerant gas and
natural gas. In 1955 Reed and BRECK reported
the structure of the synthetic zeolite A [26]. In
1959 Union Carbide marketed the ‘‘ISOSIV’’
process for normal isoparaffin separation, re-
presenting the first major bulk separation pro-
cess using true molecular sieving selectivity,
and a zeolite Y based catalyst was marketed by
Carbide as an isomerization catalyst [25].
In 1962 Mobil Oil introduced the use of
synthetic zeolite X as a hydrocarbon cracking
catalyst. In 1969 Grace described the first mod-
ification chemistry based on steaming zeolite Y
to form an ‘‘ultrastable’’ Y. In 1967 and 1969
Mobil Oil reported the synthesis of the high
silica zeolites beta and ZSM-5. In 1974 Henkel
introduced zeolite A in detergents as a replace-
ment for the environmentally suspect phos-
phates. In 1977 Union Carbide introduced zeo-
lites for ion exchange separations
The wide range of commercial applications
has stimulated intensive investigation
of the chemistry and physics of the zeolites
[27–47]. The early evolution of aluminosilicate
zeolite research, from the 1950s to the 1970s,
was largely based on increasing framework
Si/Al composition. In general, increasing
framework Si/Al composition increases thermal
stability, changes the surface selectivity from
hydrophilic to hydrophobic, increases the acid-
ity, and decreases the cation concentration and
ion-exchange capacity.
Since the 1980s, there has been an explosion
in the discovery of new compositions and struc-
tures. The first edition of the Atlas of Zeolite
Structure Types published in 1978 [48] and
prepared by the Structure Commission of the
International Zeolite Association contained 38
structure types. The current online database [7]
contains 201 structure types. Thus, 163 new
structure types have been discovered since
1978. However, many of the structure types
included in the Atlas are not truly zeolites or
molecular sieve materials. Some are not stable
to removal of the as-synthesized guest species,
typically water or organic templates, and
4 Zeolites
therefore cannot reversibly adsorb molecules or
carry out catalytic reactions.
Research has become increasingly con-
cerned with zeolite-like molecular sieves,
which have expanded the field of zeolites enor-
mously during the last few decades. In these new
materials, the aluminum and silicon of the
classical zeolites are partially or completely
replaced by other elements. For example,
metallosilicate molecular sieves have been
reported where the metals iron, boron, chromi-
um, arsenic, gallium, titanium, and germanium
are incorporated during synthesis into silica or
aluminosilicate frameworks [49–52]. Crystal-
line microporous frameworks have been
reported with compositions of: beryllopho-
sphate [53–56]; aluminoborate [57]; aluminoar-
senate [58]; galloarsenate [59]; gallopho-
sphate [60]; antimonosilicate [61]; and
germanosilicate [62], metallosulfides, and
metalloarsenides [63–65].
The aluminophosphate ‘‘ALPO’’ family [33,
34, 66–69] of molecular sieves discovered in the
1980s can be represented by the empirical
formula
Al2 O3 P2 O5 w H2 O
Substitution leads to the silicoaluminopho-
sphate family ‘‘SAPO’’ [70–73]. In the metal-
loaluminophosphate families ‘‘MeAPO’’ and
‘‘MeAPSO’’ [67], metal species include Co, Fe,
Mg, Mn, and Zn. Structure types crystallized
in the MeAPO family include framework
topologies related to the zeolites and some never
observed in zeolites. In the ‘‘ElAPO’’ and
‘‘ElAPSO’’ families the additional elements Li,
Be, B, Ga, Ge, As, and Ti have been incorpo-
rated into the AlPO4 framework. The over two
dozen structures of AlPO4-based molecular
sieves reported to date include zeolite topologi-
cal analogues and a large number of novel
structures. Most of the catalytic interest in the
AlO4-based molecular sieves have centered on
the SAPOs that have weak to moderate Brønsted
acidity. Two have been commercialized,
SAPO-11 in lube oil dewaxing by Chevron and
SAPO-34 in methanol-to-olefins conversion by
UOP/Norsk Hydro. For a review of recent de-
velopments in AlPO4-based molecular sieves
see [74, 75].
Recent developments in zeolite synthesis
and new materials include the use of combina-
torial methodologies, microwave heating, mul-
tiple templates or SDAs and concentrated fluo-
ride media in synthesis [76, 77]; synthesis using
the charge density mismatch concept [78–81];
synthesis in ionothermal media; synthesis with
complex ‘‘designer‘‘ templates or SDAs [82];
synthesis of nanozeolites; zeolite membranes
and thin films; and germanosilicate zeolites
[83, 84]
4. Structure, Composition, and
Properties
4.1. Framework Structure
Zeolites are classified structurally as tectosili-
cates [4]. The basic elements of their frame-
works are TO4 tetrahedra (T ¼ Si, Al) linked
through oxygen atoms to form three-dimension-
al structures. The Database of Zeolite Struc-
tures [8] as of February 2012 describes 201
different zeolite framework types, including
both classical zeolites and zeolite-like molecu-
lar sieves. Two of these structure types, LTA
and FAU, are shown in Figure 1.
The description and classification of the
topology of zeolites is based on the concept of
secondary building units (SBUs) and composite
building units (CBUs) composed of multiple
TO4 tetrahedra. SBUs are derived assuming the
entire framework is made up of one type of SBU
only. Those types of SBU that have been found
to exist in at least two frameworks are listed in
the database [7]. A complete list of SBUs is
given by VAN KONINGSVELD [85]. CBUs are
useful for describing and comparing framework
structures. Some of the more common CBUs are
shown in the database and extensive lists are
given [45, 85]. Polyhedral CBUs are sometimes
described using common names, three-charac-
ter codes, or descriptors. For example, the CBU
shown in Figure 1A is commonly called a
sodalite cage or a beta-cage. Two different
three-character codes are used in the literature,
sod (for sodalite) and toc (for truncated octahe-
dron). Descriptors are given as [am bn. . .] where
m is the number of a-rings, n is the number of b-
rings, etc). Sodalite has the descriptor [4668]
because it is defined by six equivalent 4-rings
and eight equivalent 6-rings.

Figure 1. A) Sodalite cage or b-cage; B) Framework structure of zeolite A (structure type LTA) with a-cage; C) Framework
structure of faujasite (structure type FAU; zeolites X, Y) with supercage
The n-rings (where n is the number of T
atoms in the ring) defining the face of a polyhe-
dral CBU are called windows or pores. Polyhe-
dra whose faces are no larger than 6-rings are
called cages. Polyhedra with at least one face
larger than a 6-ring are called cavities. Pores that
are infinitely extended in one dimension and are
larger than 6-rings are called channels. Frame-
work types can contain 1-, 2-, or 3-dimensional
channels.
In zeolite A (LTA structure type) shown in
Figure 1B, sodalite cages are linked together via
cubic units to form the larger alpha cavity with
the shape of a truncated cubo-octahedron. The
LTA structure type thus contains two types of
cages, d4r [46] and sod [4668], and one type of
cavity, lta [4126886]. The alpha cavities are
interconnected by windows formed by rings
consisting of 8 T atoms, giving a three-dimen-
sional intersecting channel system with 8-ring
pores. If the sodalite cages are linked together
by hexagonal prisms, faujasite (FAU structure
type) results (Fig. 1C). In this case, the linking
leads to a larger cavity, commonly called the
supercage because of its large diameter (ca.
1.20 nm), having windows formed by 12 T
atoms.
The pore system of mordenite (structure type
MOR) is two-dimensional; the 12-ring channels
being in effect only one-dimensional (Fig. 2A).
ZSM-5 zeolite (MFI structure type) contains a
more complex channel system. The structure is
easier to visualize if only the channel system is
represented, as shown in Figure 2B and not the
Zeolites 5
framework structure. Linear parallel 10-ring
channels are linked together by zigzag-shaped
continuous pores with 10-ring apertures perpen-
dicular to the channels, resulting in a three-
dimensional channel system.
The regular nature of the pores and their
apertures, whose dimensions are of the same
order of magnitude as molecular diameters,
enables the zeolites to function as molecular
sieves. This is the outstanding property of zeo-
lites that gives them their value as selective
adsorbents for separating substances and as
shape-selective catalysts (see Sections 8.2.1
and 8.2.3). Depending on the zeolite type and
its channel system, molecules can penetrate into
the cavities or be excluded (Fig. 3). Access into
the cavities is limited by the pore or n-ring with
the smallest free aperture along the channel. It is
common to refer to narrow-pore, medium-pore,
or wide-pore zeolites as those with pore aper-
tures formed by rings of 8, 10, or 12 T atoms,
with corresponding crystallographic diameters
of 0.35–0.45, 0.45–0.60, and 0.60–0.80 nm
[1, 86]. The aperture is calculated by subtracting
the diameter of an oxygen ion in silicate struc-
tures (0.27 nm) from the interatomic distance of
two opposing oxygen atoms across the ring. The
pore apertures of the industrially important
synthetic zeolites are listed in Table 1, together
with other characteristic data for these materi-
als [1, 86, 87]. It can also be seen from the table
that the apertures can deviate to varying extents
from circular. For example, the cross-section
of the zigzag pores in ZSM-5 is distinctly
6 Zeolites
Figure 2. A) Framework structure of mordenite (structure
type MOR) represented as linked SiO4/AlO4 tetrahedra;
B) Hollow tube representation of ZSM-5 (structure type
MFI)
elliptical. The concepts of kinetic molecular
diameter and effective pore size take account
of the fact that the adsorptive molecules and the
zeolite framework are not rigid but undergo
thermal vibrations. Therefore, the selectivity of
the exclusion of molecules whose diameters are
similar to that of the zeolite apertures deter-
mined crystallographically depends on temper-
ature. Thus, the crystallographic diameter of the
6-ring aperture of the b-cage, as in type A, X,
and Y zeolites, is given as 0.22 nm. However, at
room temperature, water molecules with a ki-
netic diameter of 0.26 nm can readily penetrate
into the b-cage, so that this should be regarded
as the effective pore aperture. The apparent pore
diameter can also be varied by using cations of
different sizes. Figure 3 illustrates this for the
example of zeolites KA, NaA, and CaA.
Several structure types with pore apertures
larger than 12-rings have been discovered, in-
cluding structures with 14-ring (AET, CFI,
DON, OSO, SFH, SFN, UTL), 18-ring (ETR,
IRR, VFI), 20-ring (-CLO), and 30-ring (-ITV)
pores. The DON structure type has been pre-
pared as an aluminosilicate (UTD-1) [88], and
the CFI structure type is found as a pure silica
(CIT-5) [89]. The other materials are only found
so far as alumino- and gallo-phosphates or as
silicates containing B, Be, Ga, or Ge.
4.2. Nonframework Cations
The cations needed to balance the negative
charge on the zeolite framework occupy definite
positions in the cavities and channels, where
they are surrounded by partially negatively
charged oxygen atoms from the rings of the
framework. The framework–cation bond thus
has a mainly ionic character. The preference of
particular cations for particular available sites
can be due to energetic, steric, and coordinative
considerations [90–93]. In the presence of ad-
sorptive molecules, a redistribution of the ca-
tions is possible. The nature and distribution of
the cations in the framework are of importance
when zeolites are used as adsorbents and cata-
lysts. Any change can lead to differences in both
apparent pore diameter and charge distribution.
Positions and distributions of cations in A-
type and faujasite-type zeolites have been re-
searched most thoroughly [90–92, 94]. In the
latter type, the most important positions are the
centers of the hexagonal prisms, in which octa-
hedral coordination is possible, and positions
close to the centers of the hexagonal surfaces in
the supercage and b-cages (see Fig. 1C). The
pattern of occupation of available sites depends
on the particular cations and on whether the
zeolite is anhydrous or hydrated.
A special situation arises if the zeolite is
converted into the so-called hydrogen form
in which the framework charge is formally
 Zeolites 7

Figure 3. Correlation between the effective pore size of industrially important zeolites and the kinetic molecular diameter of
selected compounds (room temperature)

balanced by Hþ. In this case, acidic OH groups
are bonded to the framework (see Section 8.2.3).
4.3. Chemical and Physical
Properties
Most of the chemical and physical properties of
the zeolites, and hence their areas of use, are
essentially determined by the aluminum content
of their frameworks. In the literature, this is
usually expressed by the Si/Al or SiO2/Al2O3.
According to the Loewenstein rule, Al–O–Al
groups cannot occur in crystalline aluminosili-
cates [95]. Hence, a SiO2/Al2O3 ratio of < 2 is
impossible for zeolites. As can be seen for the
synthetic zeolites in Table 1, each structure type
exhibits a phase breadth with respect to the

Table 1. Structures and compositions of some industrially important synthetic zeolites

Zeolite Structure Window, dimensionality Pore apertures, SiO2/Al2O3 Typical composition of unit cell
type of pore system nm

A LTA 8-ring, 3-D 0.41 2.0–6.8 Na12[(AlO2)12(SiO2)12]  27 H2O

P GIS 8-ring, 3-D 0.310.45 2.0–5.0 Na6[(AlO2)6(SiO2)10]  12 H2O
8-ring, 3-D 0.280.48
ZSM-5 MFI 10-ring, 3-D 0.530.56 25–¥ (Na,TPA)3[(AlO2)3(SiO2)93]  16 H2O*
10-ring, 3-D 0.510.55
X FAU 12-ring, 3-D 0.74 2.0–3.0 Na86[(AlO2)86(SiO2)106]  264 H2O
Y FAU 12-ring, 3-D 0.74 3.0–6.0 Na56[(AlO2)56(SiO2)136]  250 H2O
Mordenite MOR 12-ring, 1-D 0.650.70 9.0–35 Na8[(AlO2)8(SiO2)40]  24 H2O
8-ring, 2-D 0.260.57
*
TPA ¼ Tetrapropylammonium.
8 Zeolites
SiO2/Al2O3 ratio. A distinction can be made
between low-silica (SiO2/Al2O3 < 4), interme-
diate-silica (4 < SiO2/Al2O3 < 20), and high-
silica (20 < SiO2/Al2O3 < 200) zeolites and
zeosils, in which aluminum is present only as a
trace impurity (! Silica, Section 8.2.1) [96]. In
some intermediate-silica zeolites, a higher
SiO2/Al2O3 ratio can be produced by postsyn-
thetic dealumination.
The aluminum atoms may not be uniformly
distributed over the cross section of the zeolite
crystal. More often, especially with synthetic
high-silica zeolites, a zoning effect has been
observed [97, 98], which is important in cata-
lytic applications.
4.3.1. Physical Properties
Synthetic zeolites containing alkali metal and
alkaline-earth metal cations are normally color-
less crystalline powders. Colors only occur if
the zeolites contain transition metals as impuri-
ties or if they have been modified by ion ex-
change with these elements. As a rule, the
primary particles of industrially synthesized
zeolites have an average size of 0.1–15 mm,
although crystals with diameters of up to 5 mm
can be produced under special conditions [99].
The single crystals often form larger aggregates.
Like slurries of many other finely divided sub-
stances with surface-active groups, suspensions
of zeolites can exhibit thixotropy or rheopexy,
which is relevant in production processes.
On heating, hydrated zeolites release water.
Many zeolites can be almost completely freed of
adsorbed water without major alteration of their
crystal structure by calcination at 400–500 C,
leaving solids with large free pore volumes and
interior surfaces whose extent depends on the
framework density of the particular structure
type and on the number and nature of the ca-
tions. The cavities are then available for the
adsorption of guest molecules. The micropore
volume of, e.g., H-ZSM-5 (SiO2/Al2O3 ¼ 75)
is 0.18 cm3/g [100] and that of the NaA and
NaX zeolites (SiO2/Al2O3 ¼ 2.5), including the
b-cages, is as high as 0.29 and 0.36 cm3/g,
respectively [1].
Densities also vary with the openness of
the framework structure and the nature
of the cations, generally lying in the range
1.9–2.3 g/cm3. If the zeolite contains heavy
cations such as Ba2þ, densities can be higher.
The surface selectivity of the zeolites as
adsorbents depends on the SiO2/Al2O3 ratio.
Aluminum-rich zeolites preferentially adsorb
strongly polar molecules and are therefore
widely used as drying agents (see Section 8.2.1).
Increasing silicon content leads to increasingly
hydrophobic character, the transition from hy-
drophilic to hydrophobic behavior occurs at a
SiO2/Al2O3 ratio of ca. 20 [96].
Due to the mobility of the cations in their
cavities and channels, zeolites exhibit ionic
conductivity [1], which depends on the diameter
of the channels, the nature and concentration of
the cations, and the water content. Control of
these parameters and a wide range of other
techniques enable the conductivity properties
of zeolites to be modified to make them suitable
for future use as solid-state electrolytes,
membranes in ion-selective electrodes, and
components of cathode materials in batter-
ies [101, 102].
4.3.2. Chemical Properties
Despite their open structure, the zeolites have
remarkably good thermal stability, which varies
with the structure type, but more so with the
SiO2/Al2O3 ratio and the nature of the cations.
The effect of the SiO2/Al2O3 ratio is illustrated
by the example of faujasite. In a low-silica NaX
zeolite (SiO2/Al2O3 ¼ 2.5), structural collapse
was observed above 660 C, while a structurally
equivalent NaY zeolite (SiO2/Al2O3 ¼ 5.0) be-
came amorphous above 700 C [1]. Highly deal-
uminated Y type zeolites, however, are struc-
turally stable at > 1000 C [103]. The effect of
the cation can be seen in zeolite A, the Ca form
losing its structure above 700 C, and the Na
form above 660 C [1]. Above the decomposi-
tion temperature, recrystallization usually oc-
curs, e.g., forming b-cristobalite (zeolite A) or a
carnegieite phase (zeolite X).
The hydrothermal stability of the zeolites,
i.e., the ability to retain their structure without
undergoing a phase change in the presence of
water vapor, is of practical importance. For
example, fluid catalytic cracking (FCC) cata-
lysts, which contain Y-type zeolites, are used in
processes where steam is used to strip off

adhering hydrocarbons [104]. The same factors
that affect thermal stability also influence hy-
drothermal stability.
Strong acids decompose low-silica zeolites,
such as NaA and NaX, by dissolving the alumi-
num atoms out of the framework with conse-
quent breakdown of the crystal structure [105].
With increasing SiO2/Al2O3 ratio, the zeolites
become less sensitive to dealumination by
acids; high-silica zeolites are structurally stable
even in strong mineral acids [103].
Aqueous alkalis lead to phase transitions in
high-aluminum zeolites. Thus, sodium hydrox-
ide solution converts NaA zeolite into hydro-
xysodalite, which must be taken into account in
production (see Section 7.3.2). Very high silica
zeolites are dissolved by strong alkalis [106].
Suspensions of high-aluminum zeolites in
which the cation is Naþ have a pH of 9–12 due
to partial hydrolysis.
The ion-exchange capacity of zeolites de-
creases with increasing SiO2/Al2O3 ratio. The
catalytic properties of the hydrogen form, in
which Hþ ions formally replace the metal ions,
are discussed in Section 8.2.3.
5. Characterization
In principle, all methods used for investigating
solids can be used for zeolites. In most cases,
multiple techniques are needed to fully describe
a zeolite system [107–113].
The size and shape of the zeolite crystals or
aggregates must be investigated for most appli-
cations. This is carried out by microscopy,
generally with a scanning electron microscope
because of the small particle size. The particle
size distribution can be rapidly determined by
laser scattering or the Coulter counter method
on zeolite suspensions.
Zeolites 9
The most important technique used to
determine structure type and phase purity is
X-ray diffraction (XRD). For known structures,
a classification can be carried out by using
the published powder diffraction patterns
[114–116]. When structures of new materials
are determined, the crystals available are sel-
dom large enough for single-crystal X-ray struc-
ture analysis. Powder diffraction methods are
therefore usual, sometimes with use of synchro-
tron radiation [117]. The Rietveld method
of profile analysis of the diffraction pattern
has been developed into a very powerful
tool [118–121]. The fraction of crystalline
zeolite in a mixture can be determined by com-
parison with a standard material. This so-called
crystallinity is usually determined by compar-
ing the intensities of selected reflections [122].
The thermal stability of zeolites can be de-
termined by XRD or differential thermal analy-
sis. Zeolites can be analyzed for elements by
classical wet chemical methods, but modern
physical methods are usually preferred, i.e.,
X-ray fluorescence (XRF), atomic absorption
(AA), and inductively coupled plasma (ICP)
spectrometries. X-ray photoelectron spectros-
copy (XPS) is particularly useful for obtaining
information about the composition of the outer
atomic layers of a zeolite crystal.
The determination of the SiO2/Al2O3 ratio of
zeolites is of importance in many of their
applications. While the SiO2/Al2O3 ratio of the
bulk sample can easily be analyzed by elemental
analysis, more detailed information can be ob-
tained by high-resolution magic angle spinning
(MAS) NMR spectroscopy. Thus 29Si MAS-
NMR spectroscopy is very suitable for deter-
mining the SiO2/Al2O3 ratio of the zeolite
framework, especially if the sample also con-
tains aluminum that is not part of the frame-
work. 29Si and 27Al MAS-NMR spectroscopy
also give important information on the short-
range structural environment of the silicon and
aluminum atoms [123–127]. Thus, the five
groups Si(OSi)4
n(OAl)n (n ¼ 0–4) give sig-
nals with different chemical shifts in the 29Si
MAS-NMR spectrum. In the 27Al MAS-NMR
spectrum, aluminum atoms in different states of
coordination give separate signals. In zeolites of
the faujasite type, the SiO2/Al2O3 ratio can also
be estimated from measurements of the crystal-
lographic unit cell [128] and from the position of
10 Zeolites
the framework-vibration bands in the IR
spectrum [129].
Information about the characteristics of the
pore system can be obtained from adsorption
measurements. The size of the apertures can be
estimated by testing their accessibility to ad-
sorptives of various kinetic diameters. One of
the most widely used methods for determining
the pore size and surface area of zeolites is
nitrogen physisorption [43, 130–132]. From the
shape of the nitrogen adsorption and desorption
isotherm the presence and shape of the meso-
pores can be deduced. The t-plot method [133]
can be used to calculate the micropore volume
(pores smaller than 2 nm) and mesopore vol-
ume (pores between 2 and 50 nm). Test catalyt-
ic reactions, the outcome of which depends on
the shape selectivity of the zeolite (see Sec-
tion 8.2.3), can also be used to characterize pore
systems. Depending on the reaction, the char-
acteristic value obtained is known as the con-
straint index, the modified constraint index, or
the spaciousness index [134].
In the development of zeolite catalysts, it is
also important to characterize their acidity prop-
erties, i.e., the nature, number, and strength of
the acid sites [135, 136]. Methods include tem-
perature-programmed desorption (TPD) of ad-
sorbed bases, such as ammonia and pyridine, 1H
MAS-NMR spectroscopy [124, 125, 137], IR
spectroscopy in the region of O–H stretching
frequencies [138, 139], IR spectroscopy with
probe molecules [107, 140], and measurement
of the catalytic activity of the zeolites in stan-
dard reactions [136].
In addition to these general methods of in-
vestigation, zeolites are also characterized in
industry by parameters that relate to a particular
application. For example, where zeolites are
used as detergent builders, these can include
calcium binding power (determined by titration)
and whiteness [141]. The suitability of a zeolite
as a catalyst is determined by testing it in the
reaction concerned [142].
6. Occurrence, Mining, and
Processing of Natural Zeolites
Zeolite minerals occur in many rocks on the
earth’s surface and on the seabed. They were
first discovered in crevices and cavities in basalt
flows, where they were formed by the hydro-
thermal decomposition of the magmatic rock. It
was only in the mid-1900s that zeolites were
found to occur in enormous quantities as sedi-
mentary rock. These zeolitic tuffs were formed
during various geological periods, mainly by the
action of water on volcanic ash. Zeolites were
also formed from poorly crystalline clays, bio-
genic silica, feldspars, and feldspathoids. More-
over, the less stable types of zeolite formed
during the initial crystallization changed into
more stable types, e.g., phillipsite or clinopti-
lolite in analcime.
The formation of zeolites was influenced by
many specific local conditions that had to be
favorable: temperature (usually in the range 25–
50 C), pressure, pH, type and concentration of
salts, and availability as well as reactivity of
silicon and aluminum sources. Suitable condi-
tions arise in various geological or hydrological
systems, which can be open or closed [35, 36,
143]. Thus, zeolites occur in deposits formed
from lakes with high salt or alkali contents in
arid and semiarid regions. Here, dissolved so-
dium carbonate-sodium hydrogen carbonate
can cause the pH to reach ca. 9.5. Zeolites have
also been formed in alkaline soils on the earth’s
surface and in ocean sediments as a result of the
action of percolating water, hydrothermal ac-
tivity, and burial diagenesis. Depending on the
system, a characteristic series of deposits vary-
ing in composition, thickness, and extent is
formed. The zeolite-containing layers can be
several hundred meters in depth and can extend
over areas of hundreds of square kilometers.
Of the nearly 60 natural zeolites know
today [144], clinoptilolite [12173-10-3] and the
structurally related heulandite, mordenite
[12173-98-7], phillipsite, chabazite [12251-
32-0], erionite, analcime, and laumontite occur
in the largest quantities. However, only the first
six of these materials are of commercial impor-
tance at present. Information on the structures
and composition ranges of these zeolites is
given in Table 2.
The quantity of natural zeolites mined
worldwide is estimated to be 2.75  106 t/a
with China producing an estimated 2  106 t/a
[146]. Natural zeolites are mined in the western
United States, Cuba, Japan, Slovakia, Hungary,
Serbia, Bulgaria, Italy, Germany, and the
CIS states, mainly by the opencast method.

Table 2. Structures and compositions of some important natural zeolites
Zeolite Structure Window, dimensionality
type of pore system
Clinoptilolite HEU (3) 8-/10-/8-ring, 3-D
Heulandite HEU (3) 8-/10-/8-ring, 3-D
Mordenite MOR (2) 12-/8-ring, 1-D
Phillipsite PHI (3) 8-/8-/8-ring, 3-D
Chabazite CHA (3) 8-ring, 3-D
Erionite ERI (3) 8-ring, 3-D
Depending on the deposit, zeolites can contain
other minerals as impurities, e.g., montmoril-
lonite, cristobalite, quartz, biotite, and potassi-
um feldspar. Mixtures of different zeolites often
occur. Zeolitic minerals are processed by crush-
ing, grinding, and classification. If they are to be
used as fillers in the paper industry, wet chemi-
cal bleaching is also necessary [35].
7. Production of Synthetic Zeolites
Synthetic zeolites are prepared by combining
raw materials containing silica, alumina, struc-
ture-directing cations, base, and water into a
reactive slurry then heating this mixture until
the amorphous solids are converted into crys-
talline aluminosilicate zeolites [147]. The zeo-
lites then undergo a variety of postsynthesis
treatments to adjust the composition of the
zeolites and form them into the shapes required
for the specific catalytic, adsorption, or ion-
exchange application [1, 148].
7.1. Chemistry of Zeolite Synthesis
Zeolite synthesis is a crystallization process
wherein sources of reactive silica and alumina
dissolve and react to give a less soluble crystal-
line aluminosilicate product. A unique feature
of this crystallization process is the presence of
solid precursor materials throughout the crys-
tallization. These solid precursors must dissolve
at a rate that allows nucleation of the desired
zeolite phase then at a rate that supports growth
of the crystals until the raw material solids are
completely consumed. Depending on the raw
materials used and the way in which they are
combined, the reaction mixture can contain
solids in which the Al2O3 and SiO2 are homo-
geneously mixed or are relatively segregated.
Zeolites 11
SiO2/ [Al2O3 Most common Typical composition of unit cell
þ Fe2O3] cations
8.0–10.2 K > Na (Na,K)6[(AlO2)6(SiO2)30]  24 H2O
5.8–8.0 Ca, Na Ca4[(AlO2)8(SiO2)28]  24 H2O
8.6–10.6 Na > K Na8[(AlO2)8(SiO2)40]  24 H2O
2.6–6.8 K, Na, Ca (Ca,K2,Na2)3[(AlO2)6(SiO2)10]  12 H2O
3.4–7.6 Ca, Na, K Ca6[(AlO2)12(SiO2)24]  40 H2O
6.0–7.0 K, Mg, Ca, Na (Ca,Mg,Na2,K2)4.5[(AlO2)9(SiO2)27]  27 H2O
The reaction/crystallization process is car-
ried out at elevated temperature in a basic
aqueous medium. This hydrothermal process is
similar to how zeolites are formed in nature, but
the commercial processes operate at significant-
ly higher pH and/or temperature to allow the
crystallization to proceed at a much faster
rate [30]. The basic chemical processes that
take place during the formation of zeolites
include the following:
. Dissolution of silicate and aluminate ions
from the solid precursors
. Nucleation of zeolite crystals
. Growth of zeolite crystals
The rate of all three of these processes in-
creases with increasing hydroxide concentra-
tion and temperature. Each process involves the
base catalyzed hydrolysis and condensation of
Si–O–H and Al–O–H bonds (e.g., Si–O–Si þ
H–O–H $ Si–O–H þ H–O–Si). The amor-
phous precursor solids are likely to undergo
continual change during the entire synthesis as
Si and Al dissolve and redeposit as more ordered
and less soluble material [149]. Nucleation and
growth of the zeolite crystals occurs when the
proper level of supersaturation is generated by
the dissolving precursor solids. The F
anion
can also be used as a low pH mineralizer instead
of or in addition to hydroxide for the preparation
of some zeolites.
Incorporation of Al3þ into the charge-bal-
anced silica structure (O2
–Si4þ–O2
) creates a

1 charge on the silica framework for each Al
substitution. This negative charge is balanced
by either hydrated inorganic cations (e.g., Na
(H2O)xþ) or alkylammonium cations. These
cations, which become incorporated into the
developing open spaces within the porous zeo-
lite structures, serve the dual role of balancing
framework charge and filling pore space.
12 Zeolites
The type of zeolite structure which forms is
dependent on the composition of the reaction
mixture, the raw materials used, and the precise
reaction conditions. Most zeolite structures are
thermodynamically metastable with respect to
other more dense structures and can be hydro-
thermally converted to those structures given
sufficient time and temperature.
7.2. Composition of Reaction
Mixtures
Each zeolite structure type has a specific
range of product Si/Al ratios in which it will
readily form. Excess Si in reaction mixtures
is required to synthesize zeolites that have a
product Si/Al > 1. This is due to a higher
solubility in base of zeolites with higher Si/Al
ratios. Dissolution of a zeolite in base is incon-
gruent and results in more Si in the solution
phase than Al.
Because the synthesis of zeolites is a crys-
tallization process, solution concentrations and
their respective levels of supersaturation should
govern the relative rates of crystal nucleation
and crystal growth [150]. Despite the impor-
tance of solution concentrations to crystalliza-
tion processes, little is known of the actual
solubilities of either zeolites or their reactive
precursors at crystallization conditions. This is
due in large part to the difficulties in measuring
solubilities of very small, metastable crystals at
elevated temperatures and in the presence of
unreacted solid raw materials [151]. In practice
the composition of reaction mixtures along with
the reaction conditions are varied systematically
until the desired zeolite and its properties are
obtained.
The cations that are present in zeolite reac-
tion compositions are often referred to as struc-
ture directing agents or templates. In addition to
specific ranges of Si/Al ratios, each zeolite
structure type has specific cations or mixtures
of cations that will favor its formation. Features
of the cations that likely affect the stability of the
developing zeolite are size, shape, charge, and
charge distribution [152].
The composition of reaction mixtures is
commonly expressed as a molar oxide ratio,
e.g., aNa2O : Al2O3 : bSiO2 : cH2O. Figure 4
shows an example of the ranges of
Figure 4. Synthesis fields a Na2O : b Al2O3 : c SiO2 : (90–
100) H2O for various zeolites (HS ¼ hydroxysodalite) at a
crystallization temperature of 100 C
Points marked with asterisks indicate typical compositions
of the products.
Na2O–Al2O3–SiO2 reaction compositions that
give the various Na zeolites.
7.3. Raw Materials
Common sources of Si used for the synthesis of
zeolites include sodium silicate (water glass),
precipitated silica, clay, fumed silica, colloidal
silica, and tetraethyl orthosilicate. Sodium sili-
cate is the most economical and widely used
source for the commercial production of
zeolites.
Sources of Al include sodium aluminate,
aluminum sulfate, alumina, clay, and aluminum
alkoxides. When low cost sodium aluminate
solutions are combined with sodium silicate
solutions, a dense gel (hydrogel) is formed that
is an ideal raw material for the synthesis of low
Si/Al zeolites.
Clays containing the mineral kaolinite,
which has a Si/Al ratio of 1.0, can serve as a
source of both Si and Al. An advantage to using
clay as a raw material is that it can be readily
formed into the desired product shape, e.g.,
extruded pellets, beads, or granules, then
converted into zeolites while maintaining the
preformed shape. With this method binder-free,
i.e., essentially 100% zeolite, formed products
can be obtained.

The choice of raw materials used for the
synthesis of zeolites is critical to obtaining the
desired structure type, composition, and crystal
morphology. Since all the raw materials are
typically added at the start of the synthesis,
i.e., at the gel make-up step, the solids present
in this reaction mixture must react and dissolve
at the proper rates to enable first nucleation then
growth of the zeolite crystals. Because different
raw materials have different surface areas and
chemical compositions, their chemical reactiv-
ity and rates of dissolution vary significantly.
Cations used for structure directing agents
include alkali metals, alkaline earths, and tetra-
alkylammonium cations. The cations may be
introduced as integral components of the Al and
Si sources, e.g., Na aluminate or Na silicate, or
as salts with common anions, e.g., hydroxides,
sulfates, nitrates, or halides. Although the
choice of the cation(s) is critical for obtaining
the desired structure type, the choice of the
anion is often based on cost, availability, metal
corrosion (e.g., halides), or the need to adjust pH
(e.g., hydroxides). For some high Si/Al zeolites,
neutral amine compounds can also be used as
structure directing agents.
7.3.1. Synthesis Conditions
Many synthesis variables beyond the reaction
mixture composition and choice of raw materi-
als determine which zeolite structure type is
formed and what size, shape, and level of ag-
glomeration the zeolite crystals adopt. These
variables include the following:
. Addition order of the raw materials
. Length of addition times
. Intensity of agitation during the gel makeup
. Gel aging
. Heat-up temperature profile
. Crystallization temperature
. Time at crystallization temperature
. Intensity of agitation during crystallization
. Cool-down temperature profile
The low solubility of zeolites and many of
the raw materials used to make zeolites requires
that syntheses be conducted at elevated tem-
peratures to obtain reasonable rates of crystalli-
zation. Typical temperatures used for zeolite
Zeolites 13
syntheses range from 50 C to 200 C, and syn-
thesis times range from one hour to several days.
Generally, the zeolites with low Si/Al, e.g., NaA
and NaX, can be prepared in short times (2–4
h) and low temperatures (< 100 C) whereas
high Si/Al zeolites, such as ZSM-5, require
higher temperatures and/or longer crystalliza-
tion times. Some zeolites also benefit from an
initial low temperature aging step that facilitates
the nucleation process. The pH of reaction
mixtures typically ranges from 10 to 14.
Reaction mixtures are generally heteroge-
neous slurries containing undissolved raw ma-
terials that are eventually converted to the crys-
talline product. Because of this heterogeneity,
the affect of agitation on the course of the
crystallization can be very pronounced. Forma-
tion of some zeolite phases can be either in-
hibited or favored with agitation [153]. Because
agitation is generally required at commercial
scale to achieve good heat transfer in large
vessels, scaleup of new zeolites prepared via
unstirred syntheses in the laboratory can be
challenging.
Commercial zeolite crystallizers are gener-
ally stirred tanks having capacities of thousands
of liters and some provision for heating the
contents, e.g., a heating jacket. Laboratory prep-
aration of zeolites is conducted in a large variety
of vessels ranging from small (< 10 mL), un-
stirred PFTE lined vessels to stirred metal auto-
claves > 3.8 L.
7.3.2. Examples of Industrial Zeolite
Syntheses
Most known synthetic zeolites have only been
prepared on the laboratory scale [154]. The
processes and potential problems in the indus-
trial production of zeolites [1, 155–157] are
illustrated here by the syntheses of the commer-
cially important zeolites NaA, NaY, and Na-
ZSM-5.
Zeolite NaA [68989-22-0] is mainly used
directly as a detergent builder ! Laundry De-
tergents, 2. Ingredients and Products, but is also
a starting material for the production of a wide
range of adsorbents (see Section 8.2.1). An NaA
zeolite detergent builder should have the fol-
lowing properties: high ion-exchange capacity
14 Zeolites

Figure 5. Electron micrograph showing crystals of deter-

gent NaA zeolite

(> 160 mg CaO/g dry weight at 20 C) [141]

with the ability to bind ions (especially Ca2þ)
rapidly, good dispersibility, low tendency of
suspensions to settle out, low abrasive proper-
ties, and good whiteness. This means that the
zeolite must consist of a single phase, as the
presence of impurities, such as hydroxysodalite,
which forms readily along with NaA, reduces
the ability of the product to bind Ca2þ ions.
Furthermore, the average particle size must be
< 4 mm, and the zeolite crystals must not have
sharp corners or edges. A scanning electron
micrograph of a material of this type is shown
in Figure 5.
In the Degussa [158], Henkel [159, 160], and
PQ processes, such a zeolite is synthesized by
reacting sodium silicate containing various
amounts of Na2O and SiO2 with sodium alumi-
nate solutions. Clays are less often used, as the
presence of impurities, especially iron, can im-
part an undesirable color to the product. A
special variation is the Mizusawa process in
which acid-treated clay is used [161].
In the production of zeolite NaA, the stoi-
chiometry of the reaction mixture can in princi-
ple be varied over a relatively wide range.
However, efficient production requires optimi-
zation of the composition from the point of view
of product quality, yield, and reaction time. A
possible stoichiometry is 3.4 Na2O : Al2O3 : 1.8
SiO2 : 90 H2O [159]. In this example, an excess
of aluminum compared with the product stoi-
chiometry (SiO2/Al2O3 ¼ 2.0) is used.
Figure 6 is a flow diagram of a process
for the production of this zeolite [162]. Gel
Figure 6. Process for the preparation of NaA zeolite [162]
a) Silica–alumina hydrogel precipitation; b) Zeolite crystal-
lization; c) Filtration; d) Mother liquor evaporation;
e) Zeolite spray drying; f) Stabilized suspension of NaA
zeolite
precipitation and aging are usually carried out
at 50–70 C. Gel precipitation is generally a
batch process, but it can also be carried out
continuously [160]. However, the subsequent
crystallization at 80–90 C is a batch operation
in stirred vessels, often > 100 m3 in volume.
Under these conditions, the zeolite is present in
crystalline form after ca. 1 h. The suspension
formed contains 120–200 kg zeolite (dry basis)/
per cubic meter. The product is recovered and
washed on a filter press, rotary filter, or band
filter. The filter cake is slurried in water and,
after the addition of stabilizers to prevent rapid
sedimentation, is usually supplied to the deter-
gent manufacturer in this form. The products are
obtained in powder form by spray drying the
zeolite suspension or by directly drying the
zeolite filter cake.
 Zeolites 15

Both the mother liquor from zeolite crystal-

lization and the wash water are alkaline as they
contain residual sodium hydroxide. If an excess
of Al2O3 is used, sodium aluminate is also
present. In this case, the filtrate is concentrated
by evaporation and recycled.
The particle size, a critical parameter when
the product is used as a detergent builder, is
influenced by the Na2O/H2O ratio in the reac-
tion mixture. High basicity favors the formation
of small particles [163]. The sequence of addi-
tion of the various components and the rate of
addition during gel preparation also exert an
influence. Other factors include temperature
and method of stirring, especially during gel
formation, and use of seed crystals [155].

Zeolite NaY is the basis for the zeolite

components of FCC and hydrocracking cata-
lysts (see Section 8.2.3). This raw material must
have high phase purity and good crystallinity.
The SiO2/Al2O3 ratio should be as high as
possible, as type Y zeolites modified for cata-
lytic purposes must have good thermal and
hydrothermal stability.
Commercially available NaY zeolites have a
SiO2/Al2O3 ratio of 5.0–5.6. In principle, ma-
terials with higher SiO2 content can be produced
by direct synthesis, but the necessary reduction
of the Na2O/SiO2 and Na2O/H2O ratios in the
reaction mixture lead to a drastic increase in
crystallization time, so that such syntheses are
not economic [164, 165]. Reaction mixtures
with composition (2.5–3.5) Na2O : Al2O3 :
(8.0–10.0) SiO2 : (120–180) H2O are usually
used for industrial production of NaY zeolite.
In early syntheses of NaY zeolite, the gel
initially precipitated had to be aged for one or
more days at room temperature. Today, seeding
mixtures are generally added instead, often in
colloidal form [166, 167]. They have composi-
tions in the range (10– 6) Na2O : Al2O3 : (10–16)
SiO2 : (180–320) H2O and strongly influence
the rate of crystallization.
The temperature during crystallization is 85–
100 C. Depending on this and on the composi-
tion and nature of the gel, a well-crystallized
NaY zeolite can be obtained in 12–24 h. In
some cases, vigorous stirring can lead to the
formation of gmelinite and phillipsite as foreign
phases. If the heating time is too long, this can
cause transformation into more thermodynami-
Figure 7. Process for the production of NaY zeolite [169]
a) Zeolite synthesis (gel precipitation, aging, crystalliza-
tion); b) Zeolite filtration; c) Zeolite storage; d) Mother
liquor and wash water storage; e) Silica–alumina hydrogel
formation; f) Silica–alumina hydrogel filtration and wash-
ing; g) Silica–alumina hydrogel slurry storage
cally stable zeolites of the P or cancrinite
type [168].
Figure 7 is a schematic flow diagram of a
process for the production of NaY zeolite [169].
Characteristic of this process is the work-up of
the mother liquor, which in the case of the
synthesis of NaY zeolite is a dilute solution of
sodium silicate.
ZSM-5 [79982-98-2]. As the SiO2/Al2O3
ratio of ZSM-5 can vary over a wide range (see
Table 1), ZSM-5, first synthesized by Mo-
bil [170], is not a single material, but a family
of zeolites of the MFI structure type. The syn-
thesis of these compounds differs from that of
NaA and NaY zeolites mainly in that it is carried
out at 120–180 C in pressure vessels. ZSM-5
16 Zeolites
can be crystallized with or without template
compounds [98, 170–173]. Tetrapropylammo-
nium salts are mainly used as template, but
hexamethylenediamine and a series of other
compounds are also suitable [174, 175]. How-
ever, the ranges of SiO2/Al2O3 ratios achiev-
able in the product by varying the initial stoi-
chiometry by the two methods are not identical.
Thus, without a structure-directing agent, SiO2/
Al2O3 ratios between ca. 25 and 100 can be
obtained, whereas with template compounds a
significantly wider range can be covered, i.e.,
from ca. 30 to the aluminum-free form (silica-
lite-1). Moreover, depending on the raw mate-
rials used and the exact synthesis conditions, the
crystal morphology and distribution of the alu-
minum atoms over the crystal cross-section can
vary greatly [98, 171]. These parameters are of
major importance in the use of ZSM-5 zeolites
in catalysts.
The composition 17.1 (TPA)2O : Na2O :
Al2O3 : 27.7 SiO2 : 453 H2O is a typical exam-
ple of a synthesis mixture for which tetrapro-
pylammonium bromide (TPABr) is used as the
template. After 5.5 d at 125 C, this gives ZSM-
5 with a SiO2/Al2O3 ratio of ca. 45 [108]. In
contrast, the synthesis mixture 11.2 Na2O :
Al2O3 : 70 SiO2 : 3213 H2O, without a template
and using colloidal silica as the source of silica,
gives a zeolite with an SiO2/Al2O3 ratio of 44
after 24 h at 190 C [172].
The crystal suspension obtained is worked up
as described for NaA and NaY zeolite. If an
organic template compound is used, it must be
calcined from the ZSM-5 pores by heating to ca.
650 C in air.
7.3.3. Post Synthesis Treatments
Following crystallization, the 0.5–10 mm
sized zeolite crystals are in a suspension with
a high pH mother liquor that typically contains
dissolved silica and/or alumina. Solid–liquid
separation and water washing can generally be
accomplished on a suitable filtration media.
Depending on what product the zeolite is to be
used in, the filter cake may undergo one or more
of the following processes:
. Drying
. Ion exchange
. Calcination
. Steaming
. Acid washing
. Forming
. Metal impregnation
Zeolites adsorb water very strongly and the
complete removal of water requires heating to
temperatures well in excess of 100 C. Complete
removal of water is only done in cases where the
adsorbed water will interfere with the intended
application. Heating at mild conditions,
100 C, will remove the intercrystalline water
and generate a relatively free flowing powder.
Control of the moisture content of zeolites is
important in all forming operations.
The cations that are present in the zeolite
pores following crystallization are generally not
the ones needed in the final product, but they can
be exchanged with other cations. The ease of
this ion exchange is dependent on the charge and
size of the cations [176]. Alkylammonium ca-
tions often are too large to be ion-exchanged and
must be thermally decomposed to remove them.
The process of ion exchange is accomplished by
placing the zeolite in a salt solution containing
the desired cation, often at elevated tempera-
ture, and allowing the mixture to come to equi-
librium. Multiple ion exchange cycles are gen-
erally needed to reach a high level of exchange.
The selectivity of the ion-exchange process can
be represented by plots showing the relative
amounts of the two cations in the solution (AS)
and in the zeolite (AZ) when equilibrated at a
fixed temperature. Figure 8 shows an example
of such an ion exchange isotherm for NaA
zeolite. Cation forms of general interest are
alkali metal and alkaline earths (for ion-ex-
change materials and adsorbents), rare earths
(for high thermal stability and acidic catalysts),
transition metals (for catalytic activity), and
ammonium (for conversion to the acid form for
catalysts).
Calcination is the process of heating
zeolites to high temperatures (> 300 C) in
order to:
. Completely remove water
. Decompose NH4þ into NH3 plus the Hþ form
of the zeolite
. Decompose organic materials, including
alkylammonium structure-directing cations

Figure 8. Ion-exchange isotherms for Liþ, Kþ, Agþ, and
Caþ on zeolite NaA at 25 C
Total concentration in aqueous phase: 0.1 N
. Change the oxidation state of transition
metals
The atmosphere used for calcinations is gen-
erally air, but can be an inert gas, vacuum, or any
level of oxidizing or reducing gases. Calcination
is also critical for many formed zeolites in order
to generate strong bonding with the binder.
The presence of elevated water vapor pres-
sure during the high temperature treatment of
zeolites (steaming) causes degradation to zeo-
lite structures. A fraction of the Al is removed
from the zeolite framework during this process,
and zeolites with relatively low Si/Al are most
affected. Although this can be an unwanted side
effect of calcination, it is also intentionally done
for zeolites such as Y to generate more thermal-
ly stable acid catalysts.
The Al that is expelled from zeolite frame-
works during steaming ends up as extraframe-
work Al within the pores of the zeolite. This Al
can be detrimental to the performance of the
zeolite and can be removed by treating the
zeolite in a mineral acid solution. Acid washing
can also be used for high Si/Al zeolites, such as
mordenite, to directly exchange cations with
protons to generate the acidic form. Other meth-
ods can also be used to directly dealuminate
zeolites, such as treatment with (NH4)2SiF6,
SiCl4, or EDTA [177].
All of the postsynthesis processes described
above can be applied to either zeolite powders or
Zeolites 17
formed zeolites. Formed materials have the
advantage of easier solid–liquid and solid–gas
separation, although zeolites embedded in a
matrix will receive different exposure to the
treatment conditions than zeolite powders.
Types of forming that are used to produce
zeolite-containing products are:
. Extrusion
. Bead forming
. Spray drying
. Granulating
Every application will require a particular
form and size of product in order to optimize
performance. Binders are used to give formed
bodies sufficient mechanical strength to with-
stand both processing and use in the applica-
tions. Binders commonly used include clays,
amorphous silica-alumina, alumina, amorphous
silica, and silica sols.
7.3.4. Environmental Aspects
In the industrial-scale production of zeolites,
such as NaA and NaY, substances present in the
mother liquors are recycled to the synthesis
process (production-integrated environmental
protection). The use of template compounds in
the production of specially zeolites presents
greater problems. The tetraalkylammonium
salts and organic amines, which are often used,
are very difficult to destroy by oxidation in the
mother liquor. There are therefore ecological as
well as economic reasons to minimize the
amounts of these compounds used in the
synthesis.
The same is true of the metal salts used in ion-
exchange processes. Here, judicious operation
can be of benefit in a multistage process [178].
Dilute solutions of ammonium salts, e.g., those
produced during the conversion of zeolites into
the catalytically active hydrogen form, can be
treated in various ways [179].
8. Commercial Applications and
Importance
The total global consumption of zeolites in 2008
is estimated at nearly 5  106 t, including about
18 Zeolites
1.8  106 t of synthetic zeolites and 2.9  106 t
of natural zeolites [217].
Since the introduction of zeolites as industri-
al materials in 1954, the annual market for
synthetic zeolite and molecular sieves has
grown to 1.8  106 t worldwide in 2008 [217,
180]. The major application areas are as adsor-
bents, catalysts and ion-exchange materials.
The largest single market by volume (72%) is
the detergent application, where zeolite A (and
recently Type P) functions as an ion exchanger.
In 2008, 1.27  106 t were estimated to be
consumed in this particular application. Al-
though the second largest volume use is as
catalysts (17%), this is the largest value market
for zeolites, about 55% of the total. Fluid cata-
lytic cracking (FCC) catalysts, which contain
primarily thermally and hydrothermally stabi-
lized zeolite Y, represent more than 95% of the
total zeolitic catalyst consumption. The remain-
ing of the catalyst usages come from hydro-
cracking and bulk chemical syntheses in chem-
ical and petrochemical areas. Catalyst con-
sumption in 2008 is estimated at 3.03 
105 t. Adsorption applications are varied and
include drying and purification of natural gas;
petrochemical streams, such as light olefins;
refrigerants; bulk separations like that of xylene
and of normal paraffins; and in air separation for
industrial gas production.
World consumption of natural zeolites
was estimated at about 2.9  106 t in 2008,
with the largest part in China and Cuba, and it is
mostly used for enhancing the strength of
cement.
The price of zeolites varies considerably
depending on the applications. The typical price
of the catalysts in the United States varies from
about $3–4/kg for FCC to about $20/kg for
specialty catalysts, adsorbents from about $5–
9/kg, up to tens of dollars per kilograms for
specialty adsorbents and about $2/kg for deter-
gents. Natural zeolite in bulk applications sell
for $0.04–0.25/kg and in industrial adsorbent
applications for $1.50–3.50/kg [217].
8.1. Natural Zeolites
The major uses for natural zeolites are as a
cement additive, to produce a slower-hardening
and stronger product, as a nutrient release agent
in soil conditioners, and as an odor control agent
in animal litter. The consumption of clinoptilo-
lite, which has a wide range of uses, far exceeds
that of any other natural zeolite [27, 35, 181].
For example, it is used in agriculture as an
animal feed additive and for soil improvement
(mainly in Japan). The latter application de-
pends on two effects: it increases the pH of the
soil and, being an ion-exchange material, stores
ammonium and potassium ions, thereby
prolonging the activity of fertilizers. The ability
to take up ammonium ions is also the reason for
the use of clinoptilolite and phillipsite in fish
farming and cat-litter production.
If high purity, constant composition, and
high capacity are not essential, natural zeolites
can compete with their synthetic counterparts
in a number of industrial applications. Exam-
ples include the drying of gases or liquids with
clinoptilolite tuffs and the selective adsorption
of CO2 and SO2 by clinoptilolite or mordenite.
In these applications, the stability of these
zeolites towards acids is advantageous. Clin-
optilolite is sometimes used for decontaminat-
ing radioactive wastewater because of its se-
lectivity for 90Sr and 137Cs ions [27, 35, 145,
181]. Natural zeolites are also used as fillers in
paper and plastics and as constituents of poz-
zalanic cements and lightweight building
blocks.
8.2. Synthetic Zeolites
World consumption of synthetic zeolites in the
fields of ion exchange, adsorption, and catalysis
has grown continuously. The major uses of
synthetic zeolites are as a builder in home
laundry detergent powders (about 72% of the
total), for production of catalysts (about 17% of
the total), and in adsorbent/desiccant applica-
tions (about 10% of the total).
In the separation processes, zeolites function
as adsorbents in the adsorptive separations and
as zeolite membranes and mixed matrix mem-
branes in membrane separations. In the catalysis
processes, zeolites function as catalyst in indus-
trial isomerization, industrial C–C bond forma-
tion, and industrial C–C bond breaking and
rearrangement. More detail information of the
zeolites in separation and catalysis can be found
elsewhere [37].

8.2.1. Adsorption
Distillation is used in 90–95% of all processes in
the chemical industry [182, 183]. However, due
to technological and economic limitations, dis-
tillation is not always feasible. In this situation,
zeolite adsorption is one of the options because
of its extensive and flexible applications. Zeo-
lite adsorption technologies have a wide range
of applications throughout a variety of indus-
tries, including the chemical, petroleum, and
allied industries.
The degree of gas or liquid phase adsorption
is almost infinite due to the number of ways of
modifying the zeolite characteristics. Key zeo-
litic adsorbent characteristics include frame-
work structure, zeolite particle sizes, chemical
composition, binder, counter exchange ion, and
water content. These variables are carefully
modified to selectively adsorb one particular
component over others. The adsorbed compo-
nent can then be removed or desorbed from the
adsorbent using regenerating agents. The recov-
ering of the adsorbed can be done at a constant
temperature/pressure using either solvent (dis-
placement)/gas (purge swing), at pressure (pres-
sure swing adsorption, PSA), or at temperature
(temperature swing adsorption, TSA). There are
many adsorption mechanisms that zeolite sepa-
ration processes can account for. This depends
on many factors, such as zeolite structures,
zeolite pore sizes, zeolite Si/Al ratios, ex-
changed cations, and the physical and chemical
properties of adsorbates and desorbents. In gen-
eral, the mechanisms present in zeolite adsorp-
tion can be classified as:
. Equilibrium-selective adsorption
. Shape-selective adsorption
. Rates-selective adsorption
. Ion exchange
. Reactive adsorption
Equilibrium-Selective Adsorption. The
foundation of equilibrium-selective adsorption
is based on differences in the equilibrium se-
lectivity of the various adsorbates with the
adsorbent. Although all the adsorbates have
access to the adsorbent sites, the specific adsor-
bate is selectively adsorbed based on differ-
ences in the adsorbate–adsorbent interaction.
This in turn results in higher adsorbent selectiv-
Zeolites 19
ity for one component than the others. One
important parameter that affects the equilibri-
um-selective adsorption mechanism is the in-
teraction between the acidic sites of the zeolite
and basic sites of the adsorbate. Specific physi-
cal properties of zeolites, such as framework
structure, choice of exchanged metal cations,
SiO2/Al2O3 ratio, and water content can be
manipulated to influence the acidity of zeolites,
which in turn affects separation performance.
Many industrial zeolite adsorptive separa-
tions are documented [185]. Some of the sepa-
ration highlights are the UOP Parex pro-
cess [184], p-xylene separation using X- or
Y-zeolite, the UOP MX Sorbex, m-xylene sep-
aration using Y-zeolite, the UOP Olex, olefin
separation using X-zeolite, and the UOP Sarex,
fructose separation using Y-zeolite.
Until late 1990s, purified m-xylene was pro-
duced predominantly by the HF/BF3 process
developed by Mitsubishi Gas Chemical Co. The
separation is based on the complex formation
between m-xylene and solvent HF/BF3. How-
ever, concerns about the process operation,
environment, metallurgy, and safety render the
process commercially unattractive due to its use
of HF/BF3. These concerns led to many devel-
opments in the adsorptive separation process for
m-xylene separation [186–191]. The UOP MX
Sorbex process, developed by UOP and com-
mercialized in 1998, already accounts for more
than 70% of the world’s m-xylene capacity. A
95% m-xylene recovery with 99.5% purity can
be achieved by the MX Sorbex process.
The commercial liquid adsorptive separation
process of C10–C14 n-olefins from C10–C14 n-
paraffins is another unique example of how
zeolite adsorption can be applied. Distillation
is not an option to separate C10–C14 olefins from
C10–C14 paraffins because of their close boiling
points. In this case, the UOP Olex process using
NaX adsorbent is used to separate C10–C14
olefins from C10–C14 paraffins.
Dehydrated (‘‘activated’’) zeolites of types A
and X are widely used in industry as drying
agents in closed or open systems, i.e., for the
static or dynamic adsorption of water. Their use
is favored if small amounts of water have to be
removed from gases or liquids. The adsorption
isotherms in Figure 9 show that, unlike silica gel,
zeolite NaA is able, for example, to reduce the
dew point temperature of the gas to extremely
20 Zeolites
Figure 9. Adsorption isotherms for H2O at 25 C on zeolite
NaA and silica gel at low partial pressures
low values. However, as water is very strongly
adsorbed and is therefore difficult to desorb,
zeolites cannot be considered for coarse drying
in regenerative processes.
In drying operations, measures must often be
taken to prevent larger molecules from being
adsorbed and possibly undergoing catalytic re-
actions. This can be achieved using 3A zeolite
whose pore diameter has been reduced to ca.
0.30 nm, e.g., in the drying of alkenes.
A similar situation exists for the removal of
atmospheric moisture from the panes of insu-
lating glass [192], an important example of
static adsorption. Here, the coadsorption of
nitrogen and oxygen or insulating gases, such
as argon and SF6 is undesired. Other examples
of static adsorption of water by type A zeolites
are the drying of coolant cycles and removal of
moisture from solvent-free, noncellular poly-
urethane systems, in which reaction of the iso-
cyanate component with water, forming CO2
bubbles, must be avoided [193]. In this case, the
zeolite powders remain in the cast resins or
sealing and coating compounds.
Dynamic water-adsorption processes in-
clude drying of air, natural gas, cracked gas,
Table 3. Commercial purification processes with synthetic zeolitic adsorbents (excluding drying)
Components removed Crude gas
CO2 natural gas, air
H2S, organic sulfur compounds natural gas, hydrogen
SOx, NOx waste air from H2SO4/HNO3 plants
Solvents, odoriferous substances industrial waste air
Dioxins waste air from incinerations
Hg natural gas, cracked gas, hydrogen, naphtha
waste gas from incinerators
alkenes, and organic solvents using TSA and
PSA methods with type A zeolites as the sor-
bents [1, 194–197].
The large amount of heat liberated during the
adsorption of water by high-aluminum zeolites
could in future be used for zeolite-based heat
storage and heat pumps. If, in another arrange-
ment, a water reservoir were brought into con-
tact with an activated low-silica zeolite via the
gas phase, the evaporation, accelerated by the
presence of the zeolite, would cause a large drop
in temperature. This effect could be used for
cooling [197].
Zeolites of types A and X are well estab-
lished in purification processes (Table 3). They
are used to remove carbon dioxide from gas
streams [198] and H2S and organic sulfur com-
pounds, mainly from natural gas. Problems can
arise in H2S adsorption if CO2 is also present, as
this reacts with H2S on the zeolite to form
COS [199]. As the activity of calcium-ex-
changed zeolite A is less than that of zeolite
NaA in this reaction, 5A sieves are mainly used
in this process.
The removal of solvents, dioxins, and ele-
mental mercury from moist waste-air and ex-
haust-gas streams by hydrophobic, high-silica
zeolites, such as dealuminated Y zeolite, is a
relatively new field [201, 205]. Compared with
other adsorbents, these materials have the ad-
vantage of high thermal capacity, nonflamma-
bility, low catalytic activity, and pronounced
hydrophobic properties. Regeneration is possi-
ble even if the compounds adsorbed have high
boiling points or can form polymers as the
zeolite absorbent can be treated at high tem-
peratures. Moreover, they are structurally stable
in the presence of acidic components, such as
SO2 and HCl in incineration off-gases.
Zeolitic adsorbents of the 5A type are used in
a number of important industrial processes for
the separation of mixtures of substances
Zeolites References
4A, 5A, X [198]
5A [199]
not published [200]
dealuminated Y zeolites, silicalite-1 [201, 202]
dealuminated Y zeolites [203]
modified Y zeolites [204]
[205]
 Zeolites 21

Table 4. Some important commercial separation processes with zeolitic adsorbents

Process Mixture Phase* Technology Zeolites References

H2 production by removal of other gases reformer, refinery, and G PSA 5A [197, 206, 208]
(e.g., N2, CH4, CO, SO2, H2O, O2, CH4, C2H6) coke-oven gases
O2 production air G VPSA** 5A, modified [197, 209, 210]
X zeolites
Ozone production O3/O2 G PSA not published [206]
Separation of n- from isoalkanes C6–C10 distillate G VPSA** 5A [199]
C10–C18 kerosene G purge swing 5A
C5–C6, C10–C15, C10–C23 L Sorbex (Molex) 5A [212]
hydrocarbons
Separation of xylene isomers C8 aromatics L Sorbex (Parex) Sr/BaX [212]
Separation of alkenes from alkanes C8–C18 hydrocarbons L Sorbex (Olex) Ca/SrX [212]
Fructose/glucose molasses, hydrolyzed L Sorbex (Sarex) CaY [212]
starch
*
G ¼ gas phase, L ¼ liquid phase.
**
Vacuum pressure-swing adsorption.

(Table 4). They are alternatives to carbon mo- n-alkanes from isoalkanes on 5A zeolites is one
lecular sieves and activated carbons for the of examples in shape-selective adsorption. For
recovery of hydrogen from reformer, refinery, example, PSA processes have been developed
and coke-oven gases in various PSA process- by UOP (Isosiv), Texaco (TSF), Leuna (Parex-
es [206–208]. Here, the separation effect is Leuna), ELF (N-Iself), Exxon, and BP
based on the fact that the gaseous components [199, 206]. In these processes, regeneration is
listed in Table 4 are adsorbed better than sometimes performed by displacement media,
hydrogen. such as NH3 or short-chain n-alkanes. The
The production of oxygen from air by vacu- Molex process of UOP is a liquid-phase process
um pressure swing adsorption (VPSA) process- designed on the principle of simulated counter-
es (! Oxygen, Section 4.2) represents a grow- current chromatography (Sorbex technology)
ing market for zeolites. Type 5A molecular [212, 213]. All these processes are because n-
sieves are mainly used, but the use of specially alkanes are adsorbed by 5A zeolites, whereas
optimized lithium-containing X zeolites is in- isoalkanes are too bulky to enter the pore system
creasing [197, 206, 209–211]. The separation of (see Fig. 10) and therefore break through
O2 from N2 is possible with these materials immediately.
because the nitrogen molecule, which has a
quadrupole moment, is more strongly bound
than the oxygen molecule. The purity of the
oxygen produced can exceed 95%, but argon
cannot be separated. VPSA processes are more
economic than the cryogenic production of
oxygen for flexible small to medium-sized
plants [210].
The O2/N2 separation on 4A zeolite to pro-
duce nitrogen is based on the kinetically pre-
ferred adsorption of the smaller O2 molecules.
This process is hardly used on an industrial
scale, but zeolites can be useful for oxygen
removal in the production of ozone [206].

Shape-selective adsorption, also known

as molecular sieving, is a process that separates Figure 10. Effect of calcium ion exchange on zeolite
NaA [1]
molecules based on inclusion or exclusion N2 adsorption: 2.0 kPa,
196 C; n-heptane adsorption;
from specific zeolite pores. The separation of 6.0 kPa, 25 C; isobutane adsorption: 53.3 kPa, 25 C
22 Zeolites
Rate-Selective Adsorption. Example of
rate-selective adsorption is demonstrated using
silicalite adsorbent for separation of C10–C14
n-paraffins from non-n-paraffins [214, 215]
Silicalite is a 10-ringed
 
zeolite with a pore
opening of 5.4 A  5.7 A. In the n-paraffins/
non-n-paraffins separation, n-paraffins enter
the pores of silicalite freely, but non-n-
paraffins such as aromatics, naphthenes, and
isoparaffins diffuse into the pores slower.
However, the diffusion rates of both normal
and non-n-paraffins increase with temperature.
Thus, one would expect to see minimal sepa-
ration of n-paraffins from non-n-paraffins at
high temperatures but high separation at lower
temperature.
Ion Exchange. In general, zeolites have
higher ion exchange selectivity for higher
charged cations. For cations having the same
valence, the ion exchange selectivity often
depends on the hydrated ionic radius. This is
seen from the zeolite ion exchange selectivity
decreasing with ionic radii [216], Csþ > Rbþ
>Kþ > Naþ > Liþ and Ba2þ > Sr2þ > Ca2þ >
Mg2þ
One of the important uses of zeolites
based on their ion-exchange properties is as
builders in detergents. The large application
of zeolites as ion exchangers in detergents
leveled off in demand in North America, West-
ern Europe, and Japan in the late 1990s, but
should continue to grow during the 2000s,
particularly in Asia, Australia and Latin Amer-
ica [217]. The other applications of zeolites as
ion exchangers in the nuclear industry, in
radioactive waste storage and cleanup, and in
metals removal and recovery, will probably
remain a relatively small fraction of the
worldwide market for molecular sieve
materials.
Reactive adsorption is to combine the unit
operations of reaction and zeolite adsorption
into a single process operation with simulta-
neous reaction and separation. For example,
Ag-substituted zeolite have been used to re-
move trace iodides by reaction and precipitation
from vapor and liquid streams to facilitate safe
operation of nuclear reactors [218] and to purify
acetic acid produced by methanol carbonyla-
tion [219, 220].
8.2.2. Membranes
There has been a strong focus on developing
continuous zeolite membrane process to
replace traditional zeolite adsorption that
requires significant cost and energy. Besides
zeolite membrane, mixed matrix membranes
are developed currently. Mixed matrix mem-
branes are composed of polymer and zeolite
matrix.
Zeolite Membranes. Zeolites can be formu-
lated into a membrane configuration due to their
microstructure, which consists of uniform mo-
lecular-sized pores connected by continuous
diffusion pathways. The pore sizes of these
materials are in the order of the molecule size
of many industrially important compounds,
which provide molecular sieving capability and
unique adsorption properties [221]. Additional-
ly, the operating conditions able to be sustained
by inorganic membranes far exceed that of
polymeric membranes, which are commonly
used in commercial separation processes. De-
velopment of new separation technologies, such
as high temperature gas separations and cata-
lytic membrane reactors requires materials that
are able to withstand extreme operating envir-
onments and zeolites present themselves as
capable candidates [222].
A majority of the zeolite membranes re-
ported to date are made from MFI, LTA, FAU,
or MOR [223–229]. For example, the pore size
of MFI zeolites is approximately 0.5–0.6 nm
and is larger than CO2, CH4, and N2. A separa-
tion factor of about 10 for CO2/CH4 separation
was obtained using a high-silica MFI membrane
at 393 K [190]. This separation can be
explained by competitive adsorption of CO2
and CH4. LTA zeolites have pores in the
range of 0.3–0.5 nm, and are able to distinguish
small molecules, such as H2 and N2A H2/N2
ideal separation factor of 7.1 was reported for a
Naþ-type LTA zeolite membrane and the value
was improved to 7.5 by ion exchange with
Kþ [229].
Mixed matrix membranes are composed
of zeolites that dispersed in the polymer
phase. Zeolite–polymer mixed matrix mem-
branes [230, 231] combine the superior selec-
tivity and permeability of zeolites with the low

cost and ease of processability of polymer
membranes. The dispersed zeolite phase in a
zeolite–polymer mixed matrix scenario can
have a selectivity that is significantly higher
than that of the continuous polymer matrix.
Therefore, the addition of a small volume frac-
tion of zeolite particles to the polymer matrix
can significantly increase the overall separation
efficiency. The superior properties of zeolite–
polymer mixed matrix membranes depend on
the proper selection of the zeolite material used
as the dispersed phase and the polymer material
used as the continuous phase in the mixed
matrix membranes. A variety of zeolites based
on an aluminosilicate composition [232–234]
and nonzeolitic molecular sieves, such as alu-
minophosphate molecular sieve (ALPO) [235]
and silicoaluminophosphate molecular sieve
(SAPO) [236, 237] have been used to prepare
mixed matrix membranes. Some of these mixed
matrix membranes have shown remarkably
improved properties that have surpassed the
polymer upper bound curve. Additional zeo-
lite–polymer mixed matrix membranes are
described in [238].
As well as the industrial-scale processes
mentioned, there is a growing list of potential
separation processes based on zeolitic adsor-
bents, zeolite membranes, and mixed matrix
membranes, some of which are at the pilot plant
stage.
8.2.3. Catalysis
Apart from the very alumina-rich types, such as
A and X, which are unstable in acidic media,
zeolites can be transformed into the hydrogen
form [105]. In this form, they are solid acids that
can show both Brønsted and Lewis acidity [239–
242]. Brønsted acid sites are protons attached to
framework oxygen atoms.
Zeolites 23
The number and strength of these sites de-
pends on the SiO2/Al2O3 ratio in the framework.
Decreasing framework aluminum content is as-
sociated with a decrease in the number of acidic
OH groups, but generally the strength of the
remaining sites initially increases [242, 243].
Structurally related zeolite-like materials in
which aluminum is isomorphously replaced by
gallium or boron have weaker Brønsted acidity.
Methods used industrially to produce
Brønsted centers include:
. Careful ion exchange of intermediate-silica
and high-silica zeolites (e.g., mordenite) with
mineral acids (Eq. 1)
. Removal of ammonia from the ammonium
form at ca. 400 C (Eq. 2) or the decomposi-
tion of tetraalkylammonium cations
. Ion exchange with polyvalent cations, usually
of rare earth (RE) metals, followed by a
dehydration (Eq. 3)
. Reduction of noble metal cations with hydro-
gen (Eq. 4)
Naþ ½O
ZþHþ !½þ H
O
ZþNaþ ð1Þ
NHþ
þ

4 ½ O
Z!½ H O
ZþNH3 ð2Þ
½REðH2 OÞ6 3þ ½
O
Zð
O
Þ2 3
ð3Þ
!½REðOHÞðH2 OÞ5 2þ ½HO
Zð
O
Þ2 2

Pt2þ ½ð
O
Þ2 ZþH2 !Ptþ½ðþ H
OþÞ2 Z ð4Þ
½ð
O
Þn Z ¼ zeolite framework
Calcination of the hydrogen form above ca.
400 C causes decomposition of the acidic hy-
droxyl groups with liberation of water. This
dehydroxylation leads to formation of Lewis
acid sites. As dehydroxylation takes place at
similar temperatures to those used in deammo-
niation (Eq. 2), both types of acidic sites may be
formed at the same time. The question whether
these consist of three-coordinate Al or Si sites
within the framework structure or of AlOþ
species outside the framework structure con-
tinues to be the subject of debate [242].
Base catalysis by modified zeolites has not
yet been used in industry. Suitable zeolites are
ion-exchanged with rubidium and cesium ions
or contain sodium clusters or cesium oxide as
24 Zeolites
active species in their pores [244]. Bifunctional
catalysts in which the acidity of the zeolites is
combined with the hydrogen-transferring func-
tion of noble metals are important in large-scale
industrial processes, such as hydrocracking or
C5/C6 alkane hydroisomerization.
A unique feature of the use of zeolites as
catalysts is that the reactions can be shape-
selective [240, 245, 246]. Shape selectivity in
catalysis is closely related to the molecular-
sieve effect in adsorption. Thus, it can occur if
the pores of the catalyst have similar dimensions
to those of the molecules or transition states
taking part in the reaction:
1. In reactant shape selectivity, only reactants
that can penetrate into the pore system by
virtue of their slender shape and which can
thus diffuse to the catalytic sites of the
interior surfaces take part in the reaction
2. If the more bulky of two possible products is
not formed, this is known as product shape
selectivity
3. Restricted transition state shape selectivity
occurs if the reaction pathway in the zeolite
is directed by spatial requirements of the
possible transition states
In the first two points, the selectivity is
ultimately a result of diffusion limitation. Shape
selectivity has so far mainly been observed in
reactions in which the catalyst is ZSM-5. How-
ever, the phenomenon is not limited to the use of
this material, as shown by shape-selective reac-
tions on erionite, ferrierite, mordenite, and other
zeolites and zeolite-like materials.
Zeolite catalysts are used in the four fields of
technology:
Oil Refining. Zeolite-containing catalysts
play a central role in several oil-refining pro-
cesses (Table 5) [247, 248]. The most important
Table 5. Zeolite catalysts in oil refining
Oil fraction Zeolite-catalyzed process
Naphtha C5/C6 alkane isomerization
reforming of C6/C7 alkanes
M-forming
Gas oil, lubricating oil dewaxing/hydrodewaxing
hydrogenation of aromatics/hydrodecyclization
Vacuum distillates, residues FCC
hydrocracking
residue hydroprocessing
is FCC, which converts vacuum distillates and
residues into gaseous alkenes, gasolines, and
diesel fuel. Y type zeolites have been used as
active components in FCC catalysts since
1964 [104, 249–251]. These materials consti-
tute 5–40% of the catalyst, which is spray-
granulated to give a mean particle size of
60 mm.
The zeolite catalysts have higher activity and
give higher gasoline yields and less coke for-
mation than the amorphous alumina–silica and
high-alumina catalysts formerly used. Today,
mainly USY zeolites are chosen for FCC cata-
lysts. The extensive use of USY zeolites has
reduced the consumption of RE-HY zeolites
[83984-84-3] in this application. Hybrids of the
two types are also used. The trend towards the
use of USY zeolites, which began in the early
1980s, was a result of the prohibition of tetra-
alkyllead compounds as antiknock agents, ne-
cessitating an increase in the octane number of
gasoline. The disadvantage of RE-HY zeolites
is their high activity with respect to hydrogen
transfer between alkenes and naphthenes, which
leads to the formation of aromatics and alkanes.
The latter lower the research octane number
(RON) and motor octane number (MON) of the
gasoline. The use of the less active USY types
avoids this effect, which has been explained in
terms of the greater distance between the active
sites. Moreover, the USY types have higher
hydrothermal stability and give a further reduc-
tion in coke formation and an increased gasoline
yield.
There has been much discussion of the use of
ZSM-5 as an additional catalyst, mainly in
combination with RE-HY catalysts. ZSM-5 is
generally used in the form of a separate spray-
granulated material with a binder content of ca.
75%. The proportion of this zeolite in the total
catalyst formulation is 0.5–3.0%. The original
Zeolites
Pt/H-mordenite, H-ZSM-5
Pt/K-L, Pt/BaK-L
H-ZSM-5
H-ZSM-5, Pt/H-mordenite
noble metal–zeolite
RE-HY, USY, H-ZSM-5
Pd-, Pt-, Ni/Mo-, Ni/W-USY
specially modified USY zeolites

aim was ‘‘octane boosting’’ by shape-selective
cracking of unbranched hydrocarbons. Addition
of ZSM-5 led to an increase in RON but does not
always affect MON. However, another interest-
ing effect is the increase in the proportion of C3/
C4 alkenes, mainly propene, in the product
spectrum. These alkenes can be used, for exam-
ple, in the alkylation of isobutane and can thus
contribute to the increase in the octane number
of the gasoline pool. However, the use of ZSM-5
does cause a slight reduction in the gasoline
yield on cracking. Besides ZSM-5, other zeo-
lites, such as b-zeolite, have been tested for
possible use in the FCC process [104]. Recent
development has extended the use of ZSM-5 to
meeting increasing demand for light olefin via
improved catalyst and process. Several licen-
sors have offered such technology for light
olefin production with the propene make in the
range of 12–20%.
Residues from the distillation of crude oil
contain high molecular mass carbon compounds
and are contaminated with nickel, vanadium,
sulfur, and nitrogen compounds. When these
residues are cracked — a process that will
increase in importance — basically the same
zeolites are used as those for the catalytic crack-
ing of gas oils [249, 252]. The main differences
are in the catalyst matrix, which must have large
pores and be catalytically active to precrack
large molecules. The matrix must also contain
additives to bond with the metals as well as
chemically reduce SOx and must include pro-
moters of CO oxidation.
The hydrocrack process converts high-boil-
ing-point feedstock to diesel, kerosene, and
fuels. The process has become increasingly
important with increasing demand for high
quality distillate fuel, such as higher cetane
number, and smoke point, and use heavier feed-
stock. It can also upgrade light cycle oil coming
of FCC units for diesel pool blending or for
catalytic naphtha reforming. The process is
often used to prepare lube oil feedstock derived
from unconverted fraction of mild hydrocrack-
ing. The basic process scheme encompasses
hydrotreating to remove organic sulfur and
nitrogen compounds and hydrocracking. Tradi-
tional process flow schemes include once-
through, single-stage recycle, two-stage recycle
and separate hydrotreating, designed to achieve
production of specific product slates via
Zeolites 25
managing sulfur and nitrogen compounds and
gaseous components including H2S and NH3
derived from their conversions. Typical cata-
lysts for hydrocracking are bifunctional and
consist of acidic zeolite Y finished with either
noble (Pt and Pd) or base metals (Ni, Mo, and
W). The zeolite acidity in the catalysts is tai-
lored by varying the zeolite contents and via
various dealumination techniques to achieve a
proper acid-metal function balance critical to
maximize specific product slates at given levels
of specific types of sulfur and nitrogen com-
pounds. Often amorphous silica alumina is in-
corporated into catalyst formulation to reduce
the size of the bulky high-boiling-point compo-
nents sufficiently for zeolite to be effective. The
choice of metals depends primarily on the levels
of sulfur and to a lesser degree on nitrogen
compounds under which the hydrocracking cat-
alyst serves. Noble metals are used in processes
involving more elaborate management of sulfur
and nitrogen compounds. In processes where
contents of sulfur and nitrogen compounds are
relatively high, the base metals are used in the
hydrocracking catalyst formulation. Compre-
hensive reviews of the subject can be found in
[253, 254, and references therein].
Catalytic dewaxing is designed to improve
the cold flow properties of diesel fuel and lube
oil by selectively converting normal and less
branched paraffins through cracking or isomer-
ization. The catalysts for conversion of normal
paraffins are bifunctional and are based on
reactant, product, or transition state shape-
selective principle. Their efficiency is also af-
fected by the nonselective reactions occurring at
the outer surface of the molecular sieves. The
catalyst comprises of acidic zeolites chosen
from MFI, AEL, MTT, TON or a combination
of the aforementioned, and metals chosen from
noble or base metals. Hydroisomerization of
paraffin has been an area of intense research
including molecular modeling to gain funda-
mental understanding of shape-selective catal-
ysis by MARTENS and coworkers specifically in
regard to pore-mouth and key-lock selectivity.
See [255, 253, and reference therein] for recent
reviews on the subjects.
Another important process in oil refining is
the isomerization of C5/C6 n-alkanes with Pt/H-
mordenite or H-ZSM-5. Shell has combined
this with the adsorptive separation of n- and
26 Zeolites
isoalkanes (UOP Isosiv process) to give the TIP
process (total isomerization process) [247]. The
isomerization is carried out to product high-
octane gasoline blend components, because
the most highly branched isomers have the
highest octane value. The reaction is thermody-
namically limited with formation of the highest
branched paraffins favored at lower tempera-
tures [256].
The zeolites Pt/K-L and Pt/BaK-L are used
commercially for converting C6/C7 paraffin to
aromatics via dehydrocyclization reac-
tion [257]. They are much more efficient than
the conventional reforming catalysts (e.g., Pt/
Cl–Al2O3). The zeolites are represented in
commercial operation by the UOP RZ Platform-
ing process and Chevron Phillips Chemical’s
(CP Chem) AROMAX process. Residual acidi-
ty in the catalyst has been shown to be detri-
mental [258]. The system is very sensitive to
sulfur, and thus elaborate removal of sulfur
close to extinction is required [257]. M-forming
is operated as a postreforming process with H-
ZSM-5 as catalyst. This consists of shape-
selective cracking of n-alkanes with simulta-
neous alkylation of benzene and toluene by the
short-chain alkenes produced [240, 259].
Conversion of Gases. As the global crude
production has come close to its peak, future
energy and petrochemical supply is expected to
come from other resources, such as coal, shale
oils, oil sands, and natural gas. Consequently,
the technology to convert varying sources of
reservoirs to liquid fuel and especially petro-
chemical intermediates have become increas-
ingly more important and is expected to play a
bigger role in the next few decades (! Coal
Liquefaction). With such a backdrop significant
research and technology development has been
focusing on methanol-based conversion pro-
cesses. Methanol conversion was first explored
by Mobil to produce gasoline (methanol-to-
gasoline, MTG) at a time when the crude supply
was disrupted. The MTG process was eventual-
ly commercialized in New Zealand [260]. The
catalyst is based on MFI, a medium pore zeolite.
The catalyst and process conditions of MTG
technology was later modified by Mobil to make
it suitable for light olefin production [261, 262].
Lurgi has reactivated the development of meth-
anol-to-propene process (MTP), representing
yields of 71% propene and 25% C4þ for gaso-
line blending [263, 264]. To achieve a combined
ethylene and propylene selectivity of greater
than 90% at complete methanol conversion, the
UOP/HYDRO MTO process uses a fluidized
bed reactor and regenerator design to maintain
steady-state production, provide temperature
control of the exothermic reactions and allow
facile movement of the catalyst between cata-
lyst and regenerator zones [265, 266]. Often a
small pore molecular sieve, such as SAPO-34
was found to favor the light olefin production. In
the aforementioned processes methanol is first
converted to dimethyl ether and then to light
olefins, which are coupled and dehydrocyclized
to aromatics and paraffin via hydride-transfer
reaction. Recent studies demonstrated the im-
portance of a hydrocarbon pool of adsorbed
methylated aromatics in the conversions of
methanol to higher olefin [267, 268]. Several
commercial projects of MTP and MTO have
recently been announced. Reviews of the tech-
nology have been published [269–271].
While MTO and MTP processes are aimed to
make light olefins for downstream polymer
production, light olefins coming off FCC are
sent to alkylation and oligomerization units for
fuel production. There has been substantial
effort to replace the liquid phase acid catalyst
in motor fuel alkylation process with a more
environmentally friendly process using zeolite-
based catalysis. It is generally recognized that
large pore zeolites, such as zeolite X and Y,
EMT, and BEA are most effective in carrying
out alkylation with frequent regeneration using
isobutane and/or H2 to remove and decompose
the carbonaceous deposits [272–286]. To date,
no solid acid based alkylation process has been
commercialized. The oligomerization of light
olefins has been carried out by solid phosphoric
acid (SPA) since its debut in the1930s due to its
superior selectivity to gasoline [287, 288]. The
commercial use of zeolite-based catalysts has
emerged relatively recently. The Mobil olefin to
gasoline/distillate (MOGD) process and the
conversion to distillate (COD) process of Pet-
roSA use ZSM-5 zeolite [289]. IFP Polynaphtha
and Selectopol processes also use a zeolite
based catalyst. Exxon-Mobil olefin to gasoline
(EMOGAS) process appears to use 10-MR ze-
olite and claims to give good quality gasoline
and catalyst stability. The high selectivity for

dimer formation is probably due to spatial
constraint of 10-MR zeolite as illustrated by
ZSM-57 [290].
Light paraffin (C3-5) from the gas field or
light paraffin/olefin (C3-5) from steam cracking
or FCC can be converted to a product stream
rich in aromatics, which can be isolated via
simple distillation. This approach represents
special cases for aromatic production and is
typified by UOP-BP Cyclar [291–293] and
Asahi ALPHA-ARO [294, 295] based on opti-
mization of acidity of MFI, metal function and
binder designed to maximize aromatics with
minimal coke formation.
Petrochemistry and Synthesis of Organic
Intermediates. Zeolites have played an im-
portant role in producing petrochemical inter-
mediates specifically xylene, ethylbenzene
(EB), and cumene for phthalic acid, styrene,
phenol, and detergent production. The process
for p-xylene production is especially important
due to an increasing demand with population
growth, while the market for m- and o-xylene
remains relatively small [296]. p-Xylene is
produced of the trans-alkylation, isomerization
and p-xylene extraction sections. The catalysis
is mainly based on the acidic zeolite with metal
function to facilitate either ethylbenzene
isomerization or olefin saturation. Mordenite
and MTW are often mentioned in carrying out
the trans-alkylation of heavier aromatics (A9-
A10) with toluene (A7) with the addition of MFI
to crack benzene coboils to improve benzene
purity. In the trans-alkylation, weak hydrogena-
tion is often incorporated into the catalyst for-
mulation to selectively saturate a very small
amount of olefinic products to improve catalyst
life. Ancillary commercial production is also
derived from the route of toluene disproportion-
ation to selective p-xylene production. Critical
reviews of trans-alkylation and disproportion-
ation can be found in [297–303]. Several zeo-
lites are often mentioned in the literature for
ethylbenzene dealkylation (MFI and IM-5
in [303–308]) or isomerization (mordenite and
EUO-1 in [309, 310]). A relatively strong metal
function is required to maintain a naphthene/
aromatics equilibrium that allows isomerization
of ethylbenzene to xylene. On the contrary, a
relatively weak metal function, such as rheni-
um [311], and bimetallic platinum [312] is
Zeolites 27
incorporated to hydrogenate olefins from the
dealkylation step to attain long catalyst life.
The processes for EB and cumene have gone
through significant advances by operating at
low benzene recycle in liquid phase using zeo-
litic catalysts ranging from zeolite Y to beta and
MWW. The combination of liquid phase oper-
ation with the nanocrystallite of zeolite beta or
surface cups of MWW allows the commercial
production of aromatic derivatives for pro-
longed periods of time without regeneration.
A more detailed description of advancement in
industrial alkylation of aromatics can be found
in [313–316].
The impetus for developing solid especially
zeolite-based acid catalysis process has been
coming from the need for having environmen-
tally friendly processes of improved efficiency.
These catalysts eliminate the use of acid cata-
lysts, such as H2SO4, HF, H3PO4 on silica, and
AlCl3, which are often health and environmental
hazard [317]. Other more prominent examples
are the caprolactam syntheses for nylon 6 based
on the processes developed by: (a) EniChem
direct ammoximation of cyclohexanone from
ammonia and hydrogen peroxide using TS-1 to
produce cyclohexanone oxime [318] and (b)
Sumitomo chemical vapor phase Beckmann
rearrangement to convert cyclohexanone oxime
using MFI based catalyst [319, 320]. Neither
processes use H2SO4 and do not yield ammoni-
um sulfate.
Environmental Protection. Advances have
been made in the use of zeolitic catalysts for
selective catalytic reduction of NOx to nitrogen
in the exhaust gases of lean-burn and diesel
engines [321–324]. Metal-modified zeolites,
especially Cu-ZSM-5 materials, have been in-
tensively investigated. Suitable reducing agents
include hydrocarbons, oxygen-containing,
water-miscible organic compounds, CO, and
H2. However, the durability of the new catalyst
under working conditions is still insufficient for
broad application. Therefore, only stationary
systems and mobile systems with diesel en-
gines, where the heat and water–vapor stress is
comparatively low, are equipped with these
catalysts [324]. Special zeolites have also been
used for the reduction of NOx with ammonia in
commercial applications [325]. Zeolite-based
catalysts for reducing NOx from vehicle
28 Zeolites
emissions had long suffered the debits of poor
hydrothermal stability and low sulfur tolerance.
Recent work has been focused on improving
such drawbacks and significant progresses spe-
cifically in urea-selective catalytic reduction
(SCR) have been made using Mn-containing
zeolitic catalysts and Cu-containing 8-MR zeo-
lite, such as CHA, and molecular sieve, such as
SAPO-34 [326–328]. The infrastructure re-
quired to employ urea as reducing agent for
reducing NOx needs also be incorporated as part
of the emission control solution [329].
8.2.4. Other Uses
Zeolites can act as carriers or reservoirs for
reactive substances. For example, zeolites con-
taining silver, copper, or zinc are used commer-
cially as antibacterial powders applied in man-
made fibers for textiles for domestic or personal
use [330, 331].
9. Toxicology
Epidemiological [332] and experimental inves-
tigations [333, 334] have shown that natural
erionite, as found in Cappadocia (Turkey), can
cause formation of mesotheliomas and bronchi-
al carcinomas. The oncogenic activity of these
minerals is explained in a similar way to that of
asbestos, which has fibrous crystal morphology.
This crystal form is extremely rare in zeolites.
Natural erionite is so far the only example
of a zeolite with toxic effects [335]. Zeolite
NaA, which is used as a detergent builder, was
found to have negligible acute, subacute, chron-
ic, or inhalative toxicity in comprehensive
tests [141, 159, 336]. Furthermore, regular med-
ical checkups of workers exposed to zeolite
NaA for a period of years in production areas
gave no indication whatsoever of fibrogenic
or silicogenic effects [333]. In Germany, the
MAK is 6 mg/m3, i.e., the general dust thresh-
old [334, 335].
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