Zeolites 1.

2 Synthetic Zeolites

The word ‘‘zeolite’’ comes from two Greek words The foregoing classification does not include many
meaning ‘‘boiling stones.’’ The name was given in zeolite phases which have been synthesized in the
1756 by a Swedish mineralogist, Axel von Cronstedt, laboratory. In some cases the phases are identical in
to a mineral which released water visibly when heated structure to a natural analogue but many have no
(the property of intumescence). The mineral later (currently) known natural counterpart. This may
acquired the name stilbite. change and there is an increasing number of zeolites
Since that date many similar minerals have been first recognized as a synthetic species which have
discovered and the word zeolite now describes a family subsequently been found in nature. A full list of
of minerals. They are commonly formed as a result of synthetic zeolites will not be included for reasons of
volcanic activity, either by the action of meteoric space. Table 2 gives some illustrations of zeolites
water in the environs of a volcano, or by the alteration which can be made with differing atoms in their
of wind-blown volcanic dusts deposited in saline lakes. tetrahedral positions, including some initially identi-
The latter mode of formation has created massive fied from laboratory synthesis but which have later
deposits on the earth’s surface. Some of these deposits been found as natural minerals.
are mined commercially as building stone, and for A definitive list of natural and synthetic zeolite
other uses such as soil remediation agents, waste- structures, with their idealized compositions and full
water treatment, and animal feed supplements. crystallographic data, has been compiled by Meier et
Historically zeolites were defined as aluminosilicates al. (1996). Each framework structure has been allo-
possessing three-dimensional frameworks of linked cated a three-letter code by the Structure Commission
silicon–aluminum–oxygen tetrahedra. This restrictive of the International Zeolite Association. The Structure
definition has been widened to include all crystalline Commission maintains a website with structural
materials characterized by frameworks of linked tetra- information.
hedra, each consisting of four oxygen atoms sur-
rounding a cation which can be Al, Si, P, Be, Zn, Mg,
Co, B, etc. The frameworks contain channels and 2. Structural Architecture
cavities in which are found water molecules and
cations. The water can be lost reversibly and the The molecular structures of zeolites are characterized
cations can usually undergo facile ion exchange. The by the unique ways in which their component tetra-
channels are in the microporous region and are large hedra are linked to each other to create open micro-
enough to accommodate guest molecules, which can porous frameworks. The void volume of some zeolites
be organic molecules. can be as high as 50% of the total crystal structure.
A further extension to the original definition has They contain repeating elements of structure which
been to accept some frameworks which are incomplete are known as secondary building units (sbu). These are
in so far as some of the apical oxygen atoms to the shown in Fig. 1. It is common to simplify the tetra-
tetrahedra are occupied by OH or F groups. hedral linkages to lines which represent the oxygen
Commonly conference reports and scientific jour- atoms, in much the same way as lines are used to
nals will consider frameworks containing octahedra represent the tetrahedral carbon bonds in organic
(e.g., titanosilicates) and mesoporous substances molecules. This is illustrated in Fig. 2. This method of
(e.g., MCM-41; a Mobil company code) alongside representation highlights the ways in which the tetra-
the more traditional zeolites because they have hedra make rings of oxygen atoms, and the resulting
related properties. This article will not include these restrictions to the channels and cavities making up the
materials. interior void of the structure. These restrictions are of
molecular dimensions. They are responsible for the
ability of zeolites to act as molecular sieves and
1. Classification perform selective sorption of molecules on the basis of
their size to achieve useful separations. Similarly
1.1 Zeolites Which Are Natural Minerals
cation-sieving can occur in certain structures.
The International Mineralogical Association has a
Commission on New Minerals and Mineral Names
which has suggested an approach to natural zeolite
3. Synthesis
classification. The zeolites can be grouped into series
within which various cation compositional ranges can Earlier methods used to synthesize zeolites tended to
occur. These are listed in Table 1 with the appropriate mimic their formation in nature by making use of
cations. They are all aluminosilicates with complete hydrothermal conditions to crystallize out zeolite
frameworks. In addition, zeolite species can be recog- phases from aqueous gels composed of aluminum and
nized. A full list of these can be found in Coombs et al. silica sources under highly alkaline conditions. Alter-
(1998). ation of Si\Al compositions, amount of water, and

1
Zeolites

Table 1
Zeolite series, their three-letter codes, and compositional variants (species).
Cation forms Cation forms
Series Code (species) Series Code (species)
Brewsterite BRE Sr,Baa gmelinite GME Na,Ca,K
Chabazite CHA Ca,Na,K heulandite HEU Ca,Na,K,Sr
Clinoptilolite HEU K,Na,Ca levyne LEV Ca,Na
Dachiardite DAC Ca,Na paulingite PAU K,Ca
Erionite ERI Na,K,Ca phillipsite PHI Na,Ca,K
Faujasite FAU Na,Ca,Mg stilbite STI Ca,Na
Ferrierite FER Mg,K,Na
a As an example of the link between zeolite series and zeolite species, the names of the species of zeolites in the brewsterite series will be
brewsterite–Sr and brewsterite–Ba.

Table 2
Synthetic zeolite frameworks containing various tetrahedral atoms.
Framework Code Material a
Chabazite CHA AlPO -34, CoAPO-44, CoAPO-47, GaPO , MeAPO-47,
%
MeAPSO-47, SAPO-34, SAPO-47 %
Faujasite FAU SAPO-37, beryllophosphate X, zincophosphate X,
Pahasapite RHOb berylloarsenate RHO, beryllophosphate RHO,
gallosilicate ECR-10
a The symbols refer to synthetic phases: A l Al, P l phosphate, S l Si, Me l Mn, Mg. Other numbers and codes are synthesis batch numbers or
company codes. b RHO is the code for a synthetic zeolite structurally characterized before pahasapite was found in nature.

Later many zeolites have been synthesized by similar

routes but with the inclusion of an organic molecule in
the gel as a template, or ‘‘void-filler.’’ This approach
has generated a number of zeolites with low aluminum
contents in their tetrahedral sites (high-silica zeolites).
(a) (b) (c)

4. Industrially Significant Zeolites

4.1 Synthetic Zeolite A (LTA)
The structure of zeolite A, which has no natural
counterpart, is shown in Fig. 3. It is created by the
joining together of subunits which are the main
(d) (e) structural unit of sodalite—a felspathoid. These units
are joined by all their rings of four oxygen atoms into
a cubic array like that adopted by the sodium chloride
structure. Fig. 3 shows that the consequence of this
is a series of cavities—those from the sodalite cage
(Fig. 2) itself and those in the central cavities they
surround. Entry to the sodalite cage ( β-cage) is via a
six-oxygen window of 0.23 nm approximate diameter.
That to the main cavity (α-cage) is through an eight-
(f) (g) (h) oxygen window with a diameter of 0.41 nm. The void
volume is 48%. As synthesized, the cavities are
Figure 1 occupied by sodium ions and water molecules.
The secondary building units recognized in zeolite This is the commercial product Molecular Sieve 4A,
frameworks: (a) single four-oxygen ring (S4R), (b) single well-known as an effective laboratory desiccant. Zeo-
six ring (S6R), (c) single eight ring (S8R), (d) double four lite crystals (about 5 µm) are bound together with a
ring (D4R), (e) double six ring (D6R), (f ) complex 4–1, clay (e.g., 10–20% of attapulgite or kaolinite) to form
(g) complex 5–1, and (h) complex 4–4–1.
beads or extrudates. They are pre-activated to remove
the inherent water prior to use.
differing cation(s) coupled with temperature, autogen- The cation present can be changed by cation
ous pressure, and time variations resulted in a wide exchange which moderates the effective eight-oxygen
range of products. window size. Introduction of the larger potassium

2
 Zeolites

basis of its size and polar nature in the presence of

other larger\less polar molecules—a molecular
sieving.

(b) Gas purification. The best known of all gas puri-

fications employing a zeolite substrate is in natural
gas treatment where, in addition to the peak-shav-
ing mentioned above, 4A ‘‘sweetens’’ the gas by re-
Figure 2 moving hydrogen sulfide. There are many other
A ‘‘ball and stick’’ representation of the structure of a examples of similar removals of sulfur and nitrogen
sodalite unit ( β cage) in which the tetrahedra can be compounds from gas streams.
indentified (left) with a framework diagram for
comparison.

(c) Bulk separations. The window size of 5A is

convenient to execute the important separation of
n-paraffins from i-paraffins. Many commercial pro-
cesses have been developed to carry this out as part
of feedstock preparation for the detergent and
chemical industries.
Another large-scale sieving separation comes in the
use of zeolite A to enrich the gases of the air (oxygen,
nitrogen, and inert gases). This can be carried out
cryogenically but pressure-swing processes are gaining
Figure 3 in use. Oxygen supplies for patients with breathing
The structure of zeolite A (LTA) as a stereopair. difficulties and for field hospitals (as in the Gulf
War) can be achieved by pressure-swing operations.
Other systems provide oxygen for welding and water-
cation reduces the working diameter to about 0.3 nm oxygenation, and nitrogen for large-scale chemical
in Molecular Sieve 3A. Replacement of about 40% of plant use. Zeolite A has long been an important
the sodium ions by calcium results in a widening to gas–solid chromatographic support for the analysis
about 0.5 nm, and hence Molecular Sieve 5A. This of permanent gases.
increase in effective window size arises from the
positioning of the calcium cations away from one
which constricts the 8-oxygen ring.
(d ) Liquid phase separations. Zeolite 5A can be used
in small-scale plants for the Union Oil Products’
(UOP) Molex process, which is designed for the sep-
(a) Desiccant uses. Zeolite A is widely used as a
aration of n-paraffins from i-paraffins, naphthalenes,
desiccant in sealed units for refrigerant gases, in
and other aromatics.
heavy duty oil-filled transformers, double glazing
units, vehicle air-brakes, and air conditioning systems.
On a larger scale, zeolite beads are used to dry
industrial feedstock gases, such as hydrogen and
oxygen. The processes are dynamic with continuous (e) Cation sieŠing. The use which accounts for the
regeneration via temperature- or pressure-swing. Both highest industrial production of zeolite 4A is as a
3A and 4A are used to dry liquid propane gas (LPG), powder for inclusion in industrial and domestic de-
halocarbons, and natural gas. 3A is preferred for the tergent packs. It acts as a water softener (builder)
drying of ‘‘cracked’’ gas (refinery olefin streams), selectively to remove calcium (and to a lesser extent
ethylene, propylene, and methanol. 4A dries other magnesium). This accounts for nearly 1 million tons
alcohols and benzene. It also is preferred for natural per annum. A synthetic gismondine—zeolite MAP—is
gas drying when ‘‘peak-shaving’’ is required. This is a modern competitor to A for this purpose.
the adjustment of the gas calorific value by removing Zeolite A also has been used for clean-up after the
water and carbon dioxide. Three Mile Island accident to remove radioactive
The basis of the desiccant action described above caesium selectively from contaminated waters in the
relies on the scavenging of the water molecule on the reactor.

3
Zeolites

HEU has not yet been commercially synthesized. It

is a very abundant mineral and is mined commercially
in many countries. MOR has been used both as a
natural mineral and as a synthetic phase.
Their relatively high silicon content enables them
to withstand exposure to acid gases and they have
been used for acid-gas drying and removal of sulfur
and nitrogen oxides. HEU has the useful property of
being able to separate nitrogen from natural gas. HEU
also has a selectivity for caesium (and strontium). This
ion-sieving has been used to clean up after the
Figure 4 Chernobyl accident and in the Site Ion-Exchange
The structure of zeolites X and Y (FAU) as a stereopair. Plant at British Nuclear Fuel’s Sellafield site. It
also has selectivity for the ammonium cation which
4.2 Synthetic Zeolites X and Y (FAU ) promotes its use in waste-water treatment, soil
amendment, and as an animal feed additive.
Zeolites X and Y form a series of structures which are
isostructural with the rare natural mineral faujasite. X
and Y differ only in silicon\aluminum ratio (and hence
cation content) with X having Si\Al " 1.0–1.4 and Y 5.2 Chabazite (CHA)
Si\Al " 1.5–3.0.
Although a laboratory synthesis is available for this
Their structure resembles that of zeolite A but with
zeolite, such use that has been made of its properties
the β-cages joined via half of their six-rings to create an
has been from natural sources. It has found use as a
diamond-like array (Fig. 4). Access to the main cavity
cheap drying agent and as a selective caesuim cation
is controlled by a 12-oxygen ring with a crystallo-
exchanger in the nuclear industry. It has been used in
graphic diameter of 0.74 nm. The void volume is 53%.
this way in an admixture with zeolite A in the Three
Mile Island clean-up and for low-activity waste
streams at the Oak Ridge National Laboratory,
(a) Industrial use. The zeolite X is commercially Tennessee.
available as Molecular Sieve 13X (sodium form) and
10X (calcium form). Molecular sieve 13X contributes
to gas purification, being able to scavenge larger 5.3 ZSM-5
molecules containing sulfur and nitrogen. It has also
been used for air-enrichment and in sealed window Zeolite Socony Mobil-5 is a high-silica synthetic
units. zeolite catalyst. It is mentioned here because it is a
Ion-exchanged forms (K, Ba, Sr) of both X and Y shape-selective catalyst that acts as a molecular sieve
can separate liquid mixtures and have been developed to tailor both reactants and products. This will be
by UOP to separate p-xylene from its isomers (Parex described in more detail elsewhere in this encylopedia.
process), ethylbenzene from its isomers (Ebex), and in The high silica content confers a hydrophobic nature
the Sarex process to separate fructose from other to enable its use in separating organic from aqueous
sugars. phases, such as in fermentation processes.
The major use of zeolite Y is as a catalyst of great
significance to the oil industry. This is covered
elsewhere in this encyclopedia. 6. Other Comments
The nuclear industry has also made use of gas sorption
by various zeolites to scavenge and contain tritium,
5. Other Zeolites of Commercial Significance tritiated water, and radioactive krypton from nuclear
plant-off gases. Silver-loaded zeolites have been used
5.1 Clinoptilolite (HEU ) and Mordenite (MOR)
to scavenge radio-iodine species. Some of these uses
Both these zeolites have silica-rich frameworks based have included the deliberate engineering of the pore
on five-oxygen rings linked together: 5–1 for mor- sizes by deposition of other phases at the pore
denite and 4–4–1 for clinoptilolite (Fig. 1). The openings.
structures have lower void volumes than those of
zeolites A, X, and Y. HEU has channels bounded
by two eight-ring windows (0.26i0.47 nm, 0.33i
7. Conclusion
0.46 nm) and one by a 10-ring (0.30i0.76 nm). MOR
has eight-and 12-ring windows of 0.26i0.57 nm and Most of the studies on the many novel synthetic
0.65i0.70 nm dimensions, respectively. zeolites have contained an over-emphasis on their

4
 Zeolites

potential use as catalysts. The future should see some International Mineralogical Association, Commission on
of them finding wider use as selective sorbents (and New Mineral Names. Miner. Mag. 62, 533–71
cation exchangers) as they offer the prospect of Dyer A 1988 An Introduction to Zeolite Molecular SieŠes.
tailoring their molecular sieve properties to meet Wiley, Chichester, UK
Karge H G, Weitkamp J (eds.) 1998Molecular SieŠes, Science
specific industrial and environmental needs. and Technology: Synthesis. Springer, Berlin, Vol. 1
Meier W M, Olson D H, Baerlocher C 1996 Atlas of zeolite
structure types. Zeolites 17, 1–230
Structure Commission of the International Zeolite Association,
Bibliography website. http:\\www.kristall.ethz.ch\IZA-SC\
Breck D W 1984 Zeolite Molecular SieŠes. R.A. Krieger, Szostak R 1984 Handbook of Molecular SieŠes. Van Nostrand
Malabar, FL Reinhold, New York
Coombs D S et al. 1998 Recommended Nomenclature for Zeolite
Minerals. Report of the subcommittee on zeolites of the A. Dyer

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Encyclopedia of Materials : Science and Technology
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