Zeolite

Natural zeolite with a United States one-cent coin

(penny) for scale

Zeolites are microporous, aluminosilicate

minerals commonly used as commercial
adsorbents and catalysts.[1] The term
zeolite was originally coined in 1756 by
Swedish mineralogist Axel Fredrik
Cronstedt, who observed that rapidly
heating the material, believed to have been
stilbite, produced large amounts of steam
from water that had been adsorbed by the
material. Based on this, he called the
material zeolite, from the Greek ζέω (zéō),
meaning "to boil" and λίθος (líthos),
meaning "stone".[2] The classic reference
for the field has been Breck's book Zeolite
Molecular Sieves: Structure, Chemistry, And
Use.[3]

Zeolites occur naturally but are also

produced industrially on a large scale. As
of September 2016, 232 unique zeolite
frameworks have been identified, and over
40 naturally occurring zeolite frameworks
are known.[4][5] Every new zeolite structure
that is obtained has to be approved by the
International Zeolite Association Structure
Commission and receives a three letter
designation.[6]

Properties and occurrence

A form of thomsonite (one of the rarest zeolites) from

India
Zeolites have a porous structure that can
accommodate a wide variety of cations,
such as Na+, K+, Ca2+, Mg2+ and others.
These positive ions are rather loosely held
and can readily be exchanged for others in
a contact solution. Some of the more
common mineral zeolites are analcime,
chabazite, clinoptilolite, heulandite,
natrolite, phillipsite, and stilbite. An
example of the mineral formula of a
zeolite is: Na2Al2Si3O10·2H2O, the formula
for natrolite.

Natural zeolites form where volcanic rocks

and ash layers react with alkaline
groundwater. Zeolites also crystallize in
post-depositional environments over
periods ranging from thousands to
millions of years in shallow marine basins.
Naturally occurring zeolites are rarely pure
and are contaminated to varying degrees
by other minerals, metals, quartz, or other
zeolites. For this reason, naturally
occurring zeolites are excluded from many
important commercial applications where
uniformity and purity are essential.

Zeolites are the aluminosilicate members

of the family of microporous solids known
as "molecular sieves" mainly consisting of
Si, Al, O, and metals including Ti, Sn, Zn,
and so on. The term molecular sieve refers
to a particular property of these materials,
i.e., the ability to selectively sort molecules
based primarily on a size exclusion
process. This is due to a very regular pore
structure of molecular dimensions. The
maximum size of the molecular or ionic
species that can enter the pores of a
zeolite is controlled by the dimensions of
the channels. These are conventionally
defined by the ring size of the aperture,
where, for example, the term "8-ring" refers
to a closed loop that is built from eight
tetrahedrally coordinated silicon (or
aluminium) atoms and 8 oxygen atoms.
These rings are not always perfectly
symmetrical due to a variety of effects,
including strain induced by the bonding
between units that are needed to produce
the overall structure, or coordination of
some of the oxygen atoms of the rings to
cations within the structure. Therefore, the
pores in many zeolites are not cylindrical.

Zeolites transform to other minerals under

weathering, hydrothermal alteration or
metamorphic conditions. Some
examples:[7]

The sequence of silica-rich volcanic

rocks commonly progresses from:
 Clay → quartz → mordenite–
heulandite → epistilbite → stilbite
→ thomsonite–mesolite-scolecite
→ chabazite → calcite.
The sequence of silica-poor volcanic
rocks commonly progresses from:
Cowlesite → levyne–offretite →
analcime → thomsonite–mesolite-
scolecite → chabazite → calcite.

Production
Industrially important zeolites are
produced synthetically. Typical procedures
entail heating aqueous solutions of
alumina and silica with sodium hydroxide.
Equivalent reagents include sodium
aluminate and sodium silicate. Further
variations include changes in the cations
to include quaternary ammonium
cations.[8]

Synthetic zeolites hold some key

advantages over their natural analogues.
The synthetic materials are manufactured
in a uniform, phase-pure state. It is also
possible to produce zeolite structures that
do not appear in nature. Zeolite A is a well-
known example. Since the principal raw
materials used to manufacture zeolites are
silica and alumina, which are among the
most abundant mineral components on
earth, the potential to supply zeolites is
virtually unlimited.

Natural occurrence

Natrolite from Poland

Conventional open-pit mining techniques

are used to mine natural zeolites. The
overburden is removed to allow access to
the ore. The ore may be blasted or
stripped for processing by using tractors
equipped with ripper blades and front-end
loaders. In processing, the ore is crushed,
dried, and milled. The milled ore may be
air-classified as to particle size and
shipped in bags or bulk. The crushed
product may be screened to remove fine
material when a granular product is
required, and some pelletized products are
produced from fine material.

As of 2016 the world's annual production

of natural zeolite approximates 3 million
tonnes. Major producers in 2010 included
China (2 million tonnes), South Korea
(210,000 t), Japan (150,000 t), Jordan
(140,000 t), Turkey (100,000 t) Slovakia
(85,000 t) and the United States (59,000
t).[9] The ready availability of zeolite-rich
rock at low cost and the shortage of
competing minerals and rocks are
probably the most important factors for its
large-scale use. According to the United
States Geological Survey, it is likely that a
significant percentage of the material sold
as zeolites in some countries is ground or
sawn volcanic tuff that contains only a
small amount of zeolites. Some examples
of such usage include dimension stone (as
an altered volcanic tuff), lightweight
aggregate, pozzolanic cement, and soil
conditioners.[10]
Artificial synthesis

Synthetic zeolite

There are over 200 synthetic zeolites that

have been synthesized by a process of
slow crystallization of a silica-alumina gel
in the presence of alkalis and organic
templates. Many more such structures
could theoretically be made.[11] In addition
to variations in structures, zeolites can
also be made with a variety of other atoms
in them to make them chemically
interesting and active. Some examples of
the so-called heteroatoms that have been
incorporated include germanium, iron,
gallium, boron, zinc, tin, and titanium.[12]
One of the important processes used to
carry out zeolite synthesis is sol-gel
processing. The product properties
depend on reaction mixture composition,
pH of the system, operating temperature,
pre-reaction 'seeding' time, reaction time
as well as the templates used. In sol-gel
process, other elements (metals, metal
oxides) can be easily incorporated. The
silicalite sol formed by the hydrothermal
method is very stable. The ease of scaling
up this process makes it a favorite route
for zeolite synthesis.

The zeolite conundrum

Computer calculations have predicted that

millions of hypothetical zeolite structures
are possible. However, only 232 of these
structures have been discovered and
synthesized so far, so many zeolite
scientists question why only this small
fraction of possibilities are being
observed. This problem is often referred to
as "the bottleneck problem". Currently
there are a number of theories attempting
to explain the reasoning behind this
question.

1. Zeolite synthesis research has primarily

been concentrating on hydrothermal
methods; however, new zeolites may be
synthesized using alternative methods.
Synthesis methods that have started to
gain use include: microwave-assisted,
post-synthetic modification, steam.
2. Geometric computer simulations have
shown that the discovered zeolite
frameworks possess a behaviour known
as "the flexibility window". This shows that
there is a range in which the zeolite
structure is "flexible" and can be
compressed but retain the framework
structure. It is suggested that if a
framework does not possess this property
then it cannot be feasibly synthesised.
3. As zeolites are metastable, certain
frameworks may be inaccessible as
nucleation cannot occur because more
stable and energetically favourable
zeolites will form. Post-synthetic
modification has been used to combat this
issue with the ADOR method,[13] whereby
frameworks can be cut apart into layers
and bonded back together by either
removing silica bonds or including them.

Uses
Zeolites are widely used as ion-exchange
beds in domestic and commercial water
purification, softening, and other
applications. In chemistry, zeolites are
used to separate molecules (only
molecules of certain sizes and shapes can
pass through), and as traps for molecules
so they can be analyzed.

Zeolites are also widely used as catalysts

and sorbents. Their well-defined pore
structure and adjustable acidity make
them highly active in a large variety of
reactions.[14]
Zeolites have the potential of providing
precise and specific separation of gases,
including the removal of H2O, CO2 and SO2
from low-grade natural gas streams. Other
separations include noble gases, N2, O2,
freon and formaldehyde.

On-board oxygen generating systems

(OBOGS) and Oxygen concentrators use
zeolites in conjunction with pressure
swing adsorption to remove nitrogen from
compressed air in order to supply oxygen
for aircrews at high altitudes, as well as
home and portable oxygen supplies.[15]

Industry
Synthetic zeolites, as other mesoporous
materials (e.g. MCM-41),are widely used
as catalysts in the petrochemical industry,
for instance in fluid catalytic cracking and
hydrocracking. Zeolites confine molecules
in small spaces, which causes changes in
their structure and reactivity. The acidic
forms of zeolites (prepared are often
powerful solid-state solid acids, facilitating
a host of acid-catalyzed reactions, such as
isomerisation, alkylation, and cracking.

Catalytic cracking uses reactor and a

regenerator. Feed is injected onto hot,
fluidized catalyst where large gasoil
molecules are broken into smaller gasoline
molecules and olefins. The vapor-phase
products are separated from the catalyst
and distilled into various products. The
catalyst is circulated to a regenerator
where air is used to burn coke off the
surface of the catalyst that was formed as
a byproduct in the cracking process. The
hot regenerated catalyst is then circulated
back to the reactor to complete its cycle.

Zeolites have uses in advanced

reprocessing methods, where their micro-
porous ability to capture some ions while
allowing others to pass freely, allowing
many fission products to be efficiently
removed from nuclear waste and
permanently trapped. Equally important
are the mineral properties of zeolites.
Their alumino-silicate construction is
extremely durable and resistant to
radiation even in porous form. Additionally,
once they are loaded with trapped fission
products, the zeolite-waste combination
can be hot pressed into an extremely
durable ceramic form, closing the pores
and trapping the waste in a solid stone
block. This is a waste form factor that
greatly reduces its hazard compared to
conventional reprocessing systems.
Zeolites are also used in the management
of leaks of radioactive materials. For
example, in the aftermath of the
Fukushima Daiichi nuclear disaster,
sandbags of zeolite were dropped into the
seawater near the power plant to adsorb
radioactive caesium which was present in
high levels.[16]

The German group Fraunhofer e.V.

announced that they had developed a
zeolite substance for use in the biogas
industry for long-term storage of energy at
a density 4x more than water.[17]
Ultimately, the goal is to be able to store
heat both in industrial installations and in
small combined heat and power plants
such as those used in larger residential
buildings.
Commercial and domestic

Zeolites can be used as solar thermal

collectors and for adsorption refrigeration.
In these applications, their high heat of
adsorption and ability to hydrate and
dehydrate while maintaining structural
stability is exploited. This hygroscopic
property coupled with an inherent
exothermic (energy releasing) reaction
when transitioning from a dehydrated to a
hydrated form make natural zeolites useful
in harvesting waste heat and solar heat
energy. Zeolites are also used as a
molecular sieve in cryosorption style
vacuum pumps.[18]
The largest single use for zeolite is the
global laundry detergent market. This
amounted to 1.44 million metric tons per
year of anhydrous zeolite A in 1992.

Non-clumping cat litter is often made of

zeolite or diatomite.

Synthetic zeolites are used as an additive

in the production process of warm mix
asphalt concrete. The development of this
application started in Germany in the
1990s. They help by decreasing the
temperature level during manufacture and
laying of asphalt concrete, resulting in
lower consumption of fossil fuels, thus
releasing less carbon dioxide, aerosols,
and vapours. The use of synthetic zeolites
in hot mixed asphalt leads to easier
compaction and, to a certain degree,
allows cold weather paving and longer
hauls.

When added to Portland cement as a

pozzolan they can reduce chloride
permeability and improve workability. They
reduce weight and help moderate water
content while allowing for slower drying
which improves break strength.[19] When
added to lime mortars and lime-
metakaolin mortars, synthetic zeolite
pellets can act simultaneously as
pozzolanic material and water
reservoir.[20][21]

Gemstones

Polished thomsonite

Thomsonites, one of the rarer zeolite

minerals, have been collected as
gemstones from a series of lava flows
along Lake Superior in Minnesota and to a
lesser degree in Michigan, U.S.
Thomsonite nodules from these areas
have eroded from basalt lava flows and
are collected on beaches and by scuba
divers in Lake Superior.

These thomsonite nodules have

concentric rings in combinations of colors:
black, white, orange, pink, purple, red, and
many shades of green. Some nodules
have copper inclusions and rarely will be
found with copper "eyes". When polished
by a lapidary the thomsonites sometimes
display a "cat's eye" effect (chatoyancy).[22]

Biological
Research into and development of the
many biochemical and biomedical
applications of zeolites, particularly the
naturally occurring species heulandite,
clinoptilolite and chabazite has been
ongoing.[23]

Zeolite-based oxygen concentrator

systems are widely used to produce
medical-grade oxygen. The zeolite is used
as a molecular sieve to create purified
oxygen from air using its ability to trap
impurities, in a process involving the
adsorption of nitrogen, leaving highly
purified oxygen and up to 5% argon.
QuikClot brand hemostatic agent, which is
used to stop severe bleeding,[24] contains a
calcium-loaded form of zeolite found in
kaolin clay.[25]

In agriculture, clinoptilolite (a naturally

occurring zeolite) is used as a soil
treatment. It provides a source of slowly
released potassium. If previously loaded
with ammonium, the zeolite can serve a
similar function in the slow release of
nitrogen. Zeolites can also act as water
moderators, in which they will absorb up to
55% of their weight in water and slowly
release it under the plant's demand. This
property can prevent root rot and
moderate drought cycles. Clinoptilolite has
also been added to chicken food, the
absorption of water and ammonia by the
zeolite made the birds' droppings drier,
less odoriferous and hence easier to
handle.[26]

Pet stores market zeolites for use as filter

additives in aquaria.[10] In aquaria, zeolites
can be used to adsorb ammonia and other
nitrogenous compounds. However, due to
the high affinity of some zeolites for
calcium, they may be less effective in hard
water and may deplete calcium. Zeolite
filtration is used in some marine aquaria to
keep nutrient concentrations low for the
benefit of corals adapted to nutrient-
depleted waters.

Where and how the zeolite was formed is

an important consideration for aquaria.
Most Northern hemisphere natural zeolites
were formed when molten lava came in
contact with sea water, thereby "loading"
the zeolite with Na (sodium) sacrificial
ions. The mechanism is well known to
chemists as ion exchange. These sodium
ions will speciate with other ions in
solution, thus the takeup of nitrogen in
ammonia, with the release of the sodium.
A deposit near Bear River in southern
Idaho, (US) is a fresh water variety (Na <
0.05%). Southern hemisphere zeolites are
typically formed in freshwater and have a
high calcium content.

Zeolite filters ammonia effectively, but

must be used with some care, especially
with delicate tropical corals that are
sensitive to water chemistry and
temperature.

Zeolite mineral species

A combination specimen of four zeolite species. The

radiating natrolite crystals are protected in a pocket
with associated stilbite. The matrix around and above
the pocket is lined with small, pink-colored laumontite

crystals. Heulandite is also present as a crystal cluster

on the backside

The zeolite structural group (Nickel-Strunz

classification) includes:[4][7][27][28][29]

09.GA. - Zeolites with T5O10 units (T =

combined Si and Al) – the fibrous
zeolites
Natrolite framework (NAT):
gonnardite, natrolite, mesolite,
paranatrolite, scolecite,
tetranatrolite
 Edingtonite framework (EDI):
edingtonite, kalborsite
Thomsonite framework (THO):
thomsonite-series
09.GB. - Chains of single connected 4-
membered rings
Analcime framework (ANA):
analcime, leucite, pollucite,
wairakite
Laumontite (LAU), yugawaralite
(YUG), goosecreekite (GOO),
montesommaite (MON)
09.GC. - Chains of doubly connected 4-
membered rings
 Phillipsite framework (PHI):
harmotome, phillipsite-series
Gismondine framework (GIS):
amicite, gismondine, garronite,
gobbinsite
Boggsite (BOG), merlinoite (MER),
mazzite-series (MAZ), paulingite-
series (PAU), perlialite (Linde type L
framework, zeolite L, LTL)
09.GD. - Chains of 6-membered rings –
tabular zeolites
Chabazite framework (CHA):
chabazite-series, herschelite,
willhendersonite and SSZ-13
Faujasite framework (FAU):
faujasite-series, Linde type X
(zeolite X, X zeolites), Linde type Y
(zeolite Y, Y zeolites)
Mordenite framework (MOR):
maricopaite, mordenite
Offretite–wenkite subgroup
09.GD.25 (Nickel–Strunz, 10 ed):
offretite (OFF), wenkite (WEN)
Bellbergite (TMA-E, Aiello and
Barrer; framework type EAB),
bikitaite (BIK), erionite-series (ERI),
ferrierite (FER), gmelinite (GME),
levyne-series (LEV), dachiardite-
series (DAC), epistilbite (EPI)
 09.GE. - Chains of T10O20 tetrahedra (T =
combined Si and Al)
Heulandite framework (HEU):
clinoptilolite, heulandite-series
Stilbite framework (STI): barrerite,
stellerite, stilbite-series
Brewsterite framework (BRE):
brewsterite-series
Others
Cowlesite, pentasil (also known as
ZSM-5, framework type MFI),
tschernichite (beta polymorph A,
disordered framework, BEA), Linde
type A framework (zeolite A, LTA)

See also
 Geopolymer, the amorphous alumino-
silicate equivalent of zeolite
List of minerals
Hypothetical zeolite
Adsorption
Solid sorbents for carbon capture
Pyrolysis

References
1. W. R. Grace & Co. Enriching Lives,
Everywhere. – Zeolite Structure Archived
February 15, 2009, at the Wayback
Machine.. Grace.com. Retrieved on 2010-
12-09.
2. A.F. Cronstedt, Kongl Vetenskaps
Academiens Handlingar Stockholm, 17,
1756, p. 120.
3. Breck, Donald W. (1973-01-01). Zeolite
molecular sieves: structure, chemistry, and
use . Wiley. ISBN 9780471099857.
4. International Zeolite Association,
Database of Zeolite Structures
5. Webmineral Zeolites, Dana Classification
6. "IZA Structure Commission" . www.iza-
structure.org. Retrieved 2017-01-23.
7. Tschernich, Rudy W. (1992). Zeolites of
the World . Geoscience Press. p. 563. Note:
237 MB (PDF).
8. Rollmann, L. D.; Valyocsik, E. W. (1995).
Zeolite Molecular Sieves. Inorganic
Syntheses. Inorganic Syntheses. 30.
pp. 227–234.
doi:10.1002/9780470132616.ch43 .
ISBN 9780470132616.
9. Zeolites (natural) , USGS Mineral
Commodity Summaries 2011
10. Robert L. Virta Zeolites , USGS 2009
Minerals Yearbook (October 2010)
11. Earl, David J.; Deem, Michael W. (2006-
08-01). "Toward a Database of Hypothetical
Zeolite Structures" . Industrial &
Engineering Chemistry Research. 45 (16):
5449–5454. doi:10.1021/ie0510728 .
ISSN 0888-5885 .
12. Molecular Sieves - Principles of
Synthesis and | Rosemarie Szostak |
Springer .
13. Roth, Wieslaw J.; Nachtigall, Petr;
Morris, Russell E.; Wheatley, Paul S.;
Seymour, Valerie R.; Ashbrook, Sharon E.;
Chlubná, Pavla; Grajciar, Lukáš; Položij,
Miroslav (2013-07-01). "A family of zeolites
with controlled pore size prepared using a
top-down method" . Nature Chemistry. 5
(7): 628–633. doi:10.1038/nchem.1662 .
ISSN 1755-4330 .
14. Bhatia, Subhash (1989-12-21). Zeolite
Catalysts: Principles and Applications . CRC
Press. ISBN 9780849356285.
15. "On-Board Oxygen Generating System
(OBOGS)." Honeywell. Archived September
10, 2011, at the Wayback Machine.
16. Levels of Radioactive Materials Rise
Near Japanese Plant . The Associated
Press via NYTimes, April 16, 2011
17. "Compact and flexible thermal
storage" . Fraunhofer-Gesellschaft. 1 June
2012.
18. Guglielmo Ventura; Lara Risegari (26
November 2007). The Art of Cryogenics:
Low-Temperature Experimental
Techniques . Surendra Kumar. pp. 17–.
ISBN 978-0-08-044479-6. Retrieved 4 June
2012.
19. Jana, Dypayan (2007). "Clinoptilolite – a
promising pozzolan in concrete" (PDF). A
New Look at an Old Pozzolan. 29th ICMA
Conference. Quebec City, Canada:
Construction Materials Consultants, Inc.
Retrieved 7 October 2013.
20. Andrejkovičová, Slávka; et al. (2012).
"Air Lime Mortars with Incorporation of
Sepiolite and Synthetic Zeolite Pellets"
(PDF). Acta Geodynamica et Geomaterialia.
9: 79–91.
21. Ferraz, E.; et al. (2014). "Synthetic
zeolite pellets incorporated to air lime–
metakaolin mortars: mechanical
properties" . Construction & Building
Materials. 69: 243–252.
doi:10.1016/j.conbuildmat.2014.07.030 .
22. Dietrich, R. V. (2005-07-14).
"Thomsonite" . Retrieved 2 October 2013.
23. Handbook of zeolite science and
technology, Scott M. Auerbach, Kathleen A.
Carrado, Prabir K. Dutta, eds. CRC Press,
2003, p. 16. ISBN 0-8247-4020-3
24. Rhee P., Brown C., Martin M., et. al.
(2008). "QuikClot use in trauma for
hemorrhage control: case series of 103
documented uses". J. Trauma. 64 (4):
1093–9.
doi:10.1097/TA.0b013e31812f6dbc .
PMID 18404080 .
25. Rowe, Aaron (24 April 2008).
"Nanoparticles Help Gauze Stop Gushing
Wounds" . Wired.com. Retrieved
1 November 2013.
26. "Chapter VIII: Using Zeolites in
Agriculture" (PDF). Retrieved 28 March
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27. IMA Database of Mineral Properties
28. Nickel-Strunz classification 10 ed,
mindat.org
29. First, E. L.; Gounaris, C. E.; Wei, J.;
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PMID 21881655 .

 This article incorporates public domain

material  from the United States
Geological Survey document: "Zeolites"
(PDF).

Further reading
Zeolites in Sedimentary Rocks. Ch. in
United States Mineral Resources,
Professional Paper 820, 1973.
Natural and Synthetic Zeolites. U.S.
Bureau of Mines Information Circular
9140, 1987.
Frederick A. Mumpton (1999). "La roca
magica: Uses of natural zeolites in
agriculture and industry" . PNAS. 96 (7):
3463–3470.
doi:10.1073/pnas.96.7.3463 .
PMC 34179  . PMID 10097058 .
"Zeolite-water close cycle solar
refrigeration; numerical optimisation
and field-testing", Jean-Baptiste
Monnier; Dupont, M. Proc. Annu. Meet. –
Am. Sect. Int. Sol. Energy Soc.;
Vol/Issue: 6 pp 181–185; American
 Solar Energy Society meeting; 1 June
1983; Minneapolis, MN, USA
Cheetham, A.K.; Peter Day (1992). Solid
State Chemistry. Clarendon Press.
Rhodes, Christopher J. (2007). "Zeolites:
Physical Aspects and Environmental
Applications". Annual Reports on the
Progress of Chemistry, Section C. 103:
287–325. doi:10.1039/b605702k .

External links
Wikimedia Commons has media related
to Zeolite.

International Zeolite Association

 Database of zeolite pore
characterizations
The Synthesis Commission of the
International Zeolite Association
Federation of European Zeolite
Associations
British Zeolite Association
Database of Zeolite Structures

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