Mission 4: ZEOLITES

Name: Mohamad Qulam Zaki Bin Mohamad Rasidi

Students ID: CES140822150
Course Code: SCH4U
Chemistry Gr 12 Independent Study Unit (ISU)
Teachers name: Miss Kayla Herdman

Abstract
This is an article that summarizes the uses and properties of zeolites. This article is
aimed at an audience of scientists from a broad variety of disciplines, as well as members of
the general public who are interested in science. This article are outlined the introduction to the
zeolites and how their structure relate to the properties, their applications in the petroleum
industry, the reactions that involved them as the catalysts and how the use of zeolites in
removing impurities in water filters. The research had been done from various sources in order
to produce this article.

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Zeolites: The Amazing Minerals for Human Beings

Based on United States Geological Survey in February 2014, the total amount of world zeolites reserves are
unknown, but are estimated to be large with China produces 74% of world natural zeolites.

Written by Mohamad Qulam Zaki Bin Mohamad Rasidi, a freelance science writer.

eolites is a special kind of rock which has unique properties if compared with other normal rock

metal. This kind of rock are microporous which traps water inside it and aluminosilicate minerals that usually
used as catalysts, commercial adsorbents and highly demand in other industrial sectors . Back to its history,
zeolites was discovered by Swedish geologist, Axel Fredrik Cronstedt (1722-1765) in 1756. Cronstedt
observed that large amounts of steam are produced from rapid heating the material stilbite in zeolites had
been adsorbed by the materials itself. He named for the rock as zeolite because it means boiling stones
from the Greek, zeo meaning to boil and lithos meaning stones (Woodford, C., 2014).

However, nowadays in a modern era, the term zeolite refers to over 200 different minerals that are
having very interesting uses, from materials in kitchen to huge industrial production. As in October 2012,
there were 206 unique zeolites that had been found by scientists and over 40 types of zeolites are known.
The most common zeolites that can be found are analcime, chabazite, clinoptilolite, erionite, ferrierite,
heulandite, laumontite, mordenite, and phillipsite. However, the most regular zeolites that used in industry
are faujasites such as X, and Y, A and pentasil-zeolite which is known as ZMS-5 (Woodford, C., 2014).
Their unique structure such as adsorption, ion exchange, molecular sieve and catalytic properties making
them used commercially in a natural or synthetic properties.

The zeolites can be classified into two groups, which are natural zeolites and synthetic zeolites.
Natural zeolites formed from the area of geological environments that have relatively low temperature.

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Meanwhile the synthetic zeolites by mixing sodium, aluminium and silica chemicals with steams. The zeolite
produces from the factories have wider range of properties and larger cavities.

Figure 1: Stilbite, a natural zeolite

Source: http://www.id.all.biz/naturalzeolite-g43623#.VQQ90JMXc0s

Figure 2: Ceolite, a synthetic zeolite Source:

http://www.trimechindia.com/dessicant-forplant.html

Zeolites and their structure

Zeolites are hydrated crystalline aluminosilicates with open 3D framework structure made from
interlinked tetrahedral of alumina (AlO4) and silica (SiO4) by sharing all the oxygen atoms to form regular
intra-crystalline cavities and channels of molecular dimensions. In a simple words, zeolites are stones or
rocks that made up from elements such as aluminium, silicon and oxygen with alkali or alkaline-Earth metals.
The zeolites were formed when the reaction occurs between volcanic rocks and ash layer with groundwater
in basic state. They have large open pores or cavities in a very similar arrangement and roughly the same
size as small molecules.
Based on the United States Geological Survey, February 2014, the most zeolites types are chabazite,
clinoptilolite and mordenite. However, the natural zeolites are rarely in a pure state and mixed with other
minerals, quartz, metals or even other types of zeolites. The natural zeolites have irregular shape and vary in
size of pores making them unsuitable to be commercial and less efficient. The adsorption, ion-exchange and
catalysis properties of natural zeolites are less efficient compared to their synthetic. Therefore, the natural
zeolites likely were not used in the commercial industry as a main component.

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The synthetic zeolites which has pores size range about 1m to 1mm are used as they have uniformity
and high purity. The synthetic zeolites can be divided into two system which are unimodal pore system and
hierarchical pore system. In hierarchical pore system, there are divided into three different elements which
are nanosized zeolites, zeolite composites and mesoporous zeolites.

Table 1: The comparison of several synthetic zeolites based on their characteristics

Unimodal pore system
Wide-pore zeolites

Intracrystalline
micropores
Molecular

Nanosized zeolites

Material
Hierarchical pore systems
Zeolite composites
Mesoporous zeolites

Intercrystalline mespores

Intercrystalline mespores

Templating
Supramolecular
Supramolecular
solid
Indirect
Non-templating
Controlled
crystallisation
Demetallation

Figure 3: The basic zeolite structure

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Intracrystalline mespores

Supramolecular
Solid

Demetallation

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The Zeolites and their special properties based on their structure

What is the Zeolites special properties that had made them to be one of the most important substances
in various potential industries? Based on zeolites common structure, it have porous structure which can
provide a huge variety of cations including magnesium ions (Mg2+), calcium ions (Ca2+), potassium(K+),
sodium ions (Na+), and others. All of the positively charges ions can readily be switched over for others in a
solution which in contact. Example of the most regular mineral zeolites are stilbite, phillipsite, heulandite,
natrolite, clinoptilolite, chbazite and analcime with an example of mineral formula of natrolite is
Na2Al2Si3O102H2O.

Figure 4: The zeolites 3-dimension framework

Source: http://ochem.jsd.claremont.edu/tpoon.dir/tp_research.htm

The zeolites atomic basic configuration is based on tetrahedral which there are four oxygen ions
surrounded silicon ion or aluminium ion that make up a three-dimensional frameworks. In order to make a
link, two adjacent aluminium ions or silicon ions will bond with an oxygen. A bunch of tetrahedral will
construct polyhedral units which undergo further build up process and form the entire frameworks. However,
there are also other shape form that made up from the polyhedral units such as equidimensional, sheetlike
and chainlike. Cations that placed in the cagelike cavities had balanced aluminosilicate framework which
make it has a negative charge.

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Figure 5: The production of several types of natural zeolites

Credit: Thomas F. Degnan Jr., 2006

The zeolites structures volume are voids in range of 20% to 50%. It also rigid and has 3-dimensional
crystalline structure which consists of interconnected cages and tunnels. Water molecules, potassium ions,
calcium ions and huge variety of other positively charged ions can move freely in and out of the porous pores
but their framework remains rigid. The gain or lose of water molecules in their pores structure make this
special process normally called as reversible dehydration. They are behave in a predictable style as they have
special criteria of pores and channel sizes structure that nearly uniform which allowing them to create a
molecular sieve property. The ability of zeolites to sort any molecules based on their size create the term
molecular sieve. The channels dimensions of zeolite controls the maximum size of the molecules or ions.
The zeolites have the aperture ring size which they are said to have 8-ring which refer to the
tetrahedral coordinated silicon atoms or aluminium atoms with 8 oxygen atoms that built a closed loop.
However, due to various factors such as the inducing strain by the bonding between oxygen atoms
coordination to aluminium or silicon atoms, the rings are not perfectly symmetry. Therefore, most of the
pores in zeolites are non-cylindrical.
The structure of zeolites are very stable solids that can withstand many environmental conditions
such as high temperature, high pressure, low solubility and less reactive. They have relatively high melting
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points which is more than 1000C. They also do not dissolved in any kinds of solution including organic or
inorganic solvents. Although they may contain carcinogenic which normally can lead to the cancer, the
unreactive properties of zeolites will not harm any organism and effects the environment (Chris Woodford,
2014). Although they are stable and unreactive, the main things that making them useful are their unique
frameworks structure.

Zeolites and their applications in the petroleum industry

The synthetic zeolites are used as catalysts in the petroleum industry. Commonly they are used for
fluid catalytic cracking and hydrocracking process. They provide an important task to confine molecules in
small spaces that will make a huge differences in their structure and reactivity. An ion-exchange in the
zeolites will form hydrogen which is powerful solid acids. The hydrogen acids can facilitate the acidcatalyzed reactions such as isomerisation, alkylation and cracking. Most of zeolites-based catalysts used
quantum-chemical Lewis acid site reactions as their specific acid modality. The uses of zeolites in petroleum
industry are divided into three main stages of refining processes which are catalytic cracking, isomerisation
and reforming.

In catalytic cracking, zeolites are used to break up the large hydrocarbon molecules into smaller
molecules thus become more useable. The low temperature and pressure with presence of zeolites are the
condition need to be fulfilled in a catalytic cracking process. The large hydrocarbon, normally the naphtha
fraction in a liquid state need to re-vaporise before undergo a cracking process. Then, the liquid naphtha will
add with the zeolites in a chamber at the temperature about 500C. It is also called as fluid catalytic cracking
because the reaction take place in a liquid state. However, zeolites used are not in a same phase as naphtha
and it is heterogenous catalyst. Further fractional distillation and cooling are needed to separate the cracked
mixture.

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Figure 6: The zeolites are used in petroleum production; the shaded region are the
process that using zeolites as catalysts. Source: Thomas F. Degnan Jr., 2006

The bigger size hydrocarbon molecules are broken up into smaller size hydrocarbon molecules. The
example of cracking reaction that involved zeolites as its catalyst is breaking up pentadecane molecule into
ethene, propene and octane.

Example of cracking reaction of pentadecane

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Figure 7: The illustration of cracking reaction of pentadecane

In isomerisation process of petroleum industry, platinum on a zeolite base are used as a catalyst to
rearrange straight chain octane molecules into their isomers with branched chains in order to make petrol
burn better in the vehicle engines. In gasoline or petrol, the octane rating will determine the performance of
oil in vehicle engines. Octane with higher rating will burn more smoothly than the one that have lower rating.
The straight octane chains have more tendency to pre-ignition when the petrol is compressed and making
them to explode. Therefore, octane in petrol need to change into its isomer such as 2,2,4-trimethylpentane
which has rating of 100. The isomerisation process used zeolite at a temperature of 250C and a pressure of
13 to 30 atmosphere.

Figure 8: The illustration of isomerisation of heptane

In the reforming process of petroleum production, zeolites are used as one of the components in
catalyst. The main element used is a platinum that contain on aluminium oxide. The reforming process are
used to improve octane rating, same as isomerisation reaction. The isomerisation reaction will take place but

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in addition of production of benzene rings due to hydrogen loss during reaction. For example, hexane will
convert into benzene and heptane will convert into methylbenzene.

Figure 9: An example of reforming process of hexane into benzene

Figure 10: An example of reforming process of heptane into methylbenzene

Zeolites as a catalyst and the reactions involved

Zeolites unique structure had made them to be one of the most important catalyst in pharmaceutical
(drugs) and petrochemical (petroleum) industry. The pores that one of the unique structure of zeolites have
made most of the reactions to take place in them efficiently. The zeolites open pores are such millions of
test tubes which atoms and molecules chemically react in it. The fixed shape and sizes of pores making them
easily to work with selective molecules. The selectively molecules that they can take account to react in their
pores make them normally known as shape-selective catalyst and can be recyclable as they do not degrade.

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The most important reaction that used zeolites as their catalyst are cracking, isomerisation and
hydrocarbon synthesis or also known as reforming reaction in petroleum industry. Various catalytic reactions
such as acid-base and metal induced reaction can be proceed with presence of zeolites as their catalyst. The
zeolites that have hydrogen-exchanged zeolites which is framework-bound protons will produce an important
catalyst. Most of the reactions, such as cracking reaction, isomerisation and reforming use this type of zeolite
catalysts.

Oxidation and reduction process also can be catalysed by zeolites. For example, zeolites in platinum
ZSM-5 are used in caprolactam synthesis and copper zeolites are needed in decomposition of NOx. The
reactants and products can be controlled their access due to zeolites particular pore system as zeolites have
unique microporous. Theoretically, zeolites catalyst accelerate a reaction by giving an effective lower energy
pathway from reactants to products. The zeolites will allow the reactions to occur by using alternative
mechanism which include new intermediate steps, but resulting in the same products. The reaction rate will
be increased as the activation energy has been lowered by zeolites catalyst.

Most of zeolites catalysts used are heterogenous catalyst which the reactants and the zeolites catalysts
are in different physical states. For example, in cracking process of petroleum production, zeolites catalysts
are in solid state while the reactants, naphtha are in liquid state.

Figure 11: The graph illustrated the effect of zeolites catalyst in a reaction
Source: Chemistry Nelson 12

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Zeolites and their great application in removing impurities in water filters

Nowadays, there are so much methods to remove impurities in our daily household water. However,
do you know that zeolites also have a great structure and can be used as one of the substances in removing
impurities in water filters method. Zeolites can remove ions that lead to the water harness like magnesium
and calcium by ion exchange. The structure of zeolites that have many pores and huge surfaces will attract
more amount of positive ions and make them to attach. The porous structure of zeolite had made them to
have lots of surface area and leaving spaces for deposition of ions.
The sodium ions that attached in zeolites pores will exchange their position with magnesium ions or
calcium ions due to their high number of positively charge. Sodium with one positively charged will be
released while magnesium and calcium ions with two positively charged will replace the places in pores and
crevices. The zeolites which is negatively charged have more tendency to attract magnesium ions or calcium
ions in hard water than sodium ions. The sodium ions are exchanging their places with magnesium or calcium
ions, hence their known as ion exchange.

Figure 12: The water filter machine that use zeolites.

Source: http://homewaterquality.com/how-do-zeolites-removeimpurities-in-water-filters

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In water filters application in modern house, the filters that has been used for long time and its zeolites
are full with calcium ions and magnesium ion sin their pores, the heavily brined water solution are needed to
get through the zeolites bed. The calcium ions and magnesium ions will attract to the stronger negatively
charged chlorine ions and they will drop from pores. Then, positively charged sodium ions will attract back
to the zeolites bed pores.

Conclusion
Zeolites, even just a type of mineral rock that seem to be invaluable for human in the past time, had
been discover to be one of the most influential mineral rock in our everyday life. More research and studies
had been done, and need to be continued in order to find out more application in the potential industries.
There are many industrial that can implemented zeolites as one of the substances in the reaction to produce
high quality outcomes. Therefore, the zeolites production itself can be one of the most demand industry in a
current time.

References:
1. Bernal, S. (2010, August 2). How Do Zeolites Remove Impurities in Water Filters? Retrieved
March 12, 2015, from http://homewaterquality.com/how-do-zeolites-remove-impurities-in-waterfilters/
2. Chemistry Explained. (n.d.). Retrieved March 10, 2015, from
http://www.chemistryexplained.com/Va-Z/Zeolites.html
3. Clark, J. (2013, October 1). Catalysts in the petrochemical industry. Retrieved March 12, 2015,
from http://www.chemguide.co.uk/physical/catalysis/petrochem.html

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4. Database of Zeolite Structures. (n.d.). Retrieved March 10, 2015, from http://www.izastructure.org/databases/
5. David, J. (2012, May 10). Zeolites: The natural detoxifyer. Retrieved March 14, 2015, from
http://www.naturalnews.com/035814_zeolites_detox_heavy_metals.html
6. Dessicant For Plant - Trimech India. (n.d.). Retrieved March 14, 2015, from
http://www.trimechindia.com/dessicant-for-plant.html
7. Fraser,D. (2012). Biology 12. Toronto, Ont,: Nelson Education.
8. Haynes, H. (2007). Chemical, Physical, and Catalytic Properties of Large Pore Acidic Zeolites.
Catalysis Reviews, 17(1), 273-336. Retrieved March 12, 2015, from
http://www.tandfonline.com/doi/citedby/10.1080/03602457808080883#.VQIbL5MXc0s
9. Kessel,H. (2003). Nelson Chemistry 12. Toronto: Thomson Nelson.
10. Prez-Ramrez, J., Christensen, C., Egeblad, K., Christensen, C., & Groen, J. (2008). Hierarchical
zeolites: Enhanced utilisation of microporous crystals in catalysis by advances in materials design.
Chemical Society Reviews, (37), 2530-2542. Retrieved March 12, 2015, from
http://pubs.rsc.org/en/content/articlelanding/2008/cs/b809030k#!divAbstract
11. Poon, T. (2007, January 1). Thomas Poon, Professor of Chemistry (Research Interests). Retrieved
March 14, 2015, from http://ochem.jsd.claremont.edu/tpoon.dir/tp_research.htm
12. R. P. Townsend, E. N. Coker "Ion exchange in zeolites", Stud. Surf. Sci. Catal. 137 (2001), 467
13. Sherman, J. (1999). Synthetic zeolites and other microporous oxide molecular sieves. Proceedings
of the National Academy of Sciences, 96(7), 3471-3478. Retrieved March 12, 2015, from
http://www.pnas.org/content/96/7/3471.full
14. What Is Zeolite | Pure Liquid Zeolite. (2014, February 27). Retrieved March 10, 2015, from
http://www.pureliquidzeolite.com/what-is-zeolite/
15. Woodford, C. (2014, December 10). Zeolites. Retrieved March 10, 2015, from
http://www.explainthatstuff.com/zeolites.html
16. Zeolites. (n.d.). Retrieved March 10, 2015, from http://scienceviews.com/geology/zeolites.html
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17. Zeolites. (n.d.). Retrieved March 10, 2015, from http://www.asdn.net/asdn/chemistry/zeolites.shtml

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