‫فرع التلوث الصناعي والنفطي‬

‫العوامل المساعدة‬
‫موضوع التقرير‬
‫‪Zeolite catalyst‬‬
‫المرحلة الرابعة‬
‫الدراسة الصباحية‬
‫اعداد وتقديم الطالب‬
‫حسين ميثم سعيد‬
‫باشراف الدكتور‬
‫بشير يوسف‬
‫للسنة الدراسية ‪2020-2019‬‬
 Chemical engineering Zeolite catalyst

Heat a glass of water and you'll see steam rise off it sooner or later as it comes
to the boil. You certainly don't expect the same thing to happen if you heat a
rock—unless it's a special kind of rock called a zeolite, which traps water
inside it. Back In 1756, Swedish geologist Axel Cronstedt (1722–1765)—best
known as the discoverer of nickel—coined the name "zeolite" because it
literally means "boiling stone"; today, the term refers to over 200 different
minerals that have all kinds of interesting uses, from water softeners and cat
litter to animal food and industrial catalysts. What are zeolites and how do
they work. The purpose of this report is to review in structure,
nomenclature and synthetic methods of zeolite. The report shows how to
obtain synthetic methods of zeolite, their properties and broad application not
only in refineries in catalysts, in modern zeolitical Materials.. The effect of
green method during ageing and curing step is prior too conventional method
was also investigated .

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 Chemical engineering Zeolite catalyst

Content:

Subject Page
1-Introduction 4

2-Zeolites stricture& General chemical composition: 5

2-1: Zeolites stricture
2-2: General chemical composition
3-Natural & Synthesis zeolites 6
3-1:Natural zeolites 7
3-2:synthesis zeolites 8
4- Properties of Zeolites as Catalytic 8
5- Applications of zeolites 8
9
10
6- Advantages & dis-advantages 11
7- Discussion 12
8-Conclusion 13
9-Recommendation 13
10-Reference 14

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 Chemical engineering Zeolite catalyst

1-Introduction:

Zeolites have been known for about 250 years, though their active life in science
and industry started in late 1960s. The definition of zeolites experienced a few
attacks from aluminophosphates (AlPOs, SAPOs, MeAPOs etc.), and
metallosilicates (Fe-silicate, B-silicate, Ti-silicate, and others) in the 1980s, then
from mesoporous oxide materials (silicate families MCM-41, SBA-15,
mesoporous TiO2 , ZrO2, and the like), and now from the organic-inorganic
hybrid materials (metal-organic frameworks, MOFs, covalent organic
frameworks, COFs, and porous coordination polymers, PCPs), though the hybrid
materials may contain no traces of silicon or aluminum. All these new materials
should be classified as zeolite-like materials. They are not true silica-alumina
compositions and cannot be included in the family of zeolites. On the other hand,
they do exhibit a clear molecular sieve effect and extended micro/meso porosity.
In some aspects, these new materials are better or richer in properties and
structures than the classical zeolites, and provide more opportunities for variation
of the structure and composition. The new zeolite-like materials are not ―boiling
stones‖ anymore. Moreover, some of them are hydrophobic materials with
preference for adsorption of non-polar molecules rather than water. But, the
zeolite nature, or character, of these newcomers in the zeolite world can be easily
recognized by the shape-selectivity effects, huge specific surface areas and pore
volumes, and typical zeolite architecture. The new wave of materials looks like a
dangerous avalanche that can absorb the classical zeolites. But this will not
happen, because the Si-Al zeolites have already inscribed their names (faujasites,
mordenites, ZSM-5 zeolites, just to mention a few) in the history of modern
industry—oil refining, petrochemicals synthesis, air separation, detergents, and
other applications. Zeolites continue to be catalysts of choice in the conversion of
light and heavy oil hydrocarbons, and the last decade offered a number of
challenges for the use of zeolite-like materials. The conversion of biomass is
another intriguing area where zeolites and zeolite-like materials will definitely
show promising results. There is still a very large domain of fine chemicals
synthesis, as well as other areas of potential applications, where zeolites do not
provide an ideal solution. Yet, the time has not come to judge whether or not the
little brothers of zeolites are better than their elder relatives.

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 Chemical engineering Zeolite catalyst

.2-Zeolites stricture& General chemical compostion:

2-1: Zeolites stricture

Zeolites have many different structures and its basic unit is the SO4- and
AlO4- tetrahedral, linked together by the sharing of an oxygen atom. Zeolites
A, zeolites X and zeolite Y consist of a cubo-octahedral (i.e. p-cages)
having the SO4- and AlO4- tetrahedral at each corners of the framework.
The structures of zeolites A are often as a result of the linkage between
the P-cages through the quadratic surfaces which has a cubic shape. The
linkage between the over six cornered surfaces and the hexagonal prisms
leads to the formation of zeolite X and zeolite Y which correspond to
faujasite zeolite. The ZSM 5 zeolite systems have a complicated
structure and this is due to the presence of a system having two crossing
channels, one linear one zigzag.

Figure-1: Diagram showing the relationship between the Tetrahedral,

the PBU and the SBU

2-2: General chemical composition:

𝑛
M𝑥/𝑛 Si1−𝑥 𝐴𝑙𝑥 𝑂2 𝑦𝐻2 𝑂

Where M = e.g. Na+, K+, Li+, Ag+, NH4+, H+, Ca2+, Ba2+

• This means the Si/Al ratio is larger than 1 and that x is smaller than 0.5

• This rule is not always obeyed! (High aluminium e.g. Si/Al = 0.5)

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 Chemical engineering Zeolite catalyst

• High silica and pure silica zeolites have been synthesized

3-Natural & Synthesis zeolites :

3-1:Natural zeolites:

Zeolites are crystalline microporous

aluminosilicates, which allow to adsorb water
and other cations, thus filling the micropores.
There are more than 40 different types of
natural zeolites, and each has a slightly
different composition that allows the
adsorption of one or other molecules. They
have a high capacity of cationic exchange
facilitating the adsorption of water molecules,
ammonium and heavy metal ions. Natural
zeolites have the exceptional quality of ion

exchange, incorporating cations such as cadmium, mercury, nickel or arsenic

(heavy metals) and releasing calcium, magnesium or phosphates (minerals
that are healthy for the human body). This fact makes the natural zeolite used
for various natural applications related to agriculture, animal nutrition, water
purification, gas filtration or human health. |Examples of natural zeolites ,
Na2O.Al2O3.xSiO2.yH2O.

3-2:synthesis zeolites:

Zeolites occur naturally but are also produced industrially on a large scale.
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. Synthetic zeolites hold some key advantages
over their natural analogues. The synthetic materials are manufactured in a

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 Chemical engineering Zeolite catalyst

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 ued 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. There many methods used
for synthesis of zeolites :

Conventional Method: Conventional zeolite synthesis involves the various

methods like hydrothermal, One Step, Direct, Exchanging, Seeding and
aging method

1- Hydrothermal method: Zeolite was synthesized at high temperature

and pressure using autoclave.

2-One step Method: Materials were fused with sodium hydroxide in

muffle furnace.

3-Direct Method: Two raw materials directly mixed with different

condition to synthesize zeolite. 3.1.4Exchanging Method: Sodium type
zeolite (Na-Zeolite) mixed with Metal salt i.e. Cu, Fe, and Ni, etc. and
stirred at room temperature.

5-Seeding and aging Method: It is use to produce highly pure zeolite

with the absence of other impurities

Green method for Synthesis of zeolite: In current trends, the main problem in
zeolite researcher is the availability and cost of raw materials and
conventional synthetic method. In materials specifically in alumina and
silica source. Alumina sources are Dross, redmud, etc. by Green method
like Microwave and ultrasonic method

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 Chemical engineering Zeolite catalyst

1-Microwave method: Microwave irradiation activates the materials and

synthesized the zeolite. This method is used to reduce the time as well as
increase the yield of zeolite.

2-Ultrasonic method: This method is use to remove curing step (long

heating).ultrasonic sound wave irradiate with materials used for synthesis
of zeolite

4- Properties of Zeolites as Catalytic:

. Zeolites are very stable solids that resist the kinds of environmental
conditions that challenge many other materials. High temperatures don't
bother them because they have relatively high melting points (over 1000°C),
and they don't burn. They also resist high pressures, don't disssolve in water
or other inorganic solvents, and don't oxidize in the air. They're not believed
to cause health problems through, for example, skin contact or inhalation,
though in fibrous form, they may have carcinogenic (cancer-causing) effects.
Since they're unreactive and based on naturally occurring minerals, they're
not believed to have any harmful environmental impacts. Although zeolites
might sound incredibly boring, their stable and unreactive nature isn't what
makes them useful.

5- Applications of zeolites:

 Applications in fine chemical industry:

Applied in from DEG to 1,4-diethylene dioxide, from isobutene and

methanol to MTBE, and synthesis of 3,5-dimethylpyridine.

 Applications in environment protection industry:

Because of its strong adsorption capability to VOCs, ZSM-5 can be
used in removal of thiophene, phenol, trichloroethylene,
formaldehyde and H2S, and the conversion of NOx to N2. Phenol is a

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Chemical engineering Zeolite catalyst

basic raw material widely used in chemical industry, and phenolic

effluent can be produced during the processes of pharmaceutical and
refining industry.

 Applications in chemical anticorrosion industry:

Most of the liquid flow is corrosive in chemical equipment and
pipeline which can be easily corroded, and the performance and
safety of the process will be reduced. ZSM-5 obtains a good
performance of anticorrosion to most corrosive liquid acid except HF.
The anticorrosive property of the ZSM-5 coating is attributed to the
zeolite membrane which are deposited densely and continuously on
the metal surface with several nanometers thickness. The zeolite
membranes of ZSM-5 can resist the corrosion of HCl, HNO3, H3PO4
and H2SO4 effectively.

 Applications in electrochemical industry:

All solid state lithium polymer battery will be one of the most used
chemical power source in the future with good application prospect
because of its high energy density, good safety performance and
portable feature. The conductivity of the microporous membrane will
be increased effectively when the ZSM-5 is introduced. The
comprehensive performance of electrolyte prepared by ZSM-5 is
much higher than that of electrolyte prepared by Al2O3. The process
is easy and suitable for industrialization especially. And ZSM-5 has a
potential application prospect in methanol fuel cell.

 Applications in oil refining industry:

Zeolites have the greatest use in catalytic cracking. They also play a
role in hydroisomerisation, hydrocracking and aromatics processing.
The strong acidity of zeolites plays a role in hydrocarbon processing.
Asides this, they are finding increasing use in synthesis of fine
chemicals and organic intermediates in isomerisation reactions,
nucleophilic substitution and addition etc.

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 Chemical engineering Zeolite catalyst

Table 1:Zeolites applications in catalyst

Inorganic reactions: H2S oxidation, NO Hydrocarbon
conversion: Alkylation,
reduction of NH3, CO oxidation, reduction Cracking

Organic reactions: Aromatization (C4 Dehydration

hydrocarbons),Aromatics(disproportionation,
hydroalkylation, hydrogenation, hydroxylation, Epoxidation
nitration, etc.)

Beckman rearrangement Methanol to gasoline

(cyclohexanone to caprolactam)

Chlorofluorocarbon decomposition Shape-selective reforming

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Chemical engineering Zeolite catalyst

6- Advantages and limitations of zeolites as

catalysts:

 Advantages:
the main advantages of zeolites over conventional catalysts are due to the
great acid strength they can have and to their great adaptability to
practically all types of catalysis. Numerous potential applications of
zeolites have been found in the synthesis of chemicals

 The main limitations are:

1. the great sensitivity of zeolites to deactivation by irreversible
adsorption or steric blockage of heavy secondary products.
2. the impossibility of using their microporosity for the synthesis of
bulky molecules. Because of the greater polarity of functional
compounds, it is more difficult to exploit the shape selectivity of
zeolites for their reactions than in the case of hydrocarbons.

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Chemical engineering Zeolite catalyst

7-Discution:

Q: What are zeolites?

A: Zeolites are hydrated aluminosilicate minerals made from interlinked
tetrahedra of alumina (AlO4) and silica (SiO4).

Q: What is Zeolite formula?

A: The chemical formula of zeolites is Na2Al2Si2O8.
Q: What is synthetic zeolite?
A: manufactured in a thermal process. ... Synthetic zeolites are attractive
for drying and separation owing to their affinity for water and other
small diameter molecules, and also their ability to reject large
diameter molecules.

Q: Where is zeolite found?

A: Natural zeolites form on volcanic rocks due to the reaction between
alkaline and groundwater. They can also be found in shallow marine
basins after forming for thousands or millions of years.

Q: What is zeolite made of ?

A; Zeolites are crystalline solids structures made of silicon, aluminum
and oxygen that form a framework with cavities and channels inside
where cations, water and/or small molecules may reside. They are
often also referred to as molecular sieves.

Q: How are zeolites used as catalysts?

A: Zeolites are extremely useful as catalysts for several important
reactions involving organic molecules. The most important are
cracking, isomerisation and hydrocarbon synthesis. Zeolites can
promote a diverse range of catalytic reactions including acid-base and
metal induced reactions

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Chemical engineering Zeolite catalyst

8-conclution:

The report shows that zeolites have many different structures and its
basic unit is the SO4- and AlO4- tetrahedral, linked together by the
sharing of an oxygen atom and can occur naturally but are also produced
industrially. The cage-like structure of zeolites makes them useful in all
sorts of ways such as oil refining industry as they play a role in
hydroisomerisation, hydrocracking and aromatics processing, fine
chemical industry and many other applications as this report are
presented only some important directions of zeolites utilizations but the
possibilities, the use of these interesting materials are much broader. The
report shows that the importance of zeolites comes as they not only offer
higher surface areas and enhanced activity, but also provide shape/size
selectivity.

9-Recommenation:

In order for more understanding of zeolite catalyst recommended the

following:

 Study the Powder Diffraction in Zeolite or knowing at least its

fundamentals
 Understanding the origin of reactivity of zeolite materials as there
necessitates in the development of themolecular-leve.
 Study The Concept of the Potential Energy Surface.
 Reactions in Confined Space.
 Learning the Characterization of acidity with adsorbed probe
molecules

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Chemical engineering Zeolite catalyst

10-References:

 http://www.haixinmol.com/English/Products/p01/73.html?gclid=Cj
wKCAjwqML6BRAHEiwAdquMnVL5LUqJlJDD2SlsC72Qgjqy
 www.explainthatstuff.com/zeolites.html
 Arthur W. Chester l Eric G. DerouaneZeolite Characterization and
Catalysis , (2001),
 https://www.slideshare.net/hzharraz/zeolite-and-its-uses
 Kulprathipanja, S. Zeolites in Industrial Separation and Catalysis;
Wiley-VCH: Weinheim, Germany, 2010.
 Bert F. Sels, Zeolites and Zeolite-like Materials(2013)
 www.researchgate.net/publication/323417430_Zeolite_Synthesis_
Characterisation_and_Application_Areas_A_Review
 Rollmann LD, Valyocsik EW, Shannon RD (1995). "Zeolite
Molecular Sieves". In Murphy DW, Interrante LV (eds.). Inorganic
Syntheses: Nonmolecular Solids. Inorganic Syntheses. 30. New
York: Wiley & Sons.
 https://www.ques10.com/p/29776/explain-zeolite-process-of-
water-softening-include/

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