International Science conference 4th - 5th June 2009, Stara Zagora, BULGARIA

"Economics and Society development on the Base of Knowledge"

SYNTHETIC ZEOLITES AND THEIR INDUSTRIAL AND ENVIRONMENTAL

APPLICATIONS
REVIEW

Bogdan Bogdanov, Dimitar Georgiev, Krasimira Angelova, Yancho Hristov

Prof. Dr. Assen Zlatarov University,
8010 Bоurgas, Bulgaria,
e-mail: bogdanov_b@abv.bg;

ABSTRACT
Nowadays, the increasing interest in zeolite synthesis from low-cost materials has
promoted the development of various studies on their conversion into zeolitic materials, giving
rise to an extensive literature. The enhancing demands for a healthy environment, particularly
with regards to high quality drinking water and removal of pollutants from industrial,
agricultural and municipal wastewater, are a major reason to search for new materials. Nearly
every application of zeolites has driven by environmental concerns, or plays a significant role in
reducing toxic waste and energy consumption. Because of their unique porous properties,
zeolites are used in a variety of applications with a global market of several million tones per
year. Major uses are in petrochemical cracking, ion-exchange (water softening and purification),
and in the separation and removal of gases and solvents. Other applications are in construction,
agriculture, animal husbandry, medicine etc.
In this study a brief overview of the zeolite’s fields of industrial and environmental
applications covering the fundamentals and recent developments is proposed.
Key words: synthetic zeolites, structure, properties, industrial and environmental applications

INTRODUCTION
The term ‘zeolite’ was firstly mentioned by Swedish mineralogist A. F. Cronstedt in 1756 as a
name of an aluminosilicate mineral (stilbite) that seemed to steam when is heated. The word zeolite
is derived from the Greek words ‘zeo’ (boil) and ‘lithos’ (stone). Since then, about 50 naturally
occurring and topologically different zeolites have been identified as a separate group of minerals.
Natural zeolites cannot meet the huge demands in industry; therefore it becomes an urgent necessity
to use synthesized zeolites besides the natural ones.
From the early 1940's onwards systematic synthesis studies on zeolites were started [1].
Nowadays, a large number of synthetic zeolite structures and compositions are available, most of
them having no natural analogues. In comparison with natural zeolites, synthesized zeolites have
many advantages such as high purity, uniform pore size, and better ion-exchange abilities. The new
structures and compositions and hence, the new physicochemical properties enlarge the range of
applications of zeolites.
Zeolites have been well studied in terms of the relations among structure, properties and
synthesis. Nowadays 180 synthetic zeolites are known. Some of the earlier synthetic zeolites
include zeolites A, X, Y, L, ZSM-5 and omega [3].

ZEOLITE INDUSTRY
Since the first definitive synthesis of an analogue of a natural zeolite reported in 1948 by
Barrer many efforts were focused on their applications in the field of adsorption, ion exchange and
catalysis. The number of scientific publications, including several thousands PhD theses, books and
monographs, showed an exponential growth in zeolite investigations and the broad present
researchers interest in zeolite science and technology.
At the beginning researchers tried to synthesize zeolites using hydrothermal synthesis
techniques at temperatures of around 25~150 °C (usually 100 °C). In the 1940s, low-silica zeolites
were synthesized. By the end of 1954, zeolites A and X began to be produced industrially.
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 International Science conference 4th - 5th June 2009, Stara Zagora, BULGARIA
"Economics and Society development on the Base of Knowledge"

Following this, a number of companies in the United States, such as Linde, Mobil, and Exxon,
imitated the formation of natural zeolites and produced a series of synthesized zeolites with an
intermediate Si/Al ratio (Si/Al= 2~5), including NaY, mordenite, zeolite L, erionite, chabazite,
clinoptilolite, and so on, which were widely applied in the fields of gas purification and separation,
catalytic processes of petroleum refining and petrochemistry, and ion exchange. The golden age for
the development of zeolites is from 1954 to the early 1980s when zeolites with low, medium, and
high Si/Al ratios were extensively explored [4]. A variety of zeolites with a Si/Al ratio of 2~5, i.e.,
‘intermediate silica’ zeolites which include mordenite, zeolite L, erionite, chabazite, clinoptilolite,
zeolite omega, etc, have been synthesized. The progress of zeolite synthesis is considered in the
early 1960s, when scientists at Mobil Corporation started to use organic amines and quaternary
alkylammonium cations as templates in the hydrothermal synthesis of high-silica zeolites. In 1970,
Flanigen first synthesized pure-silica forms of ZSM-5 (silicalite-I) and ZSM-11 (silicalite-II). In the
past 25 years, the emergence of zeolites with low (Si/Al=1.0~1.5), medium (Si/Al=2.0~5.0), and
high Si/Al ratios (Si/Al=10~100), as well as pure-silica zeolites, facilitated the study of both the
structure and property of molecular sieves and porous compounds, and promoted their applications.
Table 1 summarizess the major discoveries and advances in synthetic zeolites.

Table 1. Evolution of Synthetic Zeolites [5, 6]

Late 40’s to Early 50’s Low Si/Al Ratio zeolites
Mid to Late 60’s High Si/Al ratio zeolites
Early 70’s SiO2 Molecular sieves
Late 70’s AlPO4 Molecular sieves
Early 80’s SAPO and MeAPO Molecular sieves
Late 70’s Metallo-silicates, aluminosilicates
Mid 80’s AlPO4 based Molecular sieves
Late 80’s Large pore zeolites
Early 90’s Mesoporous molecular sieves

ZEOLITES APPLICATIONS
There are three traditional fields of application for zeolites: separation, purification, drying
and environment treatment process; petroleum refining, petrochemical, coal and fine chemical
industries; ionexchange, detergent industry, radioactive waste storage, and treatment of liquid
waste.
Zeolites has been widely used in many applications due to their unique properties (thermal
stability, acidity, hydrophobicity/hydrophilicity of surfaces, ion-exchange capacity, low density and
large void volume, uniform molecular sized channels, adsorption for gas and vapor and catalytic
properties). Zeolites are very important: being used widely in catalysis, adsorption and ion
exchange; becoming increasingly important in several environmental applications - in water
purification, particularly for the removal of ammonia, heavy metals, radioactive species and organic
substances.
Catalysis. In the 1950s it was the first application of NaA zeolite in the separation of normal
and isoalkanes by the Linde Company. In the 1960s X- and Y- zeolites were introduced as catalysts
for cracking reactions of hydrocarbon conversion. Since then NaA, NaX, and NaY have been
widely used in the petroleum industry in reactions such as cracking, alkylation, isomerization,
shapeselective reforming, hydrogenation and dehydrogenation, methanol-to-gasoline conversion
(MTG), etc. These porous materials have also been extensively used in the detergent industry and in
a variety of adsorption and separation processes such as the drying, the removal of CO2 from
natural gas, and the separation of xylene isomers, of alkenes, and of O2/N2 from air [1-3]. Despite
this, there are still many prospects for development of molecular sieves in the above three main
traditional fields.
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 International Science conference 4th - 5th June 2009, Stara Zagora, BULGARIA
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Examples of synthesized zeolite are zeolite A (Na, Ca, K), zeolite X (Na, K, Ba), zeolite Y
(Na, Ca, NH4), zeolite L (K, NH4), zeolite omega (Na, H), zeolon (MOR-H, Na), ZSM-5, zeolite F
(K) and zeolite W (K). These materials have been widely used as commercial adsorbents for drying
and purification of gases and for bulk separation of, for example, normal-/iso-paraffins, isomers of
xylenes and olefins, and O2 from air, as catalysts for petroleum refining and petrochemistry, and as
ion exchangers. Because of their excellent ion-exchange capacities, zeolites A and X can be used as
auxiliary agents in the detergent industry, in radioactive waste treatment and storage, and in the
treatment of industrial liquid wastes. Although there are approximately 180 frameworks, currently
only a few frameworks, including LTA, FAU, MOR, LTL, MFI, BEA, MTW, CHA, FER, AEL,
and TON, have been widely used in industry [7]. Fluid catalytic cracking catalysts account for more
than 95% of zeolite catalyst consumption and consist of various forms of zeolite Y. Detergents
represent the largest volume. LTA-type zeolites substitute phosphate compounds in the water
softening process in laundry. The largest market value for zeolites is in refinery catalysis. The
second most used catalyst is MFI-type zeolite. The main applications are summarized in Table 2.

Table 2. Main commercial catalytic applications [8]

Process catalyst products
Catalytic cracking Re-Y, US-Y ZSM-5 Gasoline, fuels
Hydrocracking Y, Mordenite + Mo, W, Ni Kerosene, diesel, Benzene
Alkylation of aromatics ZSM-5, Mordenite p-xylene, ethyl-benzene
Hydroisomerization Mordenite + Pt, Pd i-pentane, i-hexane
Xylene isomerization ZSM-5 p-xylene
Catalytic dewaxing Mordenite, ZSM-5 + Ni, Improvement of cold flow
noble metals properties
Transalkylation Mordenite Xylenes, cumene

Adsorption. Adsorption is a special characteristic of zeolites which is usually quite a complex

process, generally involving much more than simple ion exchange into the pore openings of the ion
exchanger. The amount of metal ion to be adsorbed is strongly affected by nature and concentration
of the counter ion (metal ion), pH, metal solubility, presence of competing and complexing ions [9].
Since it is considered to be a particularly effective technique, adsorption is the preferred method for
heavy metal removal such as Cu2+, Pb2+, Cd2+ and PO43- [10], H2 [11], CO2, CH4 and N2[12],
NOx[13], N2 and O2 [14], volatile nitrozamines [15].
The large daily output and the limited landfill capacity have resulted in social and
environmental problems. Severe water pollution and insufficient water source are major problems
all over the world. One effective alternative to environmental problems is to convert the ash into
zeolite absorbents for environmental applications such as water purification and soil conditioning
[16, 17]. The researches are concerned mainly to the application of fly based zeolites to the removal
of heavy metals [18, 19], NH4+[20], Cs+[21], As3+ and Cr6+[22].
Ion exchange. Zeolite frameworks provide substrates that support the mobility of the
nonframework cations that make them good ion exchangers. Ammonia and its compounds in the
wastewaters and effluents have harmful effects on water resources. For that reason of researches are
made for removal of NH4+ [23, 24]. Zeolites are an excellent avenue for removal of cationic and
anionic pollutants such as Cr6+and As5+ [ 25, 26], Cu2+, Pb2+ and Cd2+ [27], Fe3+and Zn2+ [28],
Sr2+[29], etc. Researches have been made about zeolite’s exchange capacity. For example, cation
exchange capacity from 160 to 260 meq 100g-1 were obtained for NaP1, Herschelite, KM, Linde F
and K-Chabazite for the cation investigated. The results showed: NaP1:
+ +
Ba >Pb >NH4 =Cd >Zn , KM: NH4 > Pb = Ba >Cd = Zn , Linde F: NH4 = Ba2+=
2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ +

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 International Science conference 4th - 5th June 2009, Stara Zagora, BULGARIA
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Pb2+>Cd2+> Zn2+, K-Chabazite: Ba2+= Pb2+> NH4+=Cd2+>Zn2+, Herschelite: NH4+= Pb2+> Ba2+=
Cd2+> Zn2+ [30].
In the last years there has been an increase in the usage of zeolites in different compositions to
delete and bury different radio-contaminations. The presence of radionuclides in wastes is a major
environmental concern. Recent paper published researched the interaction of synthetic zeolites with
Cs+ [21, 31] and Ur6+ [32] and sowed that zeolites are very effective adsorbents for radio-
contaminant removal.
Zeolites will continue to be used in the separation and purification technology through the
chemical process industry. Future trends involve environmental and biopharmaceutical application.

ACKNOWLEDGEMENTS: The financial support of the Bulgarian Ministry of

Education and Sciences (National Science Fund), contract DO-02-110/2008, is gratefully
acknowledged.

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