International Science conference

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"Economics and Society development on the Base of Knowledge"
NATURAL ZEOLITES: CLINOPTILOLITE
REVIEW
Bogdan Bogdanov, Dimitar Georgiev, Krasimira Angelova, Krasimira Yaneva
Prof. Dr. Assen Zlatarov University,
8010 Burgas, Bulgaria,
e-mails: bogdanov_b@abv.bg;
ABSTRACT
In this review zeolites are presented as one product for environmental protection control,
separation science and technology. Due to their unique porous properties they have attracted the
attention of many researchers. Special attention is given to clinoptilolite gaining an increasing
interest in preserving and improving the environment. Major uses of clinoptilolite in the field of
catalysts, gas separation and ion exchange are reviewed, though its increasing applications in
various areas such as environmental protection, industry, agriculture, food additives and
medicine are also considered. The scope of the work is to present the zeolite science, focusing
on natural zeolite structures and properties as well as to summarize clinoptilolite applications
and its role in solving environmental problems.
Key words: zeolites, clinoptilolite, application areas - environmental protection.

INTRODUCTION
The term zeolite was originally introduced in 1756 by Swedish mineralogist Baron Alex
Frederick Cronstedt, who had the honour to discover the so called stilbite. He observed that upon
rapidly heating a large amount of steam was obtained [1]. Thus, this material was named zeolite
from the classical Greek, where (zeo) means to boil and (lithos) means stone. After
their discovery zeolites are considered as separate group of minerals found in volcanic rocks for a
period of hundred years. Natural zeolites are formed as a result of chemical reactions of the
volcanic ash and alkaline water a few thousand millennia ago. They have been used in various parts
of the world for centuries.
STRUCTURE AND PROPERTIES
Zeolites are crystalline, micro-porous, hydrated alum-silicate minerals that contain alkali and
alkaline earth metals. Their frameworks are composed of [SiO4]4- and [AlO4]5- tetrahedra, which
corner share to form different open structures. The tetrahedra are linked together to form cages
connected by pore openings of definite sizes. The pore size range from 0.3-1 nm [2]. The negative
charge on the lattice is neutralized by the positive charge of the cations located within the materials
pores. Each AlO4 tetrahedron in the framework bears a net negative charge which is balanced by
additional nonframework cations like sodium [Na+], potassium [K+], or [Ca2+]. These univalent
and/or bivalent metal cations may be replaced via ion-exchange to other ions. Because of
electrostatic forces it is not possible to make an Al-O-Al bond. They are made up of T- atoms
which are tetrahedrally bonded to each other with oxygen bridges. Other T- atoms such as P, Ga,
Ge, B and Be can also exist in the framework. A general formula for a zeolite can be written as:
M2/n:Al2O3:xSiO2:yH2O, where M is the charge balance cation, n the charge of the cation, x is
generally 2, and y is the water in the voids of the zeolites [3].
More than 50 natural zeolites are discovered, six of them in large deposits: analcime,
chabazite, clinoptilolite, heulandite, natrolite, phillipsite, and stilbite [4, 5]. Clinoptilolite has variety
of applications because of abundance and its chemical properties. Extensive deposits clinoptilolite
are found in the Western United States, Russia, Bulgaria, Hungary, Yugoslavia and Japan.
In Bulgaria, the largest zeolite rock deposits were found nearby the town of Kurdjali:
Zhelezni vrata, Beli plast, Beli bair, Golo burdo, Most, Lyaskovets and Perelik. The
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"Economics and Society development on the Base of Knowledge"
main mineral observed is clinoptilolite. A field of mordenite was found nearby the village of Malko
Popovo and phillipsite around the village of Obrochishte.
According to both of nature and deposits locations there are different kinds of clinoptilolites.
The pore diameters of clinoptilolite vary from around 0.45 to 0.6 nm, and these pores dictate the
size of ions that can enter the clinoptilolite pores and undergo ion exchange. The effective pore size
of the clinoptilolite may be altered by varying the exchanging cation.
In fig.1 components of the clinoptilolite
structure are presented. The crystal lattice
comprises channels of two different sizes, and each
type may display a different selectivity behavior
for certain cations. The movement into and along
one set of channels is governed by elliptical
windows having approximate dimensions of 7.9
by 3.5 ; the other channels have a set of windows
with dimensions of about 4.4 by 3.0 [7]. The
typical properties of natural clinoptilolite (chemical
Fig. 1. Main components of the clinoptilolite
stability in various caustic media, thermostability,
structure, where M1 to M4 describe the
high rate of sorption equilibrium) promote its use
molecular bonds between earth elements and
in the environment protection chemistry and
water within the zeolite crystal [6]
industry [8]. In fig.2 are presented pictures of
natural zeolite clinoptilolite.

Fig. 2. Pictures of natural zeolite clinoptilolite: a.Clinoptililite K; b.Clinoptililite-Na; c.Clinoptililite Ca

APPLICATIONS
In the 1950s, Ames [11,12], demonstrated the use of clinoptilolite as an ammonium
scavenging agent for remediation of ammonium pollution and determined the ion selectivity for
clinoptilolite. Nowadays clinoptilolite has found widespread environmental applications which
attract the attention of many researchers mainly due to its value to one or more of three properties:
adsorption, catalysis and ion-exchange. Major uses of this material include water softening and
purification (this kind of prophylactics is mandatory in many European capitals) [13-24],
petrochemical cracking and gas and solvent separation and removal [25-28], radioprotection [2931], soil disinfection (after the Chernobyl disaster, the soil around the power plant were treated and
neutralized using clinoptilolite), soil improvement [32-34], food supplements and additives [25],
biomedical application [35-46], etc.
Water and wastewater treatment. Most technologies using zeolites for water purification
are based on their unique cation-exchange behavior, through which dissolved cations can be
removed from water by exchanging with cations on the exchangeable sites of those industrial
materials[13-17].
The process of phosphorus removal in a system with bioaugmented activated sludge and
natural zeolite addition is studied [19]. It is consisted of: metabolic activity of activated sludge,
phosphorus uptake by phosphate-accumulating bacteria adsorbed on the natural zeolite particles and
suspended in solution, and phosphorus adsorption on the natural zeolite particles. Method for
removal of arsenate and arsenite from drinking water is reported [20]. The capability of Iranian
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natural clinoptilolites was investigated for the uptake of arsenic anions from drinking water.
Clinoptilolite is a natural zeolite that has been known for their ability to remove ammonium from
polluted waters. The capacity of zeolite and chemical regeneration for ammonium removal was
investigated in several studies [21-23]. Ammonium-exchange capacity and rates of adsorption are
critical to the assessment of the feasibility of the zeolite for application to continuous wastewater
treatment [24].
Adsorption and catalysis. Zeolites may hold water up to 60% of their weight due to a high
porosity of the crystalline structure [25]. Water molecules in the pores could be easily evaporated or
reabsorbed without damage to such structures. Zeolites assure a permanent water reservoir,
providing prolonged moisture during dry periods; they also promote a rapid rewetting and improve
the lateral spread of water into the root zone during irrigation. Natural zeolites can absorb CO, CO2,
SO2, H2S, NH3, HCHO, Ar, O2, N2, H2O, He, H2, Kr, Xe, CH3OH and many other gases and can
thus be used to collect them or control odours. The efficiency of the zeolites studied in the process
of adsorption of petroleum products from gaseous and aqueous media has been studied [26]. The
results obtained have made it possible to recommend the zeolites studied for development of
adsorbent materials. The removel of Cr (III) from aqueous solution by adsorption using Mongolian
natural zeolite is investigated. The adsorption performances is discussed in terms of the effects of
modification, pH of the solution, zeolite samples, and so forth [27]. The experimental results show
that clinoptilolite is a potential adsorbent of Pb2+, Al3+, Zn2+ and Fe2+. It is not a promising
absorbent for ethanol, acetone or water without high temperature drying. South African
clinoptilolite shows similar characteristics to clinoptilolite from other countries [28].
Nuclear waste and fallout. The removal of nuclear wastes and fallout is one of the great
priorities of the zeolites. Recently example of U6+ sorption is proposed [29, 30]. It indicates that
many other applications seem possible where the advantages of the porous bulk structure are
combined with specific properties of well-chosen surfactants. The performance of natural zeolite of
clinoptilolite type was determined by studying their surface and sorption properties. [31]. The
results reported in this paper support the possibility of removal Cs and especially Co (including
137
60
radionuclides Cs and Co) from waste waters by an application of clinoptilolite-Na.
Agriculture. In recent years attention is paid to the development of substantial agriculture
and hence the Clinoptilolite as soil amendments is applied to improve physical and chemical
properties of soils [32-34]. This operation results in increasing water retention and better
consumption during the growth period. Effect of clinoptilolite on growth and flowering of
strawberry shows that its application increases the available nitrogen, potassium, phosphorus,
calcium and magnesium of the medium [33]. The effects of natural zeolite as a bed medium in
increasing plant growth as well as improvement of water quality parameters in an aquaponic system
is investigated. Objective of other studies for increasing plant growth as well as improvement of
water quality parameters in an aquaponic system is to evaluate the use of natural zeolite as a bed
medium for planting lettuce seedlings and as an ion exchangeable medium associated with plant
roots with regard to N-compounds, the removal of other cations from water and the improvement of
water quality efficiency due to higher lettuce growth in an aquaponic system [34].
Animal feed additive. The forage for the cattle is one of the growing applications areas of
clinoptilolite. The zeolite addition improves the caloricity, digestion, appetite and animals weight.
The addition of clinoptilolite to the diet of pig, poultry and cattle, improves their weight gain and
increases feed conversionratios. Clinoptilolite acts as a mycotoxin binder, absorbing toxins which
are dangerous to animals. It also helps to control toxins in animal feed, thus lowering mortality from
digestive stress and reducing the need for antibiotics. It also absorbs other toxins produced in the
feed by molds and microscopic parasites and enhances food absorption by animals [25].
Biomedical applications. Since many biomedical processes are closely related to ion
exchange, adsorption and catalysis, it is evident that natural zeolites can make a significant breakVolume IV
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through in the pharmaceutical industry and in medicine in the near future [35, 36]. The reasons for
this are as follows: (a) zeolites have known biological properties along with long-term chemical and
biological stability, (b) they reversibly bind smallmolecules, (c) they posses size and shape
selectivities, (d) they offer the possibility of metalloenzyume mimicru, (e) they have
immunomodulatory activity [37]. The use of the natural zeolite-clinoptilolite for treatment of
cancer-bearing mice and dogs led to improvements in the overal health status, prolongation of the
life span and decease of the tumor size in some cases [38-40]. An immunostimulatory effect of
natural clinoptilolite has been detected [41-43], and it is possible that this is the mechanism of its
antimetastatic ability [44]. Of the many aspects which have been investigated, the content and
mobility of toxic metals are the least considered. Organisms absorb chemical elements from
naturalminerals, a fact documented by Mascolo et al. [45], who evaluated this behavior during
digestion of selected toxic chemical elements. By analyzing the content of toxic elements in the
urine of orally clay-treated rats, they showed that absorption of elements occurs after clay ingestion.
The authors concluded that toxic elements have hazardous effects on the blood, organs and/or the
whole body. In a subsequent study [46], the same authors gave a future elucidation on the
distribution process of hazardous elements (Hg, Pb, As, Sb, Tl, Cd). Rats fed with clays had
uncreased concentrations of the elements in their organs, in the following order:
kidney>liver>heart>brain.
CONCLUSION
Most research groups give attention to the clinoptilolite, which have been driven by
environmental concerns or play significant roles in preserving and improving the environment. It
represents a new frontier of solid-state chemistry with great opportunities for innovative research
and development.
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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