20 Recent Patents on Chemical Engineering, 2012, 5, 20-27

Recent Patents of Natural Zeolites Applications in Environment, Agricul-

ture and Pharmaceutical Industry
Reyad A. Al Dwairi1 and Aiman E. Al-Rawajfeh2*

1
Head of Natural Resources and Chemical Engineering Department, 2Director of Energy and Oil Shale Research Center
(EOSRC), Tafila Technical University, Department of Natural Resources and Chemical Engineering, P. O. Box 179,
66110 Tafila, Jordan

Received: October 14, 2011 Revised: January 23, 2012 Accepted: February 07, 2012

Abstract: The zeolites are a popular group of minerals known as hydrous aluminumsilicate. More than forty naturally oc-
curring zeolites were reported by different research groups and more than 150 zeolites have been synthesized. They have
been increasingly used in various application areas such as industry, agriculture, and environmental protection. This re-
search paper reviews the recent patents of using zeolites in environment, agriculture and pharmaceuticals. Agriculture has
more concern in the last ten years in the world, so zeolites can be used as agricultural and horticultural fungicide and as
soil amendment. The use of zeolites in water treatment is an important environmental application. The first application in
water purification by adding zeolite crystalloid coagulant ("ZCC") to water that contains particulate matter that has multi-
valent ions adsorbed on the surfaces thereof. Other application is a process for the treatment of contaminated water based
on the use of zeolites having different characteristics. Utilization of zeolites for treatment of contaminated water under dif-
ferent conditions in environmental applications is also discussed. The review also carries the recent patents available in
water treatment process, agricultural and pharmaceutical industry.
Keywords: Zeolites, Agriculture, Environment, Fungicide, Water treatment, Pharmaceutical industry.

1. INTRODUCTION industrial applications include catalysis, selective adsorption,

and fillers in paints, paper and plastics.
Zeolites are generally natural minerals group consisting
of over 50 different minerals with varying physical and
chemical properties [1] that are mined in many parts of the
world or synthesized by man. Zeolites are hydrated alumino-
silicates of the alkaline and alkaline earth cations, principally
sodium, potassium, calcium, and magnesium [2]. Natural
zeolites occurs principally in unmetamorphosed sedimentary
rocks and particularly widespread as white material covered
the volcanic rocks [3]. While the synthetic zeolite
manufactured or synthesized by one or more chemical
reactions involving breaking and/or making chemical bonds.
They combine rarity, beauty, complexity and unique crystal
habits and described as hydrated alumino-silcates complexes
of alkali and alkaline earth cations with a three-dimensional
structure framework of SiO4 and AlO4 tetrahedra as shown in
Fig. (1) [4]. The following table (Table 1) shows the chemi- Fig. (1). Tetrahedral structure of zeolite [4].
cal composition of the Jordanian zeolitic tuff [5].
This research study focuses on the recent patents of using
Different zeolitic applications depend on the unique zeolites in environment, agriculture, and pharmaceuticals.
physical and chemical properties of zeolite which include The first patent deals with the use of zeolites as agricultural
environmental, agricultural and health applications. The and horticultural fungicide. This fungicide shows a high
environmental applications include water and wastewater activity of fruits trees, vegetations, etc. and can be safely
treatment, pollution control such as heavy metal removal, applied to crops. The second application deals with using of
ammonium ion removal and air and gas purification [6-8]. phillipsitic zeolite as soil amendants. Yenomite, which is
The agricultural applications include fungicides and found in a particular area of Jordan, comprises primarily
herbicides, aquaculture, soil conditioning, animal feed phillipsite as the zeolite, optionally in conjunction with
supplements, and carriers for slow release insecticides. The palagonite. Yenomite provides surprisingly better results
compared to other zeolite-based soil amendment composi-
*Address correspondence to this author at the Energy and Oil Shale Re- tions. Other important patents including the use of zeolites in
search Center (EOSRC), Tafila Technical University, Department of Natural the protection of environment for water treatment. A new
Resources and Chemical Engineering, P. O. Box 179, 66110 Tafila, Jordan; technology was applied for this proposes using zeolite crys-
Tel: +96232250034; Fax: +96232250431; E-mail: aimanr@yahoo.com
talloid coagulants. This relates to the use of zeolite crystal-

-/12 $100.00+.00 © 2012 Bentham Science Publishers

Recent Patents of Natural Zeolites Applications in Environment, Agriculture Recent Patents on Chemical Engineering, 2012, Vol. 5, No. 1 21

Table 1. Chemical Analysis of Zeolitic Tuff from Different Parts of Jordan [5]

Area %SiO2 %Al2O3 %Fe2O3 %MgO %CaO %K2O %Na2O

Tell Rmah 42.0 12.8 12.1 10.1 8.5 0.8 4.0

Mkawer 42.7 13.9 12.7 9.2 9.8 1.9 2.1

Aarityan 38.6 12.8 12.1 9.6 9.3 1.5 2.1

Shihan 44.0 13.2 8.3 8.6 11.3 1.2 2.0

Tell Jheera 35.0 10.2 11.3 7.6 20.2 0.7 2.4

Habal Atata 48.0 10.8 8.1 7.7 10.1 0.5 1.5

Tlul Al-Shahba 41.7 11.8 12.0 10.3 9.4 1.7 2.8

Jabal Onaizah 40.0 7.9 8.8 8.6 15.8 0.9 2.7

loids as coagulants in the clarification of water or to promote
important retention, drainage, and formation in the manufac-
ture of paper and paperboard. Other technology used for
water treatment is a process for the treatment of contami-
nated water based on the use of polar zeolites having differ-
ent characteristics. This process is described for the treat-
ment of water contaminated by polar organic compounds and
/ or by heavy metals, which consists of circulating the water
through a system comprising at least two types of zeolites.
The last process used for the treatment of contaminated wa-
ter was the removal of biological pathogens from water using
Surfactant-Modified Zeolite (SMZ). A method for removing
biological pathogens from a fluid or a fluid-based gel in-
cludes filtering the fluid or fluid-based gel using SMZs. This
method includes drawing air through a fluid layer or a fluid-
based gel layer and filtering the fluid or the fluid-based gel
layer using SMZs.
The last patent discuses a method of treating, preventing,
or palliating elevated human blood lead levels, comprising
administering to a human in need thereof a pharmaceutical
formulation comprising a synthetic sodium aluminosilicate
zeolite and a pharmaceutically acceptable adjuvant.
The purpose of this work is to review the recent patents
available in using zeolites in environment, agriculture and
health applications to clear the role and the importance of
zeolites in different areas.
2. APPLICATION OF ZEOLITE IN AGRICULTURE
2.1. Zeolites as Agricultural and Horticultural Fungicide
Many known fungicides are not satisfactory because they
show efficiency only against narrow range of diseases and
the phytotoxicity to crops limits the range of the application.
Consequently, developing high-performance chemicals
which give little phytotoxicity and are effective at a low
dosage rate has been desired. The researchers [9] have
extensively worked to find chemicals which have an
excellent activity against various diseases of fruit trees and
vegetables and can safely be applied to crops, and as a result,
have surprisingly found that novel copper-containing zeolites
have an excellent fungicidal activity and yet shows no
problematic phytotoxicity. An agricultural and horticultural
fungicide consisting essentially of a fungicidally effective
amount of crystalline zeolite (phillipsite and faujasite) by a
method for controlling plant pathogenic fungi. An inert
carrier selected from the group consisting of kaoline clay,
attapulgite clay, bentonite, terra alba, pyrophillite, talc,
diatomaceous earth, calcite, corn stalk powder, walnut shell
powder, urea, ammonium sulfate, synthetic hydrated silicon
dioxide, calcium lignosulfonate, sodium laury sulfate,
polyoxyethylene sorbitan monooleate, carboxymethyl
cellulose and water.
A product obtained by copper ion exchange of
aluminosilicate, can be used as an agricultural and
horticultural fungicide. In reality, however, the copper-
containing aluminosilicate does not have a strong fungicidal
activity per copper content and it cannot compensate the
defect of the conventional inorganic copper-containing
chemicals. A chemical having sufficiently high fungicidal
activity per copper content enough to be highly effective at a
low dosage rate of copper has been developed. The
crystalline zeolite has an extremely high activity per copper
content.
A great improvement in the activity per copper content
results in various advantages in controlling crop diseases.
That is, since the agricultural and horticultural fungicide
exhibits an excellent activity against various plant diseases, it
has a number of advantages as follows:
Its dosage rate can be reduced because the phytotoxicity
to crops can be markedly improved. It can be satisfactorily
applied to various crops to which the existing metal-
containing fungicides such as a Bordeaux mixture cannot be
applied.
Because of a great improvement in its activity per copper
content, it has an advantage that it can be applied without
increasing a residual copper content to a field containing a
large amount of residual copper in the soil.
This substance can be obtained by adding an aqueous
sodium or potassium aluminate solution with an aqueous
sodium or potassium silicate solution in a prescribed
concentration ratio to an aqueous caustic soda or caustic
potash solution, carrying out hydrothermal synthesis to
produce the precursor of the present substance (zeolite) then
22 Recent Patents on Chemical Engineering, 2012, Vol. 5, No. 1
followed by ion-exchanging the zeolite with a water-soluble
copper salt in water or an alcohol. The water-soluble copper
salt used in this reaction includes for example mineral acid
salts of copper such as cupric chloride, cupric sulfate, cupric
nitrate, etc. Further, organic acid salts (e.g. cupric acetate,
cupric format), ammonia-copper complex salts, etc. may also
be used.
Because this substance exhibits an excellent effect
against plant diseases, it can be used in various applications
as an active ingredient for agricultural and horticultural
fungicides. It controls most of the plant diseases.
When this substance is used as an active ingredient for
fungicides, it may be used as it is without adding any other
ingredients. Usually, however, it is formulated before use
into granules, wettable powders, suspension formulations,
dusts, etc. by mixing with solid carriers, liquid carriers,
surface active agents and other auxiliaries for formulation.
The content of the present substance in these preparations is
from 0.1 to 99.9%, preferably from 1 to 99%.
The application method for the agricultural and
horticultural fungicide includes, for example, foliage
application, soil treatment, seed disinfection, etc., but
usually, the present fungicide may be used by any method
used by those skilled in the art. When it is used as an active
ingredient for agricultural and horticultural fungicides, the
dosage rate of the active ingredient varies with crops to be
protected, diseases to be controlled, and degree of outbreak
of diseases, preparation forms, application methods,
application time, weather conditions, and copper contents.
2.2. Zeolite as Soil Amendants
An agricultural and horticultural plant growth zeolite-
based composition containing a particular zeolitic material,
termed “Yenomite,” is described by Allen and Braum [10].
This composition exhibits a collection of outstanding
advantageous properties in agricultural and horticultural
applications. Yenomite, which is found in a particular area of
Jordan as shown in Fig. (2) [11], comprises primarily
phillipsite as the zeolite, optionally in conjunction with
palagonite. Yenomite provides surprisingly better results
when compared with the other types of zeolite-based soil
amendment, even when it is used as the mined material that
has been only subject to a grinding or crushing operation to a
desired mesh size. As mined, Yenomite contains very low
levels of undesired Na+ ions. It can, therefore, be used
without being subjected to a washing operation to remove
these ions. Yenomite also possesses a very high CEC. These
characteristics, and others, make Yenomite uniquely suitable
to use in any agricultural or horticultural operation.
Yenomite exhibits a collection of outstanding
advantageous properties in agricultural and horticultural
applications. Yenomite, which is found in a particular area of
Jordan, comprises primarily phillipsite as the zeolite,
optionally in conjunction with palagonite. As mined,
Yenomite contains very low levels of undesired Na+ ions. It
can, therefore, be used in agricultural and horticultural
operations without being subjected to a washing operation to
remove these ions. Yenomite also possesses a very high CEC
of, for example, 0.90 to 2.5 meq/g or greater. These
Al Dwairi and Al-Rawajfeh
characteristics, and others, make Yenomite uniquely suitable
to use in any agricultural or horticultural operation.
3. APPLICATION OF ZEOLITE IN ENVIRONMENT
3.1. Method of using zeolite crystalloid coagulants in
water treatment
Zeolite crystalloids are used as coagulants in the
clarification of water or to promote improved retention,
drainage, and formation in the manufacture of paper and
paperboard [12]. Coagulants and flocculants are used to
improve the efficiency of the papermaking process by
improving the first pass retention of fiber and filler, and
formation and drainage, on the paper machine forming wire.
Therefore, the demand for more efficient, inexpensive water
treatment compositions for use as coagulants and flocculants
is increasing. Widely used as coagulants and flocculants in
the clarification of raw waters, process waters, and effluent
waters are chemicals such as alum, sodium aluminate,
polyaluminum chloride, activated silica, bentonite clays,
inorganic iron salts, low molecular weight organic cationic
polymers, high molecular weight organic polymers, and
others. Some of these coagulants and flocculants may be
used by themselves; however, in many cases various
combinations of these materials may produce more efficient
results, depending upon the nature and requirements of the
water to be clarified. The manufacture of nearly all fine
paper worldwide is now done at alkaline pH levels (about 8.0
to 8.4 pH) using calcium carbonate pigment as a filler along
with bleached wood cellulose fiber (some cotton cellulose is
used in specialty papers).
Thee zeolite crystalloids or sols are used as coagulants in
the clarification of raw fresh waters, process waters, indus-
trial and municipal waste waters, etc. and also as a coagulant
in the manufacture of paper. The materials to be coagulated
will either have a suitable amount of multivalent cations on
their surfaces or a source of multivalent cations will be pro-
vided so as to allow adsorption of the cations onto the sur-
faces before the ZCC is added. In papermaking, a synthetic
linear or branched polymer source of multivalent cations
and/or cationic starch may be adsorbed onto the furnish
surfaces. The adsorbed cationic polymer and/or cationic
starch is essentially an extended source of multivalent
cations that can displace the exchangeable sodium or potas-
sium ions in the ZCC and so present additional bridging sites
for the ZCC. This enhances the clarification of the moving
stream of mixtures of cellulose fiber, inorganic filler pig-
ments (e.g., calcium carbonate, clay, and titanium dioxide),
sizing agents, starches, gums, etc., so as to promote better
retention of these solids on the traveling formation wire,
more rapid drainage of water through the traveling wire, and
improved uniformity of formation in the dried sheet of paper.
Thee presence of multivalent cations on the surface of the
solids to be coagulated is essential for the superior perform-
ance of the zeolite crystalloid sols. A key to the process is
the ability of the ZCC to exchange sodium ions or potassium
ions for all or part of multivalent cations such as calcium,
magnesium, iron, cationic starch, and cationic polymers,
either alone or in combination and, accordingly, become
bonded to other particulates and fibers having these
multivalent cations adsorbed on their surfaces and, in so
Recent Patents of Natural Zeolites Applications in Environment, Agriculture
Fig. (2). Location map of Zeolite deposits in Jordan [11].
doing, cause coagulation. (In papermaking, calcium, magne-
sium, cationic starch, and cationic polymers are preferred
cations).
The use of zeolite minerals to remove hardness ions
(namely calcium and magnesium) from water is well known
in the historical sense; zeolites were replaced long ago with
synthetic organic, ion-exchange resins. To prepare zeolite
minerals for water softening, they would be rinsed with a
concentrated brine of sodium chloride. This high concentra-
tion of sodium would cause the removal of any hardness ions
bonded within the crystal lattice and replace them with so-
dium ions. Then, the excess brine would be rinsed away, and
the water to be softened would be flowed through a bed of
zeolite mineral. Without the presence of excess sodium ions,
the hardness ions were preferentially held by the zeolite and,
accordingly, the sodium ions held in the crystal lattice would
be replaced by the hardness ions, with the sodium ions re-
maining with the now softened water.
Synthetic zeolites, in the sodium or potassium form, can
be superior coagulants for particles and fibers having multi-
valent ions on their surface either naturally, as is the case
with calcium carbonate pigments, or adsorbed as can be the
Recent Patents on Chemical Engineering, 2012, Vol. 5, No. 1 23
case with clays and cellulose fibers, for example. On the
surface of the zeolite crystal there will be many tetrahedra
points with exchangeable sodium or potassium cations asso-
ciated with the otherwise electronegative oxygen. With rela-
tively low levels of sodium or potassium ions present in the
system to be clarified, these exchange points will give up
their sodium cations or potassium cations to bind more
strongly to the multivalent cations on the surface of the par-
ticle or fiber in the system to be clarified. Being three-
dimensional, the zeolite will attach to more than one particle
or fiber and, accordingly, coagulate them.
Dilute solutions of silicate and aluminate of sodium or
potassium can control the formation of the zeolite crystalloid
sols in sizes from the 1 nm to 3 nm range, which is generally
considered to be yet a solution, up to the micron size range.
According to the invention, a particle size range of at least
about 4 nm is used, with a range of about 4 nm to about 100
nm being preferred. Dissolved material below about 4 nm in
size is effective, but the very small size of these molecules
apparently restricts their three-dimensional bridging ability.
This bridging ability, which is very valuable in papermaking
and raw water coagulation clarification, improves dramati-
cally at about 4 nm.
24 Recent Patents on Chemical Engineering, 2012, Vol. 5, No. 1 Al Dwairi and Al-Rawajfeh

The efficacy of the invention is based in part of the pres- present in the water and in particular groundwater (ions,
ence of exchangeable sodium ions or potassium ions at the humic acids, etc). If used for the formation of permeable
otherwise electronegative oxygen atom in the aluminum reactive barriers, it consequently causes an exhaustion of the
tetrahedra. If hard water is used when making the coagulant, system in short periods.
the calcium ions and magnesium ions present in the water Both systems however prove to be ineffective in remov-
will have taken the place of the exchangeable sodium ions or
ing all the polluting principles often contemporaneously
potassium ions during formation of the sol, thereby decreas-
present in contaminated groundwater beneath industrial sites,
ing or eliminating the essential ion exchange potential that
which frequently consists of apolar compounds such as halo-
results in the inventive coagulant's high efficiency.
genated solvents and compounds deriving from the oil indus-
In diluting the strength of the inventive coagulant salt try. These are often highly toxic products, some of which are
after it has been formed, it is also desirable to use water carcinogenic, whose concentration in the groundwater must
containing as small a concentration of calcium ions or mag- respect the strict limits established by the legislation. In
nesium ions as possible during the quench stage that stops order to overcome the critical problems specified above,
sol growth. The presence of significant amounts of calcium alternative procedures were proposed, which are substan-
ions or magnesium ions could decrease the activity of the tially based on the use of apolar zeolites as adsorbents for
coagulant exchange sites needed for effective coagulation. specific substances. The process allows contaminants which
are difficult to eliminate, normally present in contaminated
Thus, both in diluting the sodium silicate or potassium
groundwater beneath industrial sites, to be effectively and
silicate and sodium aluminate and in quenching the sol-
selectively removed.
forming reaction, the use of ion-exchange softened water or
deionized water is highly preferred. Zeolites have a higher absorption capacity and function-
The rate of the ZCC-formation reaction is dependent ing duration with respect to that of materials currently used
in permeable reactive barriers, such as activated carbon. The
upon concentration and temperature. In the manufacture of
properties of this reactive medium which are based on the
zeolites for water softening, relatively high concentrations of
dimension of the structural channels, suitably calibrated for
sodium aluminate and sodium silicate are used because the
organic molecules, and on the high a polarity, deriving from
goal is to produce strong, relatively large particles that can
high silica/alumina ratios, exclude any type of interaction
support one another in zeolite beds several feet high. High
concentrations instantly produce a solid mass of sodium with ions or polar compounds. The zeolite consequently has
a selective interaction with molecules of apolar contaminants
aluminum silicate (a zeolite), infused with water.
whereas it completely excludes ions and polar molecules
normally present in groundwater together with humic sub-
3.2. Process for the Treatment of Contaminated Water stances, having high molecular dimensions than those of the
based on the Use of Polar Zeolites having Different
structural channels. Although water treatment processes
Characteristics
based on the use of zeolites allow an effective and selective
A process for the treatment of water contaminated by elimination of contaminants when these are present at low
apolar compounds and/or heavy metals which is based on the concentrations, they are less effective when they are present
use of two apolar zeolites having different characteristics at high concentrations.
was patented [13]. This process treats water contaminated by A process uses at least two types of zeolites placed in
apolar compounds consisting of halogenated organic sol- succession Fig. (3) which, due to an unexpected synergic
vents and mono and polycyclic aromatic hydrocarbons, effect, allows organic contaminants to be effectively re-
chloro-aromatic compounds, aliphatic hydrocarbons, oxy- moved from water when they are present at both low and
genated compounds present in fuels and/or heaving metals high concentrations.
such as arsenic, hexavalent chromium, antimonium, sele-
nium, mercury, cadmium, cobalt, nickel, lead, manganese
and copper, which is based on the use of a system compris-
ing at least two types of polar zeolites placed in succession.
It can conveniently be used for the treatment of groundwater
contaminated by both low and high concentrations of polar
compounds using a permeable reactive barrier (PRB). Con-
ventional PRB for the decontamination of water contami-
nated by halogenated solvents are based on systems which
use metallic iron and/or granular activated carbon (GAC).
The first system, which functions according to the reducing
capacity of the metal, is only active towards reducible sub-
stances, such as organo-chlorinated products or metals with a
high oxidation number. Furthermore, when a zero-valence
iron is used, it causes a reduction in the permeability of the
barrier due to encrustations or the precipitation of minerals
which derive from the reactions between the ions of the
oxidized metal and the substances contained in the ground-
water. The second system is a specific absorbent and as such Fig. (3). Column experiment consisting of two types of zeolite Y
is poorly selective with respect to interfering substances and ZSM-5.
Recent Patents of Natural Zeolites Applications in Environment, Agriculture
Although this system excludes ions and polar molecules
normally present in groundwater, from the structural chan-
nels, where the adsorption of apolar contaminants takes
place, it has surprisingly proved to be effective in the re-
moval of ions of heavy metals such as arsenic, hexavalent
chromium, antimonium, selenium, mercury, cadmium, co-
balt, nickel, lead, manganese and copper. Zeolites which can
be conveniently used in the process of the invention are
those which have been subjected to a formulation process.
3.3. Removal of Biological Pathogens Using Surfactant-
Modified Zeolite
It is known that septic tanks, sewage effluents, and land-
fills can release microbial and viral pathogens into ground-
water. Microbial contamination of drinking water is a serious
problem with global significance [14]. In many countries
around the world, including the United States, groundwater
serves as a primary drinking water source. In the United
States, groundwater provides approximately 40% of the
water supply used for public consumption [14]. Groundwater
is susceptible to fecal contamination from a variety of
sources including leaking sewer lines, leaking septic tanks,
infiltration of surface water contaminated by human and
animal wastes, and careless disposal of septic wastes. Micro-
bial pathogens were shown to be responsible for almost 30%
of these outbreaks [16, 17].
The biological pathogens include bacteria, viruses, proto-
zoa, parasites, and microbes. The fluid may be forms of
water, such as drinking water, ground water, well water, or
waste water.
This present patent concern with water treatment field
and provides a variety of compositions and methods for use
in the removal of biological pathogens from water using
Surfactant-Modified Zeolite (SMZ). A method for removing
biological pathogens from a fluid or a fluid-based gel in-
cludes filtering the fluid or fluid-based gel using SMZs. This
method includes drawing air through a fluid layer or a fluid-
based gel layer and filtering the fluid or the fluid-based gel
layer using SMZs. A water filter, water treatment facility,
and an air filter may utilize this method.
Biological contamination occurs with improper sanitary
habits, especially prevalent in Third World countries, where
a river or lake may provide water for consumption as well as
serving as a bathing facility and bathroom. These practices
can introduce various parasites, bacteria, and viruses into the
drinking water supply.
The major factors controlling pathogen fate and transport
in ground water are attachment and detachment, inactivation,
advection, and dispersion [18]. Forces responsible for the
attachment and detachment of pathogens include electro-
static attraction and repulsion, van der Waals forces, and
hydrophobic effects [19]. Brownian movement and straining,
which depend on the size of the pathogen and the medium
particles, can also contribute to the attachment of viruses and
bacteria onto porous media.
Biological pathogens are entities such as viruses, bacte-
ria, protozoa, parasites, and various other microbes. Viruses
possess a protein coat that results in a surface charge that
varies with pH. Due to their net positive charges, materials
Recent Patents on Chemical Engineering, 2012, Vol. 5, No. 1 25
with high isoelectric points may be suited as geological bar-
riers to virus migration.
Surfactant-Modified Zeolites (SMZs) are created by
treating zeolites with a surfactant, such as hexadecyltrimeth-
ylammonium (HDTMA), which converts the negative sur-
face charge of the zeolites to the positively charged surface
of the SMZ. This development of an inexpensive means for
blocking the transmission of bacteria, viruses, parasites, and
other microbes to humans can significantly reduce disease
outbreaks associated with contaminated groundwater and
also alleviate concerns regarding bioterrorist threats to drink-
ing water supplies [20].
SMZs are made by a method of intimate mixing and
binding of materials to create a pollutant adsorption/ degra-
dation filter material. This method mixes at least one
adsorbent material (for example, natural zeolite) with at
least one surface-altering material (for example, a surfac-
tant). The resultant SMZ can be used directly for patho-
gen control.
The SMZ can be in granular form, combined with a
binder material, and/or can be formed into a solid structure.
The solid structure can be in the form of any shape suitable
for inclusion into a filtration device. The filtration device can
be a potable water filter, a point of use water filter, a water
bottle filter, or a filter packet that is to be placed into a body
of water such as a well or small pond.
The advantage of using SMZ as a filter is its low cost as
well as the instantaneous adsorption of multiple types of
contaminants.
A number of advantages are realized in the preparation of
the surfactant-modified zeolite using the present technique,
including the selection of raw materials in terms of size,
shape and composition, as well as in the ease of manufactur-
ing. It is well known that available surface area is the key to
the reactivity of adsorptive materials. Following this logic,
the selection of finely ground raw materials is superior to
larger sizes. However, finer or smaller aggregates result in
reduced hydraulic conductivity or permeability of the prod-
uct.
Passing typical ground water that contains biological
pathogens, which may carry a negative surface charge,
through inexpensive SMZ filters can result in the adhesion of
the pathogens to the positively-charged SMZ filter and the
removal of the pathogens from the drinking water. SMZs
have the desirable characteristics of possessing a large sur-
face area and remaining rigid in water, which provides an
advantage over the use of clay minerals which swell in water
and can limit the efficient flow of water.
The filtration device may be a household water filter, a
filter fitted on to the end of a faucet, or a water bottle filter
for use during a trip. The filtration device may also be one
that is placed in or around a well or other body of water for
the purpose of removing biological pathogens from a water
source.
SMZ filters can be used in industrial applications such as
filtering fluids used in cooling systems. Fluids used as a
coolants in industrial systems often pass through towers,
ponds, or other process equipment where microorganisms
26 Recent Patents on Chemical Engineering, 2012, Vol. 5, No. 1
can come into contact with the fluid, obtain nutrients, and
propagate.
4. APPLICATION OF ZEOLITE IN PHARMACEUTI-
CAL INDUSTRY
4.1. Zeolite Molecular Sieves for the Removal of Toxins
A microporous or mesoporous silicate, also known as a
molecular sieve, which is granular or powdered, is
administered to humans once or more, daily for several days,
weeks, months or years, for the purpose of treating human
diseases. The zeolitic substance is administered in the form
or a tablet, capsule or pharmaceutical suspension.
Synthetic zeolites are preferred. The granules or powder
particles are small enough that diffusion of a variety of ions
or other organic or inorganic toxins may freely pass in and
through the rigid and well-ordered crystalline structure [21].
It is understood that water may or may not comprise the
zeolitic material initially, but in an aqueous environment
such as the human digestive tract, water will virtually
completely fill the framework structure. Based on the
specific details of the framework structure, it has been shown
that there is a specificity of binding of ions, toxins and other
classes of molecules.
A gelatin capsule of the zeolite can be swallowed by a
person with a glass of water. In the acidic environment of the
stomach, the gelatin capsule dissolve thereby releasing
several hundred milligrams of the zeolite. The zeolite
absorbs water to full saturation and forms slurry.
Aluminosilicates are known to be resistant to acidic
degradation at room temperature or body temperatures and
therefore the framework structure remains intact during
passage through the stomach and is not susceptible to the
actions of oral cavity-, stomach- or pancreas-, small bowel-
and large-bowel-derived digestive enzymes and peristaltic
movements. In the intestinal juices found in the stomach,
duodenum, jejunum, ileum and colon poisonous ions and
toxins will bind to the zeolite. These poisons or toxins
include heavy metals such as lead, copper, potassium,
ammonia, mercaptans and hydrogen sulfide. Additional
toxins include those that are plant-, marine organism- and
nuclear-derived. When a poisonous ion or molecule binds to
the zeolite, it is prevented from exerting its toxic effects on
the intestinal lining or from being absorbed into the
bloodstream for systemic deposition. An important feature is
that zeolites administered as described may be employed to
remove toxic ions or molecules over the period of
administration of hours, days, weeks, months or years. The
purpose of the zeolite is not only intended to prevent the
deposition of toxic effects of a heavy metal or toxin that may
be a contaminant of ingested food, but additionally it is
envisioned to be used in the emergency treatment of toxic
ingestions, radioactive fallout (strontium and cesium), toxic
marine organism ingestions, poisoned food ingestions, etc.
For treating, preventing, and palliating high blood lead
levels (above level), preferably at least 95% of the particles
are of particle size from 90 μm to 150 μm. The formulation
may include from about 60% to about 95% by weight water.
Preferably, the formulation is a capsule or tablet
administered orally. The treatment is suitable for a human
Al Dwairi and Al-Rawajfeh
suffering from chronic lead poisoning. The human may have
a blood lead level of at least about 10 μg/dL, at least about
20 μg/dL, at least about 30 μg/dL, at least about 40 μg/dL, or
even of at least about 50 μg/dL. The human may be between
about 2 and about 15 years of age, or may be under about 6
years of age. Dosages may be, e.g., about 10 mg to about
1000 mg sodium aluminosilicate, or about 100 mg to about
900 mg, or about 200 mg to about 800 mg. Preferably, the
formulation further comprises an antimicrobial preservative
or bacteriostat.
For treating preventing, and palliating high human blood
ammonia levels, preferably at least 95% of the particles are
of particle size from 90 μm to 150 μm. The human may be
suffering from hepatic encephalopathy or cirrhosis of the
liver. The human may have a history of liver failure.
Preferably the formulation is a liquid gel administered orally.
The human may have an elevated blood ammonia level or
may be at risk for such an elevated level. The human may be
a hospital in-patient. In certain circumstances very fine
particles of < 44 μm may be preferred.
For treating, preventing, and palliating high human blood
levels of copper or arsenic, the same methods and
formulations may be used. Thus the invention relates to
treatment, prevention, and palliation in humans or animals of
excess levels of lead, ammonia, copper, and arsenic, as well
as other toxins.
Potassium regenerated sodium aluminosilicate is an
alternative for treatment of hepatic encephalopathy. An
important principle in the clinical management of hepatic
encephalopathy is treatment of the precipitating or
underlying cause of the encephalopathic episode. That is,
while a patient may have the established diagnosis of liver
failure, only when his or her mental capacity declines is the
diagnosis of HE firmly established. However, often other
dietary, pharmacological, electrolyte or infectious influences
alter the balance between normal mentation and
encephalopathy. Many times, however, the exacerbating
factor is not determined. While the treatment of HE remains
similar to that described elsewhere in this specification,
specific attention to the precipitating factor (such as a large
dietary load of protein, underlying infection, unexpected
reaction from an ingested drug or overuse of certain drugs
leading to urinary loss of potassium) is warranted by the
treating physician. Because the use of the potassium-
depleting drugs (namely spironolactone and members of the
same and different classes) is common in patients with liver
failure, they can lead to total body loss of potassium and
thereby precipitate an encephalopathic episode. The
synthetic aluminosilicate is preferably charged with sodium.
Alternatively, the synthetic aluminosilicate may be charged
with another alkali metal, e.g., Li, K, or Rb. The synthetic
aluminosilicate may alternatively be charged with an alkali
earth metals, e.g., Ca or Mg. The synthetic aluminosilicate
may be chemically modified by methods including
pegylation, silation, and glycosylation. The formulation may
contain different particle size distributions of the zeolite of
interest, and may comprise mixtures of one or more synthetic
zeolites. The formulation may contain varying amounts of
water, e.g., from about 40% or 50% (w/w) up to about 70%,
80%, or 95% (w/w).
Recent Patents of Natural Zeolites Applications in Environment, Agriculture
5. CURRENT & FUTURE DEVELOPMENTS
In this work, three different zeolitic applications recent


patents were discussed and reviewed. They are applicable for
agricultural (Horticultural fungicide and as soil amendment
(Yenomite)), environmental (polar zeolites, surfactant-
modified zeolite and zeolite crystalloids) and pharmaceutical
industry (molecular sieves for the removal of toxins)
applications.
Yaminte is a product used to improve and increase the
recovery and reduce the cost of existing technologies, new
trends in agriculture have been emerged by using zeolite as
heretical fungicide for more than 50 plant disease controlled
by zeolite agricultural and horticultural fungicides.
Water and wastewater treatment is an important problem
in the world and there is a wide interest in implementing
zeolites in environmental control, so zeolites are a good
choice to solve many problems in contaminated water
especially with huge amounts of wastewater produced from
plants in the world with no additional of other natural
resources to meet increasing water demands, and is also
growing trend for utilization of zeolites in environmental
applications results in reduction the pollution and water
contamination. The review of the patent also covers the
application of zeolite in pharmaceutical industries. Food and
health care are the most important problems facing the
increasing of the world population, it is likely that there will
be new developments in the area of zeolites as molecular
sieves and ion exchanger material to meet the challenges in
health, agriculture and water demand, so zeolites gave the
solutions for these problems especially that zeolites are
available, wildly distributed, have infinite structure and
amazing properties. Huge amounts and availability of natural
zeolites with the big group of different types of synthetic
zeolites with low cost technically gave a good chance for
more applications. Since the utilization of zeolites is wildly
used, there is a wide need of more studies for the properties
of zeolites (adsorption and ion exchange). Present review
paper can be used as reference for the future application
studies for zeolites in different areas. Detailed studies are
needed and it is highly recommended that more
investigations are crucial for the possible uses of zeolites in
new applications.
CONFLICT OF INTEREST
This work is a review of the latest patents on zeolitic
minerals applications. The two authors jointly reviewed the
literature, interpreted the results and assisted in writing and
revising the paper. The two authors have no competing
interests with any other party regarding this work.
ACKNOWLEDGEMENT
The support from Abdul Hameed Shoman Foundation is
greatly acknowledged.
Recent Patents on Chemical Engineering, 2012, Vol. 5, No. 1 27
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