zeolites and their applications

1.  Material is a broad term for a chemical substance or mixture of
substances that constitute Matter.
There are four classes of materials studied:-
(i) Metals (ii) Polymers (iii) Ceramics (iv) Composites
 All metals are good conductors of heat and electricity.
 Polymers are made from long chain molecules which may have cross
linking bonds affecting flexibility/stiffness.

2.  Ceramics is a class of material, which includes plates ,cups, bricks, earthenware
pots, engineering ceramics and refractory (furnace) materials. Ceramics are made by
heating together materials such as silica, chalk and clays. Other chemicals may be
included to act as flux and to change colour etc.
 Composites are mixtures of materials which give improved properties. One of the
materials is the matrix or binding chemical and the other is the reinforce. A good
example is GRP - glass reinforced polyester(plastic) resin. where the glass fibres
increase the strength of the polyester resin.

3. Metals
• A metal is
a material (an element, compound,
or alloy) that is typically hard
when in solid state, opaque, shiny,
and has good electrical and thermal
conductivity.
Metals are generally malleable
that is, they can be hammered or
pressed permanently out of shape
without breaking or cracking as
well as fusible (able to be fused or
melted) and ductile (able to be
drawn out into a thin wire).
Some Examples of Metals:
Ferrous metals and alloys (iron, carbon
steel, alloy steel, stainless steel, tool
and die steel)
Nonferrous metals and alloys
(aluminium, copper, magnesium,
nickel, titanium, precious metals,
refractory metals, super alloys).

4. • Polymers, both natural and synthetic,
are developed via polymerization of many
small molecules, known as monomers.
• Their consequently large molecular
mass relative to small
molecule compounds produces
unique physical properties,
including toughness, visco-elasticity,
and a tendency to
form glasses and semi-crystalline
structures rather than crystals.

5. Ceramics
• A ceramic is an inorganic compound,
non-metallic, solid material
comprising metal, non
metal or metalloid atoms primarily held
in ionic and covalent bonds.
 Crystalline ceramics
Crystalline ceramic materials
are not amenable to a great
range of processing.
 Noncrystalline ceramics
Noncrystalline ceramics, being
glass, tend to be formed from
melts.

6. • A composite material (also called
a composition material or shortened
to composite, which is the common
name) is a material made from two or
more constituent materials with
significantly different physical or chemical
properties that, when combined,
produce a material with characteristics
different from the individual
components.
Typical Engineered Composite Materials include:
Reinforced concrete and masonry Composite wood such
as plywood Reinforced plastics, such as fibre-reinforced
polymer or fibreglass Ceramic matrix composites (composite
ceramic and metal matrices) Metal matrix composites and
other Advanced composite materials.

7. • Smart materials are designed materials that have one or more
properties that can be significantly changed in a controlled
fashion by external stimuli, such as stress, temperature,
moisture, pH, electric or magnetic fields, light, or chemical
compounds.
• Terms used to describe smart materials include shape memory
material (SMM) and shape memory technology (SMT)

9.  On the Basis of Dimension

10. • Crystalline material is a material comprised of one or many
crystals. In each crystal, atoms or ions show a long-range
periodic arrangement.
• Single crystal is a crystalline material that is made of only one
crystal (there are no grain boundaries).
• Polycrystalline material is a material comprised of many
crystal (as opposed to a single-crystal material that has only one
crystal).
• Grains are the crystal in a polycrystalline materials.

11. • Nanostructured Materials are materials with a microstructure, the
characteristic length scale of which is on the order of a few (typically 1–10)
nanometers.
• 0D: quantum dots
• 1D: Nanowires
• 2D: superlattices and heterostructures
• Nano-Photonics
• Magnetic nanostructures
• Nanofluidic devices and surfaces
0D Electronic Structures: Quantum Dots

12. The folding of the sheet controls the electronic properties of the nanotubes.
• Carbon nanotubes (CNTs) are allotropes of carbon with
a cylindrical nanostructure. These cylindrical carbon molecules have
unusual properties, which are valuable for nanotechnology ,
electronics, optics and other fields of materials
science and technology.

16. Discoverer - Swedish mineralogist A.F. Crönstedt
 Upon rapidly heating, the mineral Stilbite
 produces large amounts of steam from adsorbed water
 Zeolite (zeo – boiling; lithos stone)
 Zeolites are crystalline microporous alumino-silicates, constituted by three
dimensional arrangement of TO4 tetrahedra, linked by oxygen atoms, forming
different construction units and large frameworks, where identical blocks
constitute unit cells.
General Formula: Mn+
X/n(AlO2
-)x (SiO2)y
• where, n: M cation charge
• x + y: number of tetrahedra per unit cell
• y/x: atomic Si/Al ratio
A.F. Crönstedt, Akad. Handl. Stockholm,18 (1756) 120.

17. Zeolites have pores with nanosized dimensions (0.3 – 0.8 nm) €Shape Selectivity as
crystalline materials, zeolites present a narrow range of pore sizes €gives better selectivity
than non-crystalline materials
•Ion-exchange properties
 Acidity
 Transition metals
 Zeolite framework is composed of SiO4 and AlO4 tetrahedral units (Al, Si €T-
atoms), sharing oxygen between every two consecutive-units
Catalytic
Active sites

18. How zeolites are Built
Cations (Na+, NH4, H+, transition metals) located inside the
channels or cavities of zeolites, to balance negative charges in the
framework:

19.  Zeolites are most useful and versatile heterogenous catalyst due to its high
internal surface area, strong acid sites, selective sorption and molecular
sieving properties. High internal surface area and acidity give rise to high
activity, while selective sorption and molecular sieving result in high reaction
selectivity.

20.  Zeolites are natural minerals that are mined in many parts of the world; most zeolites
used commercially are produced synthetically.
 When developing applications for zeolites, it is important to remember that not all
of these minerals are the same.
 There are nearly 50 different types of zeolites (clinoptilolite, chabazite, phillipsite,
mordenite, etc.)
The basic differences between natural and synthetic zeolites are:
 Synthetics are manufactured from energy consuming chemicals and naturals are
processed from natural ore bodies.
 Synthetic zeolites have a silica to alumina ratio of 1 to 1 and clinoptotilite (clino) zeolites
have a 5 to 1 ratio.
 Clino natural zeolites do not break down in a mildly acid environment, resistant resistant
silica to hold it’s structure together. The clino natural zeolite is broadly accepted for use
in the agriculutral industry as a soil amendment and as a feed additive.

21. There are two main method for the synthesis of Zeollites:
1. Hydrothermal method
2. Microwave Method
3. Sol-gel method
Hydrothermal Method: Schematic diagram of autoclave

22. Hydrotherm
al MethodAn aluminate solution and a
silicate solution are mixed
together in an alkaline medium to
form a milky gel or in some
instances, clear solutions. Various
cations or anions can be added to
the synthesis mixture. The
structure-directing agent is also
added as a template in the
mixture. Synthesis proceeds at
elevated temperatures (60-200 °C)
where crystals are formed through
the nucleation step.

23. Microwave
Method
Microwave heating has the
advantage of short reaction time,
producing small particles with
narrow size distribution and high
purity. Moreover, microwave heating
has found a number of application in
synthetic chemistry.

24.  A regular, non viscous synthesis mixture of zeolite is placed in
the Teflon Autoclave.
 The autoclave is closed with thermocouple connected.
 An initial heating step up to 1000 W is applied.
 All samples were washed by five repetitions of centrifugation
with relative centrifugal force of 48,500 g for 2 h, then
decanting, and redispersion in ethanol and water with
ultrasonication before analyses preparations were performed.

25. Sol-Gel Process
Sol- Gel
Method

26.  Classification on the bases on the pores structure:
Microporous Zeolites
Mesoporous Zeolites
 Classification on the bases of structural building unit:
Primary Building Unit (PBU)
Secondary Building Unit (SBU)
Sodalite Cage Building Units
 Classification on the bases of ring structure:
Small-pore zeolites, with 8-membered oxygen rings and a “free” diameter of
3 - 4.5 Å
Medium-pore zeolites, with 10-member oxygen ring and a “free” diameter of
4.5 - 6 Å
Large-pore zeolites, with 12-member oxygen rings and a “free” diameter of
6 - 8 Å

27.  Classification on the bases on Si/Al ratio
 Classification on the bases on crystal structure
Geometry (Octahedral, Tetrahedral etc)
S.
No
Name Si/Al ratio Examples
1. Low silica zeolites (Si/Al – 1–1.5) A, X
2. Intermediate silica zeolites (Si/Al – 2–5) (a) Natural zeolites: erionite, chabazite,
clinoptilolite, mordenite (b) Synthetic zeolites: L,
Y, omega, large port mordenite
3. High-silica zeolites (Si/Al=10–4000) (a) By direct synthesis: ZSM-5, ZSM-1I, EU-I,
EU-2, Beta (b) By then no chemical framework
modification: mordenite, erionite, highly silicious
variant of Y
4. All silica “zeolite” Si/Al=1000 to ∝ Silicate

28. Generally, Zeolites are characterized by the help of X-Ray diffraction (XRD), Fourier
Transform-Infrared Spectroscopy (FT-IR), Scanning electronic Microscopy (SEM)
and BET surface area analyses.
XRD:- X-ray powder diffraction (XRD) is a rapid analytical technique primarily used
for phase identification of a crystalline material and can provide information on unit
cell dimensions.
FT-IR:- FTIR Spectroscopy, is an infrared spectroscopy method used to identify
organic, polymeric, and in some cases, inorganic materials.
SEM:- SEM provides detailed high resolution images of the sample by rastering a
focussed electron beam across the surface and detecting secondary or backscattered
electron signal.
BET:- Brunauer–Emmett–Teller (BET) theory aims to explain the
physical adsorption of gas molecules on a solid surface and serves as the basis for an
important analysis technique for the measurement of the specific surface area of
materials.

29. 0 10 20 30 40 50
0
500
1000
1500
2000
2500
3000
Intensity(a.u)
2 Theta (deg.)
Fe-Erionite
Cu-Erionite
Na-Erionite
H-erionite
0 10 20 30 40 50
100
200
300
400
500
600
700
800
900
Intensity(a.u)
2 Theta (deg.)
PPy-Erionite
PANI-Erionite
Powder X-ray diffraction patterns of calcined zeolites
(zeolite Erionite, zeolite BETA, zeolite LTL), their ion exchanged forms (Na-
Erionite, Fe-Erionite, Cu-Erionite, H-Erionite, Na-LTL, Fe-LTL, Cu-LTL, H-
LTL, Na-BETA, Fe-BETA, Cu-BETA, H-BETA) and composites of PANI-
Erionite, PANI-LTL, PANI-BETA, PPy-Erionite, PPy-LTL, PPy-BETA are
shown below.
XRD Spectra of Ion Exchanged Forms of Zeolite Erionite and
Composites of PANI-ERI and Ppy-eri

30. 0 10 20 30 40 50 60 70 80 90
0
100
200
300
400
500
600
700
800
Intensity(a.u)
2 Theta (deg.)
H-LTL
Na-LTL
Cu-LTL
Fe-LTL
0 10 20 30 40 50 60 70 80 90
0
100
200
300
400
500
600
Intensity(a.u)
2 Theta (deg.)
PANI-LTL
PPy-LTL
XRD Spectra of Ion Exchanged Forms of Zeolite LTL and
Composites of PANI-LTL and Ppy-ltl
 In all the cases the degree of crystallinity is very high rather all the
materials are crystalline in nature except composites whose
crystallinity is decreased due to amorphous nature of polyaniline
and polypyrrole.

31. 0 10 20 30 40 50 60 70 80 90
-100
0
100
200
300
400
500
Intensity(a.u)
2 Theta (deg.)
Fe-BETA
Na-BETA
Cu-BETA
H-BETA
0 10 20 30 40 50 60 70 80 90
-50
0
50
100
150
200
250
Intensity(a.u)
2 Theta (deg.)
PANI-BETA
PPy-BETA
XRD Spectra of Ion Exchanged Forms of Zeolite BETA and
Composites of PANI-BETA and Ppy-beta
 It was found from XRD that the structure is stable even after
calcinations at 550 0C for 5 h in a stream of dry air. Of all the
zeolites, zeolite LTL has maximum peak intensity for the major
diffraction peaks. Therefore zeolite LTL can be considerd to have
maximum crystallinity in terms of peak intensity and sharpeness.

32. 500 1000 1500 2000 2500 3000 3500 4000 4500
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Fe-BETA
Na-BETA
Cu-BETA
H-BETA
Transmission(%)
Wave number cm
-1
500 1000 1500 2000 2500 3000 3500 4000
5
10
15
20
25
30
35
40
45
50
PANI-Erionite
PPy-Erionite
Transmission(%)
Wave number cm
-1
Fe-Erionite
Na-Erionite
Cu-Erionite
H-Erionite
FTIR Spectra of Ion Exchanged Forms of Zeolite Erionite and
PANI-ERI and PPy-ERI
 The presence of water molecules attached to zeolite framework is
confirmed by a strong characteristic structure sensitive band due to
water bending vibrations at 1700-1750 cm-1.
 An absorption band at 1500-1600 cm-1 in case of Erionite and
zeolite BETA was attributed to (N-H) deformation of organic
templates TMACl and TMAOH respectively used during their
synthesis.

33. 500 1000 1500 2000 2500 3000 3500 4000
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Fe-BETA
Na-BETA
Cu-BETA
H-BETA
Transmission(%)
Wave number cm
-1
500 1000 1500 2000 2500 3000 3500 4000
10
20
30
40
50
60
70
80
90
100
110
PANI-BETA
PPy-BETA
Transmissioncm
-1
Wave number cm
-1
FTIR Spectra of ion exchanged forms of zeolite BETA and PANI-BETAand PPy-BETA
500 1000 1500 2000 2500 3000 3500 4000
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Fe-LTL
Na-LTL
Cu-LTL
H-LTL
Transmission(%)
Wave number cm
-1
500 1000 1500 2000 2500 3000 3500 4000
0
10
20
30
40
50
60
70
80
90
100
PANI-LTL
PPy-LTL
Transmission(%)
Wave number cm
-1
FTIR Spectra of ion exchanged forms of zeolite LTL and PANI-LTL and PPy-LTL

34. The Surface Morphology
 Surface morphology of calcined zeolites (zeolite Erionite, Zeolite
BETA, zeolite LTL), their H forms and metal ion exchanged forms
and composites were obtained by SEM (JEOL JSM 5800, SEM
EDAX) instrument.
 From SEM images, all the three zeolites appear to have relatively
non uniform surface, slightly uneven pore morphology and
difference in particle size.
 Zeolite BETA particles appear to be flakes and sometimes as
spheres having particle size of 50µm.
 Zeolite LTL particles appear to be twigs having particle size of
5µm.
 Zeolite Erionite appear to have rod shaped structure with excellent
crystal edges and having particle size of 2µm.

35. PANI-ERI composite
Zeolite erionite
Zeolite LTL
PANI-LTL composite
SEM Images of Zeolites and Their Composites

36. Zeolite BETA PANI/BETA composite
SEM Images of Zeolites and Their Composites

37. Eleme
nt
Weigh
t %
Atomi
c %
C K 55.56 64.21
NK 12.32 12.21
OK 21.39 18.56
NaK 0.20 0.12
AlK 0.30 0.15
SiK 7.21 3.56
ClK 3.02 1.18
PANI-Erionite
composite
Element Weight
%
Atomic
%
CK 7.21 11.09
NK 12.13 16.00
HK 38.70 44.67
NaK 2.41 1.93
AlK 13.48 9.23
SiK 25.69 16.90
KK 0.37 0.17
PANI-
LTL
composite
Element Weight
%
Atomic
%
OK 46.24 65.38
AlK 1.76 1.48
SiK 29.35 23.63
CL 13.29 3.43
NK 3.94 2.78
HK 3.02 1.93
KK 0.94 0.55
NaK 1.46 0.82
PANI-BETA
composite
EDX spectra of zeolite-polymer composites

38. Thermo gravimetric analysis (TGA) samples were first
dried at a temperature of 450 0C to remove moisture and
impurities.
 TGA was performed by heating the sample from 200 0C to
800 0C. TGA spectra of all the three zeolites (zeolite
Erionite, BETA and LTL) were carried out.
 TGA of the zeolites was carried out and it shows two steps
in weight loss.
 The first weight loss around 150 0C can be assigned to the
bound water or oxidant.
 The second weight loss around 250 0C can be assigned to
the decomposition of the structure of template.

39. Thermo gravimetric analysis (TGA)
TGA Spectra of Zeolite Na-BETA TGA Spectra of Zeolite Na-erionite
TGA Spectra of Zeolite Na-erionite

40. BET surface area analysis (BET)
6 8 10 12 14 16 18
0.000
0.005
0.010
0.015
0.020
0.025
dv/dw(cm
3
g-A
0
)
Pore width (A
0
)
Na-erionite
BET Surface Area and Pore Width of Erionite
 Brunauer–Emmett–Teller (BET) theory explains the
phenomenon of physical adsorption of a gas molecule on the
surface of a solid and is used as a basis for the measurement
of specific surface area of a material.
0.0 0.2 0.4 0.6 0.8 1.0
85
90
95
100
105
110
115
120
125
130
135
140
145
150
155
QuantityAdsorbed(cm³/gSTP)
Relative ptessure (P/Po)
H-Erionite
Na-Erionite
Cu-Erionite
Fe-Erionite

41. 6 8 10 12 14 16 18
0.0020
0.0025
0.0030
0.0035
0.0040
0.0045
0.0050
0.0055
0.0060
dv/dw(cm
3
-g-A
O
)
Pore width (A
O
)
Na-BETA
0.0 0.2 0.4 0.6 0.8 1.0
0
50
100
150
200
250
300
350
400
H-BETA
Na-BETA
Cu-BETA
Fe-BETA
QuantityAdsorbed(cm³/gSTP)
Relative Pressure (P/Po)
BET Surface Area and Pore Width of BETA
The peaks for pore width are observed between 0.4 – 1.0 nm.
According to the definition by IUPAC, the adsorbent pores are
classified into three groups: micropore (diameter ˂ 2 nm), mesopore
(2-50 nm) and macropore (˃ 50 nm) indicating that the zeolites
prepared in this method contain only micropores.

42. 6 8 10 12 14 16 18
0.00030
0.00035
0.00040
0.00045
0.00050
0.00055
0.00060
dv/dw(cm
3
-g-A
0
)
Pore width (A
0
)
Na-LTL
0.0 0.2 0.4 0.6 0.8 1.0
0
50
100
150
200
250
300
350
QuantityAdsorbed(cm³/gSTP)
Relative Pressure (P/Po)
H-LTL
Na-LTL
Cu-LTL
Fe-LTL
BET surface area and pore width of LTL

43. Application of zeolites are in catalysis, ion exchange and adsorption.
Catalysis:-
 Zeolites are extremely useful as catalysts for several important reactions involving
organic molecules.
 The most important are cracking, isomerization and hydrocarbon synthesis.
Ion exchange:-
 Hydrated cations within the zeolite pores are bound loosely to the zeolite framework,
and can readily exchange with other cations when in aqueous media.
 Applications of this can be seen in water softening devices, and the use of zeolites in
detergents and soaps.
Adsorption:-
 Zeolites are used to adsorb a variety of materials. This include applications in drying,
purification, and separation.
 They can remove water to very low partial pressures and are very effective desiccants,
with a capacity of up to more than 25% of their weight in water.

44. Zeolites application in field of
water purification, waste
management, horticulture,
catalysis process, anti-oxidant,
agriculture etc.
Using zeolites waste management
can control by catalysis, ion-
exchange and adsorption process.
Waste materials are as radioactive,
toxic gas/ chemicals, Pesticide/
herbicide management

45.  Novel nanoporous zeolite materials used for the treatment of waste including
radioactive, toxic gas/ chemicals separation, Pesticide/herbicide management, sewage
treatment etc.
 Zeolite acts as auxiliary as well as functional support in gas sensing.
 The modification of zeolite structure increases its sorption capacity, sensitivity and
recyclability.
 The parent sodium form was also modified to proton form to increase their catalytic
activity and further applying for organic drug synthesis.
 Natural microporous zeolites first gained widespread attention in radioactive waste
applications after the pioneering research of Ames in the late 1950's.
 Zeolite-rich rocks can retard, via simple cation exchange, the migration of radionuclides
occurring in solution as simple cations (e.g. Cs+, Sr2+, and Ba2+).

46.  Advances in nanoscale science and engineering suggest that many of the
current problems involving water quality could be resolved or greatly
improved using nanoporous materials.
 Currently, the most widely used method for the removal and separation of
toxic metal ions/organic compounds is the solid phase extraction
technique.
 Nanoporous materials have unique properties like large specific surface
area, high adsorption capacity and low temperature modification, so they
are promising solid-phase extractants and have contaminant scavenging
mechanisms.
Solid Phase Extraction
Technique For Waste
Management

47. • So, our research is concerned with synthesis, characterization and
application of nanoporous materials (zeolites) for preconcentration,
separation and determination of metal ions from industrial waste water.
• Heavy metal ion contamination such as cadmium, zinc, lead, copper, iron,
nickel and cobalt represents a significant threat to the ecosystem.
• Adsorption is one of the widely used processes for toxic metal removal
from contaminated water, since it is a simple and economically feasible
method.
• In this context zeolites are finding tremendous applications for adsorption
of metal ions.

49.  High cation-exchange
capacities (~2 meq/g),
clinoptilolite and mordenite
have high selectivities for Cs,
Ba, and Sr.
 The high selectivities of
clinoptilolite and mordenite
zeolites can sorb Cs, Ba, and Sr
from solutions, even when
these cations are present in
small amounts together with
large amounts of other
competing cationic species.
 High cation-exchange
capacities and their selectivity
for Cs and Sr are key in their
use in radioactive waste
applications.
Radioactive Wastes

50. • The natural resources for power production are getting exhausted
day by day. The consumption of resources for power production is
so large that by next decade one will have to depend wholly on
radionuclides. However these radionuclides are hazardous to
living system. So remediation of these radioisotopes is necessary.
• Radiation Hazard can be defined as the release of radioactive
substances or high-energy particles into air, water, or earth as a
result of human activity, either by accident or by design.

51. The sources of radioactive isotopes include:
 Nuclear weapon testing or detonation.
 The nuclear fuel cycle, including mining, separation and
production of nuclear materials for use in nuclear power plants
or nuclear bombs.
 Accidental release of radioactive material from nuclear power
plants.
Sources

52. • Since, even a small amount of radiation exposure can have serious
(cumulative) biological consequences; the radioactive wastes remain
toxic for centuries.
• Radiation Hazard is a serious environmental concern even though
natural sources of radioactivity far exceed artificial ones at present. The
problem of Radiation Hazard is compounded by the difficulty in
assessing its effects.
• Radioactive waste may spread over a broad area quite rapidly and
irregularly (from an abandoned dump into an aquifer) and may show its
effect upon humans and organisms for decades in the form of cancer or
other chronic diseases.

53. A closed loop of Indian Nuclear Fuel Cycle

54. • Half-lives of the order of years to decades of isotopes of
elements that can seek tissues or organs biologically (being akin
to other elements chemically) are the most hazardous from point
of view of radiation.
• For example, 90Sr, being chemically akin to Ca, can seek the
bone and lodge itself there for years causing radioactive damage
to surrounding tissues.

55. • The nuclear reactions that are fission of nuclei like 235U, 239Pu and
fusion of elements like hydrogen result in release of enormous
energy and radioactive elements.
• The nuclear fuel cycle in India begins with the mining of uranium
and the processing of mined uranium into U3O8.
• The resulting spent fuel is then reprocessed to recover uranium
and plutonium.
• At each and every step of nuclear fuel cycle the different types of
nuclear waste are generated. These wastes may be classified into
different categories on the basis of their actual level as given
below:
• Potentially active waste (PAW)
• Low level waste (LLW)
• Intermediate level waste (ILW)
• High level waste (HLW
Radioactive waste

56. Different levels of Radioactive waste

57. Total nuclear waste generation in India

58. • The high level waste (HLW) generated from the reprocessing of
spent nuclear fuel contains long lived radionuclides such as, 90Sr
(29 y), 129I (1.57 x 107 y), 137Cs (30 y), 135Cs (2 x 106 y), 99Tc (2.1
x 105 y) as well as minor actinides.
• This HLW is proposed to be buried in the deep geological
repository after vitrification in a suitable matrix, e.g., borosilicate
glass, synroc, etc. However, with time these radionuclides may
leach out from the waste and may be released into the natural
environment thereby contaminating it. There is strong indication
that contaminants can be transported via soil contents like
colloids.
• Most experimental evidence for colloid-facilitated transport of
contaminants has been obtained from saturated porous media,
either saturated laboratory column studies or groundwater studies.
Migration of radionuclide in the Environment

59.  The different processes that may control amounts and forms of
radionuclide's present in the environment and influence their
migration behavior are:
• Precipitation: It occurs when there is sufficient concentration of
the metal ions in solution to exceed the solubility product for the
solid phase formation, which causes retarding effect on release and
on migration rate.
• Adsorption: The metal ions may get sorbed onto colloidal
particles, coming from weathering of host rocks, present in
aqueous phase. The interaction of these elements in the aqueous
solution with solid surfaces is generally described in terms of
physical sorption, chemical sorption and electrostatic sorption.
This may decrease the migration.

60. • Complexation: The metal ions have tendency of complexation with
different inorganic and organic ligands present in aqueous phase. The
predominant inorganic ligands are hydroxide, carbonate, sulphate,
phosphate, chloride, fluoride and nitrate, whereas the organic ones are
low molecular weight oxalate, citrate etc. and high molecular weight
humate and fulvate. Complexation increases the amount of metal ions in
solution and hence, having tendency to increase the migration rate.
• In nuclear waste repositories, carrier colloids will be produced by
degradation of engineered barrier materials and waste components: iron
based waste package materials can produce iron oxyhydroxide colloids,
degradation of bentonite backfills can produce clay colloids and
alteration of HLW glass can produce a variety of silicate particulates. The
most common colloidal materials in the ground water are hydrous oxide
of iron, aluminium and silica as well as organic macromolecules such as
humic acid. Inorganic colloids in ground water have shown strong
adsorption of the metal ions.

61. Engineered barrier system for radioactive waste repository

62. • In order to minimize the leakage of radioactive isotopes from
geological repositories, their migration in the environment, hence
the harmful effects of radiation, there is a need to search for
suitable backfill materials. The backfill materials will act as
barrier between the repositories and the rest of the environment.
• To achieve this goal we are working with the synthesis of such
backfill materials and sorbents which may prove to be very
effective to act as barrier and thus can save the environment from
such harmful radiations.
Remedy for
Radioactive waste

63. • Zeolites are the important clay materials present everywhere in
underground water having strong tendency of sorption of
radionuclide's as well as toxic metal ions.
• They have negligible desorption property of metal ions in water
which indicate that may be used as the backfill materials in the
repository process.
• Zeolites may be of different types and different size on the basis
of their synthesis such as micro porous, mesoporous &
nanoporous which in turn affects the sorption behavior of the
metal ions. The sorption tendency may be optimized by studying
the sorption capacity of the materials in different conditions,
hence, may be more beneficial to reduce the migration of
radionuclide's in the environment.

64.  Petroleum refinery process in which heavy oil is passed through metal
chambers (called catalytic crackers or cat crackers) under pressure and
high temperature in the presence of catalysts such as alumina, silica, or
zeolites. This boiling breaks up heavy, large, and more complex long-
chain oil molecules into lighter, smaller, and simpler short-chain
molecules such as those of gasoline.
 Catalytic cracking cracks low value high molecular weight hydrocarbons
to more value added products (low molecular weight) like gasoline, LPG
Diesel along with very important petrochemical feedstock like propylene,
C4 gases like isobutylene, Isobutane, butane and butane. Main reactions
involved in catalytic cracking are-
 Isomerisation
 Dehydrogenenation
 Hydrogen transfer
 Cyclization
 Condensation
 Alkylation and dealkylation

65.  Hydrocracking is one of the most versatile processes for the conversion of low
quality feed stocks into high quality products like gasoline, naphtha, kerosene, diesel,
and hydro wax which can be used as petrochemical feed stock. Its importance is growing
more as a refiners search for low investment option for producing clean fuel.
 Hydrocracking processes uses a wide variety of feed stocks like naphtha,
atmospheric gas oil, vacuum gas oils, coke oils, catalytically cracked light and heavy
cycle oil, cracked residue, deasphalted oils and produces high quality product with
excellent product quality with low sulphur contents.

66. Adsorption (molecular sieve)
 Adsorption in zeolites is significantly different from adsorption in e.g. silica
gel or active coal, which have a broad size distribution of pore sizes, and
where the size of the pores are in the range of 10 nm.
 In zeolites the porosity is determined by the crystalline structure, i.e. the
pores are arranged in a regular fashion with only one (or a few) discrete pore
sizes. Also the pores have molecular dimensions.
 The implication of this is the use of zeolites as adsorbents and molecular
sieves.
 Mainly used for water adsorption (very low equilibrium water vapour
pressure) Gas (hydrogen?) storage materials Molecular sieving effect due to
size limitation imposed by framework structure and cation size and position.
Also weaker interactions: N2-O2 separation.

67. Sorption- Zeolite For
Pesticide Control

68. • It has been found that the Surfactant - admicellar sorbent gave great pesticide
sorption; thus, higher concentration of surfactant has been used to modify zeolite.
• Surfactant-modified zeolite could adsorb all of the target pesticides while
unmodified zeolite adsorb only two pesticides because of hydrophilic surface.
• All the studied pesticides are slightly polar compounds which disfavor to interact
with polar surface of zeolite by electrostatic forces.
• While slightly polar compounds adsorbed on the admicellar sorbent via partition
into hydrocarbon phase of the micelles. The effective retention of pesticides on the
Surfactant-modified zeolite was acquired by hydrophobic interaction and π-cation
interaction between the aromatic rings in analytes and the quaternary ammonium
group in Surfactant (i.e. CTAB).
Efficacy of Zeolite for Sorption of Pesticide

69. • The high surface area and reusability of zeolite were utilized sufficiently
for the sorption of pesticide and slow release minerals.
• The created sorbent established high sorption capacity resulted from high
surface area of material.
• In addition, the developed system offers cost effectiveness due to the
reuse of sorbent material.
• Other advantages of the developed approach were high enrichment factor,
time-saving, and use small volume of the eluent which amount of organic
waste was reduced as well.

70. Decontamination of
Chemical Warfare Agents
• Chemical warfare agents are lethal/toxic compounds basically used to kill,
injure or harm people as well as other living organisms.
• They are also hazardous to the environment (i.e. contaminate air, water and
land). Therefore, there is increasing interest in the effective detection as
well as degradation of these compounds.
• Nerve agents (organophosphates) have highest toxicity than other CWAs.
Nerve agents are basically of two types: G agents (Fluorine or Cyanide
containing OPs) and V agents (sulfur containing OPs).

71. Showing detail CWAs Description and their toxic effects

72. Decontamination Methods
against CWAs• There are three fundamental methods of decontamination of
chemical warfare agents-
Mechanical decontamination,
physical decontamination and
chemical decontamination
Decontamination methods and their types

73.  The chemical reactions applied as chemical decontamination procedures
are:
Nucleophilic and elimination reactions
Electrophilic reactions (oxidations)
Thermal destruction
Photochemical and radiochemical reactions
 Different CWAs are degraded by different chemical processes
 HD gas is degraded by dehydrohalogenation, aerobic oxidation by the help
of catalyst, oxidation by using hydrogen peroxide, photo oxidation (TiO2
have this property).
 G agents are degraded by two methods: Enzymatic hydrolysis and Non-
enzymatic hydrolysis. Enzymatic hydrolysis involve organophosphorous
hydrolase enzyme (Microbial degradation). Hydrolysis catalyst yield large
amount of acidic products therefore buffer is required to maintain the pH of
the reaction in neutral to slightly alkaline range. Non- Enzymatic
hydrolysis involves chemical compounds (i.e. iodosylcarboxylates) that
promote catalytic hydrolysis in which nucleophilic substitution and
hydrolysis reaction takes place.

74. Chemical reactivity of nanoparticles with CWA
simulants
 For each sample, add 5 μL of CWA simulants and 20 mL of n-hexane into 100 mL
Erlenmeyer flask. Consider to the volume and density of CWA simulants, the
weights of particles needed for establishing the different weight ratios of CWA
simulants: Nanoparticle (1:1, 1:2, 1:4, 1:16 and 1:32) and add to the above
solutions.
 To do a complete reaction between particles and CWA simulants, all samples should
be attached to a shaker and shake for a definite period.
 After that, the presence of the CWA simulants in the samples is to be investigated
by the UV/VIS spectrometer/GC-MS.CWA simulants like various Nerve agents,
Blister agents and Pulmonary/ Chocking agents will be taken for the study.

75.  The counter-cations in zeolites are mobile, and may easily be exchanged.
 This results in ion exchange capability utilized e.g. in detergents and in
waste water purification
Thermal Ion Exchange (TIE)

77. • As a result of different zeolites (zeolite-β, MCM-41, MOR, Y, ZSM-5, HSZ-
360, SAPO-34, HSOD, MCM-22 etc.) diverse pharmaceutically important
derivatives which are well known drug intermediates has been reported i.e.
tetrahydropyran, quinoxaline, quinoline, quinazolines, coumarins, isopylindole,
pyridines, Nopol, Napthalene, Toluidine, carbazone, oxadiazoles, triazole,
benzodiazepine, oxazole, porphyrins, calyx-pyrolls, spiro-ketals, anilide, pyrroles
(lamellarin R, Tubulin Polymerization inhibitor), xylidine, pyrazine, piperazine,
terpinol, terpinyl acetate, imidazole, styrene, limonine, furfural, xylene, β-pinene,
epinephrine, paracetamol, α-pinene, anisole, acridinediol, chromene,
dihyropyridine, chalcones etc.
• Different derivatives obtained were synthesized with the help of these
reactions i.e. Friedel craft acylation, Friedlander condensation, Knorr-Paal
condensation, Biginelli condensation reaction, Propargylation and
cycloisomerisation reaction, Pechmann reaction, Mukaiyama type aldolization,
Prins condensation reaction, Carbonyl-Ene reaction, Hantzsch condensation,
oxidation reactions, Arylation, Acetoxylation, Nitration, Formylation,
methylation, esterification, Vapour phase condensation reaction, Claisen-Schmidt
condensation reaction, Fischer’s method, Ring shift isomerization, cyclization
reaction etc.

79. Zeolites
Zeolite
BETA
Zeolite
Erionite
Zeolite
LTL
Polymers
Polyaniline Polypyrrole
Target gases used NO2, CO and SO2

80.  Composites were prepared by dry mixing polymer powder with
the zeolites with weight ratios equal to 10, 20, 30, 40 and 50 %
(w/w).
 The dry mixed composites were subsequently pressed into pellets
with a diameter of 12 mm and a nominal thickness of 2 mm,
using a hydraulic press machine at a pressure of ~280 Mpa

81.  Hence, adding zeolite to polymer provides adsorption sites for the
gas molecules to interact with polymer chains
 Therefore sensitivity increases. NO2 behaves like an electrophile;
therefore it is expected to with draw electrons from PANI.
Concentration (ppm)
2.5 25 48 100
Sensitivity(%)
0
20
40
60
80
100
PANI
PANI-Cu-LTL
PANI-H-LTL
PANI-Fe-LTL
PANI-Na-LTL
PANI/LTL VS NO2

82. Concentration (ppm)
2.5 25 48 100
Sensitivity(%)
0
10
20
30
40
50
60
70
80
PANI
PANI-H-ERI
PANI-Cu-ERI
PANI-Fe-ERI
PANI-Na-ERI
Concentration (ppm)
2.5 25 48 100
Sensitivity(%)
0
10
20
30
40
50
60
70
80
PANI
PANI/H-BETA
PANI/Cu-BETA
PANI/Na-BETA
PANI/Fe-BETA
PANI/ERI VS NO2 PANI/BETA VS NO2
Concentration (ppm)
5 50 100 500 1000
Sensitivity(%)
-20
0
20
40
60
80
PANI
PANI-H-ERI
PANI-Cu-ERI
PANI-Fe-ERI
PANI-Na-ERI
PANI/ERI VS CO
Concentration (ppm)
5 50 100 500 1000
Sensitivity(%)
0
20
40
60
80
PANI
PANI-H-BETA
PANI-Cu-BETA
PANI-Na-BETA
PANI-Fe-BETA
PANI/BETA VS CO

83. Concentration (ppm)
5 50 100 500 1000
Sensitivity(%)
0
20
40
60
80
100
PANI
PANI-H-LTL
PANI-Cu-LTL
PAI-Fe-LTL
PANI-Na-LTL
PANI/LTL VS CO The sensitivity of PANI
towards CO increases from
2.11 to 45.00 % as the CO
concentration was increased
from 5 ppm to 1000 ppm.
When the concentration is
increased, more and more
CO molecules come in
contact with polymer chains
and the sensitivity increases.
The sensitivity of PANI towards CO increases when zeolite is
added to it. Since zeolite is having a porous structure, the gas
molecules are provided with high surface area to get adsorbed and
interact with polymer chains.

84. Concentration (ppm)
5 50 100 500 1000
Sensitivity(%)
-20
0
20
40
60
80
PANI
PANI-H-ERI
PANI-Cu-ERI
PANI-Fe-ERI
PANI-Na-ERI
PANI/ERI VS SO2
Concentration (ppm)
5 50 100 500 1000
Sensitivity(%)
-20
0
20
40
60
80
100
PANI
PANI-H-BETA
PANI-Cu-BETA
PANI-Na-BETA
PANI-Fe-BETA
PANI/BETA VS SO2
Concentration (ppm)
5 50 100 500 1000
Sensitivity(%)
-20
0
20
40
60
80
100
120
PANI
PANI-H-LTL
PANI-Cu-LTL
PANI-Fe-LTL
PANI-Na-LTL
PANI/LTL VS SO2

85. Concentration (ppm)
2.5 25 48 100
Sensitivity(%)
0
10
20
30
40
50
60
70
PPy
PPy-H-ERI
PPy-Cu-ERI
PPy-Fe-ERI
PPy-Na-ERI
Sensitivity of PPy and PPy/zeolite
Erionite (Si/Al= 9)
composites towards NO2
Concentration (ppm)
2.5 25 48 100
Sensitivity(%)
0
10
20
30
40
50
60
70
PPy
PPy-H-BETA
PPy-CU-BETA
PPy-Na-BETA
PPy-Fe-BETA
Sensitivity of PPy and
PPy/zeolite BETA (Si/Al= 13)
composites towards NO2
Sensitivity of Polypyrrole/Zeolite Nanocomposites
Towards NO2
Concentration (ppm)
2.5 25 48 100
Sensitiity(%)
0
10
20
30
40
50
60
70
80
PPy
PPy-H-LTL
PPy-Cu-LTL
PPy-Fe-LTL
PPy-Na-LTL
Sensitivity of PPy and
PPy/zeolite LTL (Si/Al= 3.1)
composites towards NO2

86. Concentration (ppm)
5 50 100 500 1000
Sensitivity(%)
0
10
20
30
40
50
60
70
PPy
PPy-H-ERI
PPy-Cu-ERI
PPy-Fe-ERI
PPy-Na-ERI
Concentration (ppm)
5 50 100 500 1000
Sensitivity(%)
0
20
40
60
80
PPy
PPy-H-BETA
PPy-Cu-BETA
PPy-Na-BETA
PPy-Fe-BETA
Sensitivity of PPy and PPy/zeolite erionite (Si/Al= 9)
composites towards CO
Sensitivity of PPy and PPy/zeolite BETA (Si/Al= 13)
composites towards CO
Sensitivity of Polypyrrole/Zeolite
Nanocomposites Towards CO

87. Sensitivity of Polypyrrole/Zeolite Nanocomposites Towards SO2
Concentration (ppm)
5 50 100 500 1000
Sensitivity(%)
-10
0
10
20
30
40
50
60
70
PPy
PPy-H-ERI
PPy-Cu-ERI
PPy-Fe-ERI
PPy-Na-ERI
Sensitivity of PPy and PPy/zeolite
erionite (Si/Al= 9) composites towards
SO2
Sensitivity of PPy and PPy/zeolite BETA (Si/Al=
13) composites towards SO2
Concentration (ppm)
5 50 100 500 1000
Sensitivity(%) 0
10
20
30
40
50
60
70
PPy
PPy-H-BETA
PPy-Cu-BETA
PPy-Fe-BETA
PPy-Na-BETA

88.  This concept was coined in 1991 by Professor Paul T. Anastas
(Yale,U.S.), an organic chemist. Therefore, he is also known as Father of
Green Chemistry. To achieve goals of Green Chemistry, Prof. P. T.
Anastas and J. C. Warner proposed set of twelve principles.
 Green Chemistry can be defined as a practice of synthesizing materials in
such a way so that they should be safe, non polluting, sustainable and also
consuming lesser amount of material and energy during processing.

90. Conclusion
• The foremost merits of using Zeolite for various applications are
significant and novel due to its competency, environment friendly,
recyclable as well as thermally stable properties.
• Water and wastewater treatment, Radioactive Hazards, Pesticide
control, Pharmaceutical drug synthesis, Toxic Gas Sensing, CWA
decontamination are the important problems worldwide and there is
a wide interest in implementing Zeolites, so zeolites being a good
choice to solve various problems taken for research studies. Thus,
there is a growing trend for utilization of zeolites for the
environmental applications resulting in the reduction of pollution
and water contamination.