CHAPTER -1

INTRODUCTION
1.1 CATALYST:
Automotive catalyst technology to meet ultra-low emission vehicle (ULEV)
emission levels for conventional gasoline fueled vehicles requires major
improvements in catalytic activity and reactor engineering. A major challenge is in
reducing vehicle cold-start emissions. ULEV emission levels can be exceeded in
the first minute of the Federal Test Procedure (FTP) cold-start if the catalyst does
not achieve its light-off temperature. To achieve these cold-start emission
reductions, several approaches are actively being evaluated including electrically
heated catalysts 1-3, fuel burners 4, 5 and hydrocarbon adsorbers 6. Some of these
techniques have demonstrated the ability to substantially reduce cold-start
emissions; however, they also add substantial complexity and cost to the emission
control system. Additional work has concentrated on the development of advanced
catalyst technology based on high loading of palladium 7, 8. These palladium
catalysts have demonstrated improved warmed-up hydrocarbon activity and lower
light off temperatures compared to conventional platinum/rhodium catalysts. It
must be recognized; however, that automotive catalyst light-off during vehicle
cold-start is a dynamic process dependent not only on catalyst activity but the
transfer of exhaust gas heat to the catalyst surface and the thermal mass of the
catalyst/substrate combination. A major limitation of conventional ceramic or
metal monolithic automotive catalyst technology is the large thermal mass
associated with the catalyst substrate 9. This result in a major delay in cold-start
catalyst light-off times due to the large amount of exhaust energy required to heat
the

catalyst

to

reaction

temperatures.

The

development

of

alternate

catalyst/substrate technology with reduced thermal mass, high heat transfer rates

and high catalyst activity could result in significant advancements in achieving

emission levels at and below the ULEV standard.
The reduction of Automobile pollution using catalytic converter in the latest
vehicle speaks in high volume towards its successes. The uses of catalytic
converter are becoming compulsory for all the heavy vehicles in order to prevent
global warming. The modeling of catalytic converter as well as its simulation of
surface reaction is very important to determine the conversion rate or the amount
of pollutants reduction in the core of catalytic converter of the flue gasses from the
engines. The catalytic converter model is simulating for the implementation of new
catalytic converter technology. For this aspect, the role of exhaust gas after
treatment method for the catalytic converter components is playing a very vital
across the world.

FIG 1.1: CATALYTIC CONVERTER

1.2 MAIN POLLUTANTS IN THE EXHAUST OF

GASOLINE ENGINES

Ideally, the emissions of an internal combustion engine only consist of

carbon dioxide (CO2), water (H2O), and nitrogen (N2), when it is operated at
stoichiometry. Under lean operation, i. e., with excess air, additional oxygen (O2)
is emitted. Under rich operation, i. e., with excess fuel, mainly additional carbon
monoxide (CO) and hydrogen (H2) arise. In reality, the combustion is never
complete, since the air-to-fuel mixture is not entirely homogenous. Thus, the
gasoline is not entirely burned, resulting in carbon monoxide (CO), hydrogen (H2),
and hydrocarbon (HC)2 emissions. The correct chemical expression for unburned
hydrocarbons is CxHy. For simplicity, the term HC will be applied throughout the
thesis. Notice that here, only the compounds containing hydrogen and carbon are
considered. In reality, other carbon-containing compounds are emitted, as well.
However, they are not considered in this thesis. The term HC refers both to the
singular and plural form.

Since the combustion in the cylinder occurs at high temperatures, oxides of

nitrogen (NO, NO2 and very little N2O) are generated, as well. Their formation is
highly dependent on the operating condition of the engine. In the following, they
will be collected in the term NOx. All the emissions mentioned occur
simultaneously, at any operable air-to-fuel ratio.

1.2.1 CARBON MONOXIDE (CO) AND HYDROCARBONS (HC)

Carbon monoxide is an odourless and colourless gas. Since it exhibits a
higher affinity to haemoglobin than oxygen, it is very toxic. It blocks the supply of
oxygen to the body tissue, thus leading to suffocation. A concentration of a few
thousand ppm is already fatal. Carbon monoxide is generated when the combustion
occurs under oxygen-deficient conditions. Thus, CO is mainly generated when rich
air-to-fuel mixtures are burned. However, even under lean conditions, CO occurs
because of incomplete combustion. The group of unburned hydrocarbons (HC)
contains many compounds consisting of carbon and hydrogen. Themost important
groups are alkanes, alkenes, alkynes, and aromatics. Molecules which only contain
single hydrogen-carbon bonds, i. e., the alkanes, are called saturated. Alkenes
and alkynes are unsaturated. Hydrocarbons consist mainly of partially oxidised
fuel molecules.
However, few molecules arise from unburned fuel, such as benzene (C6H6).
In addition to the hydrocarbons, oxygenates occur also, i. e., organic compounds
containing oxygen, such as formaldehyde (HCHO). Usually their fraction is low as
compared to the HC concentration. Like CO, HC occur under rich operating
conditions, i. e., when excess fuel is present. Additionally, they occur when the
combustion is locally disturbed or hindered. This can for example be caused by the
cylinder geometry, by quenching of the flame or by absorption of fuel in the oil.
Alkenes and alkynes are slightly sweet smelling, whereas alkanes are odourless.
Many HC cause coughing, drowsiness or even have a narcotic effect. Benzene is
toxic and carcinogenic. It is believed that internal combustion engines in cars are
the cause of about 80% of the benzene in the atmosphere. Apart from the direct
impact on the human health, some HC such as alkenes react with NOx in the
4

atmosphere to form secondary pollutants such as tropospheric ozone and

photochemical smog. Ozone in turn has again a significant impact on the human
health, affecting the respiratory tract.

1.2.2 HYDROGEN (H2)

Hydrogen is not a real pollutant. It is not toxic and has no significantly
malign effect on the atmosphere. Therefore, it is not regulated by legislation. Its
very high agility as compared to other species and its considerable chemical
activity are the causes of these sensor signal distortions.

1.2.3 NITROGEN OXIDES (NOX)

Nitrogen Oxides mainly occur in the form of nitric oxide (NO) and nitrogen
dioxide (NO2). Nitrous oxide (N2O) only occurs in small amounts in the raw
emissions of an internal combustion engine. However, the concentration may
increase in a three-way catalytic converter under certain circumstances. Nitrogen
dioxide is reddish-brown with a pungent smell and toxic, damaging the lung tissue.
Already small concentrations of around 1 ppm are harmful. Nitric oxide is
odourless and colourless and relatively harmless, as compared to NO2. Both NO
and NO2 play an important role in the formation of acid rain, photochemical smog
and the depletion of the ozone layer. Nitrous oxide is an important greenhouse gas.
Usually, the fraction of NO in the NOx emissions of a gasoline engine is well
above 98%. Therefore, only NO will be considered, the other nitrogen oxides will
be neglected in this thesis.

1.3 CATALYTIC CONVERTER:

Catalytic converters, fitted in series with the exhaust pipe of gasoline fueled
vehicles, convert over 90 percent of hydrocarbons (HC), carbon monoxide (CO)
and nitrogen oxides (NOx) from the engine into less harmful carbon dioxide
(CO2), nitrogen and water vapour. Since catalytic converters were first fitted to
cars in 1974, more than 12 billion tons of harmful exhaust gases have been
prevented from entering the earths atmosphere. More than 96 percent of cars
manufactured today are equipped with catalysts.

A catalytic converter

(colloquially, "cat" or "catcon") is a device used to reduce the toxicity of emissions

from an internal combustion engine. Catalytic converters are also used on
generator sets, forklifts, mining equipment, trucks, buses, trains, and other engineequipped machines. A catalytic converter provides an environment for a chemical
reaction wherein toxic combustion by-products are converted to less-toxic
substances.

1.4 ZEOLITE (ZSM-5):

ZSM-5, Zeolite Socony Mobil5, (framework type MFI from ZSM-5 (five))
is an aluminosilicate zeolite

belonging to the pentasil family of zeolites.

Its chemical formula is NanAlnSi96nO19216H2O (0<n<27). Patented by Mobil Oil

Company in 1975, it is widely used in the petroleum industry as a heterogeneous
catalyst for hydrocarbon isomerization reactions.

FIG 1.2 : A typical zeolite structure

1.4.1 POTENTIAL APPLICATIONS:

GENERAL APPLICATIONS:
Zeolites have a wide range of commercial uses (InterSun 2007), including:

AQUACULTURE:
Ammonia filtration in fish hatcheries
Biofilter media

AGRICULTURE:
Odor control
Confined animal environmental control
Livestock feed additives

HORTICULTURE:
Nurseries, greenhouses
Floriculture
Vegetables/herbs
Foliage
Tree and shrub transplanting
Turf grass soil amendment
Reclamation, revegetation, and landscaping
Silviculture (forestry, tree plantations)
Medium for hydroponic growing

HOUSEHOLD PRODUCTS:
Household odor control
Pet odor control

INDUSTRIAL PRODUCTS:
Absorbents for oil and spills
Gas separations

ENVIRONMENTAL APPLICATIONS:
Although environmental applications of zeolites are small compared with
applications of their catalytic properties, considerable research and some
implementations have taken place including:

RADIOACTIVE WASTE:
Site remediation/decontamination
8

WATER TREATMENT:
Water filtration
Heavy metal removal
Swimming pools

WASTEWATER TREATMENT:
Ammonia removal in municipal sludge/wastewater
Heavy metal removal
Septic leach fields

SYNTHESIS:
ZSM-5 is a synthetic zeolite, closely related to ZSM-11. There are many
ways to synthesize ZSM-5, a common method is as follows:
SiO2 + NaAlO2 +NaOH +N(CH2CH2CH3)4Br +H2O ZSM-5 + analcime
+ alpha-quartz
ZSM-5 is typically prepared at high temperature and high pressure in
a Teflon-coated autoclave and can be prepared using varying ratios of SiO2 and Al
containing compounds.

ZSM-5 SPECIAL PROPERTIES

Zeolite ZSM-5 is a special type of zeolite. It is a "high-silica"- zeolite, which
gives it most of its special properties. Zeolite ZSM-5 is moderately hydrophilic to
highly hydrophobic (depending on the Si/Al ratio), whereas zeolites like the types
A, X and Y are very hydrophilic. The number and type of cations compensating
the lattice charge are an important factor as to this property. Zeolite ZSM-5 has a
9

very high temperature (>1000C) and acid stability (down to pH=3). The last
property makes it possible to obtain the hydrogen form directly by exchanging the
zeolite in a dilute hydrochloric acid solution without large Al-losses. To convert
the "low-silica"-zeolites to the hydrogen form they have to be exchanged with an
ammonium salt solution and then calcined to decompose the ammonium ions.

The ZSM-5 structure allows the introduction of alternative T-atoms (B, Ga,
Fe etc.) during synthesis. The structural properties of the zeolite remain
unchanged, just the unit cell dimensions change slightly. Passage of higher
substituted aromatics (when formed at an intersection) is even more limited, so
these will probably be converted before leaving the zeollte. Therefore, alkylatipn
of toluene with methanol and disproportionate of toluene will yield a xylenes
mixture with a higher p-xylene content than the thermodynamic equilibrium. The
catalytic dewaxing of heavy oil fractions is a (hydro-) cracking process in which
only the linear ("waxy") hydrocarbons are involved. Branched hydrocarbons are
too large to enter the zeolite's pores. The products of a dewaxing unit are a fraction
with a boiling range comparable to that of the feed fraction 'and a gasoline fraction.
The pour point of the gas-, fuel- or lubricating oil will be lowered (e.g. for a
lubricating oil from 7C to -12C and for a middle distillate ' from 32C to -18C),
which drastically improves the properties of these oils at low temperatures.
Dewaxing of gas oil (diesel fuel) lowers the temperature at which "fogging"
occurs. This phenomenon is encountered during the winter when the linear
paraffins form clouds and plug the fuel lines of the car. In this thesis the unique
catalytic properties of ZSM-5 type zeolites will be demonstrated in two.
New gas phase reactions, namely the conversion of ethanol and ammonia to
pyridines

and the

ammoxidation of toluene to benzonitrile.Further chapters

describe the detection and analysis of ZSM-5 zeolites using infrared spectroscopy
10

and experiments on the synthesis of zeolite ZSM-5 using a range of templates and
a range of substituting T-atoms introduced during synthesis. Some data will be
given on experiments with molecular ..' sieves from the SAPO- and MeAPO group,
as these systems might offer the possibility of synthesizing materials with anion
exchange properties (here the lattice has to carry a surplus of positive charge). It
will be shown that the SAPC type materials can be effectively used in the
catalytic ammoxidation of toluene

RADIONUCLIDE APPLICATIONS:
As a potential remedial measure, the zeolite clinoptilolite was tested in a
greenhouse pot experiment for its effectiveness in selectively taking up cesium
from two British soils: a lowland loam and an upland peat. Rye-grass grown on
10% clinoptilolite-treated soils resulted in grass leaf tissue cesium concentrations
below 30 mg Cs kg-1 grass in all cases. Where no clinoptilolite had been added,
cesium in grass leaf-tissue reached 1,860 mg kg-1 in rye grown on peat and 150
mg kg-1 in rye grown on loam. In contrast, the addition of calcium carbonate to the
Cs treated, clinoptilolite-free peat soil enhanced the grass concentration of Cs by
approximately five times, but this effect was not observed with the concentration
of Cs in grass grown from loam soils with the same treatments. However, despite
this apparent beneficial result of adding the zeolite, adverse side effects were
observed. Since the zeolite is in the sodium form, sodium ions are released and the
risk of sodium toxicity to plants increases as cation exchange proceeds. Further,
since clinoptilolite binds heavy metals in general, essential heavy metals (such as
zinc) would be markedly decreased by the application of zeolite, which in turn
could result in deficiency problems in animals. It was also noted that since grazing
animals consume a 62 considerable amount of soil in their diet, the consumption of
11

radionuclide-laden zeolites could itself bring risks. In general, it has been noted
that the main research behind the use of natural zeolites as a remediation tool for
contaminated soil has been conducted largely through laboratory and greenhouse
trials. There is very little evidence in the literature to support the long-term use of
natural zeolites in real remediation projects (Stead et al. 2000). It was also noted
that the future potential of using zeolites has not been fully appreciated, and that
there is an urgent need to undertake field trials and evaluate the in-situ efficiency
for these remediation purposes. Since zeolites are natural materials and are mainly
used in industrial processes, little research is focused on their fate and transport,
though an extensive volume of work exists on their geological origin and behavior.
Extensive data exists on operation and maintenance parameters. As would be
expected, specific details are highly dependent on waste streams involved. Three
references (IAEA 1967, IAEA 1984, IAEA 2002) discussed below provide an
excellent overview of the issues involved.

IMPACTS, HAZARDS, EFFICACY AND LIMITATIONS:

Zeolites are a bulk commodity. World production is on the order of 4 million
tons per year, with China producing and using about 2.5 million tons (primarily as
a low-grade additive to pozzolan cement); U.S. consumption is about 0.5 million
tons. The primary industrial use is as a petrochemical catalyst and the second
largest use is as a detergent builder. Thus, the use of zeolites in radionuclide
remediation would be expected to have little impact. Most zeolites, particularly
those with current widespread uses, are regarded as a safe material; they are
currently being marketed as a health food and references to their medicinal use
date back thousands of years. Zeolites are also used as a feed additive for cattle,

12

pigs, chicken, and fish. It should be noted, however, that one zeolite, erionite, is
regarded as a carcinogen due to its fibrous nature and high iron content. Regarding
efficacy, though zeolites have had limited uses in environmental remediation
outside of their use in the nuclear industry as an ion exchanger for liquid
radioactive waste management, they are seen as having significant potential. Even
the drawbacks mentioned in the work of Campbell and Davies (Campbell and
Davies 1997) should be surmountable. To eliminate the sodium toxicity risk to
soil, the zeolite could be preconditioned into the ammonium form, which would
likely lead to plant growth improvements. Overcoming the concern of nutritionally
important soil nutrients binding together would require that the zeolite used
(possibly synthetic) would be designed to have a very high specificity for the target
radionuclide and little else. Alternatively, soil quality could easily be monitored
and appropriate amendments made.

13

CHAPTER-2
LITERATURE REVIEW
Zeolites are one of the few nanotechnologies that have been investigated for
environmental remediation purposes. Because of their ion exchange properties, and
the fact that they are a seemingly benign natural product that can bring certain
improvements (such as increasing the soil cation-exchange capacity and soil
moisture, improving hydraulic conductivity, increasing yields in acidified soils,
and reducing plant uptake of metal contaminants) to soil properties (Allen and
Ming 1995), zeolites have been examined for their ability to remediate heavy
metals in soil (Weber etal. 1984).
The origin of this work was the observation that radioactive cesium (137Cs)
from the Chernobyl accident of 1986 has unexpectedly remained in a bioavailable
form in upland, sheep-grazing soils of Great Britain.
Based on this work, Campbell and Davies (Campbell and Davies 1997)
performed an experimental investigation of plant uptake of cesium from soils
amended with clinoptilolite and calcium carbonate.
In 1994, Francois et al. used star and rod-coil polymers to obtain the honeycomb
film by the BF method. At the beginning, the work in this field mainly focused on
changing polymers, solvents and substrates to achieve all kinds of honeycomb
structure films.

14

CHAPTER -3
3.1. COMPONENTS USED:
3.1.1. TEST VEHICLE:
The test vehicle chosen for this project was a 2011 Maruti Suzuki EECO
certified to the low emission vehicle (LEV) standards. Specifications for the engine
are listed below:
Engine Type

Overhead-cam in-line 4 cylinder with OBD II

Displacement

2.0 liter

Valves

16

Horsepower (SAE net)

110 @ 5,000 rpm

Torque (SAE net lb.ft.)

125 @ 3,750 rpm

Fuel system

Sequential electronic fuel injection

Engine control

EEC-V computer

FIG 3.1: TEST VEHICLE

15

3.1.2. CATALYTIC CONVERTER:

Selection of catalytic converter also plays a key role in our project. Catalytic
converter which we selected for our project is petrol engine catalytic converter.
Reason behind this is that only petrol engine shows the exact composition of
exhaust impure gases during emission testing.

3.1.3. ZEOLITE ZSM-5:

FIG 3.2: ZEOLITE ZSM -5 SAMPLE

Zeolites are crystalline aluminosilicates, compositionally similar to clay
minerals, but differing in their well-defined three-dimensional nano- and microporous structure. Aluminum, silicon, and oxygen are arranged in a regular structure
of [SiO4]- and [AlO4]- tetrahedral units that form a framework with small pores
(also called tunnels, channels, or Cavities) of about 0.1-2 nm diameter running
through the material.

16

3.1.4. MULTIGAS ANALYSER:

TECHNICAL SPECIFICATIONS
MEASURED GAS

HC Hydrocarbons
CO Carbon Monoxide
CO2 Carbon Dioxide
O2 Oxygen

RANGES

CO(%)

CO2(%)

HC(ppm)

O2(%)

0 to 10

0 to 20

0 to 10000

0 to 25

0.02

0.30

0.10

0.01

0-1

0.01

ACCURACY /
PERFORMANCE
RESOLUTION
RPM

0 - 10,000 rpm with DIS/Wankel and 4 stroke selection

OIL TEMPERATURE

0 120 C

TABLE 3.1: MULTIGAS ANALYSER SPECIFICAITON

LAMBDA
Calculated using Brett Schneider formula.
Resolution 0.001
Fuel type selection: Unleaded Petrol, L.P.G. or C.N.G.
ENVIRONMENTAL
Operating temp. +5 to +40 C
Storage temp. -20 to +55 C

17

WARM-UP TIME
<60 seconds
RESPONSE TIME
11 seconds to 95% of final reading with 8 meter sample hose
FLOW RATE
8 litres/min nominal
5 litres/min minimum
OPERATING PRESSURE
750 - 1100 mbar
1013 mbar nominal
POWER REQUIREMENTS
100 - 240 volts AC, 50 - 60 Hz
POWER CONSUMPTION
60 watts maximum
SIZE
343mm (13.5") W x 220mm (8.7) D x 17Omm (7") H

WEIGHT
5.2kg

18

CHAPTER -4
4.1 METHODOLOGY:
PROBLEM IDENTIFICATION AREA

CATALYTIC
CONVERTER

CATALYST

COATING
TECHNIQUE

PETROL
ENGINE
CATALYTIC
CONVERTER

ZEOLITE
(ZSM-5)

DIP
COATING
TECHNIQUE

COATING
PROCESS

EMISSION
TESTING

RESULTS AND
DISCUSSSIONS
CONCLUSIONS

19

STAGE I :
4.1.1 CUTTING PROCESS:

FIG 4.1 CUTTED SHIELD

Cutting processes work by causing fracture of the material that is processed.
Usually, the portion that is fractured away is in small sized pieces, called chips.
Common cutting processes include sawing, shaping (or planing), broaching,
drilling, grinding, turning and milling. Although the actual machines, tools and
processes for cutting look very different from each other, the basic mechanism for
causing the fracture can be understood by just a simple model called for
orthogonal cutting.
A hand cutter is used to cut the catalytic converter shield. After cutting it,
honey comb structure (ceramic monolith) is taken out for coating purpose.

20

HONEYCOMB STRUCTURE (CERAMIC MONOLITH):

FIG 4.2 : HONEYCOMB STRUCTURE

Honeycomb structures are natural or man-made structures that have the
geometry of a honeycomb to allow the minimization of the amount of used
material to reach minimal weight and minimal material cost. The geometry of
honeycomb structures can vary widely but the common feature of all such
structures is an array of hollow cells formed between thin vertical walls. The cells
are often columnar and hexagonal in shape. A honeycomb shaped structure
provides

material

with

minimal

density

and

relative

high

out-of-

plane compression properties and out-of-plane shear properties.

Man-made honeycomb structural materials are commonly made by layering a
honeycomb material between two thin layers that provide strength in tension. This
forms a plate-like assembly. Honeycomb materials are widely used where flat or
slightly curved surfaces are needed and their high Specific strength is valuable.
They are widely used in the aerospace industry for this reason, and honeycomb
materials in aluminum, fibre glass and advanced composite materials have been
featured in aircraft and rockets since the 1950s.
21

STAGE II:
4.1.2 COATING REMOVAL PROCESS:
SODIUM HYDROXIDE:

FIG 4.3: SODIUM HYDROXIDE

Concentrated sodium hydroxide solution is used to remove the PGM. The
composition ratio of NaOH solution and water are 2:1. The ceramic is made to
immerse in mixture for the time period of 30 minutes. Then it is washed in water
and then heated in the oven at a temperature of 200 0 c for the time period of 1 hour.

22

STAGE III:
4.1.3 COATING PROCESS :( ZSM-5)

FIG 4.4: COATING METHOD

Catalytic converters are used in automobile and industries for pollution

abatement. They usually consist of cordierite ceramic extruded to form a structure
of honeycomb-like cells that extend as channels along the catalytic converter
length. A paint-like liquid containing the precious metal catalyst is coated on the
channel walls. During operation, exhaust gases are conveyed with low pressure
drop through the catalytic converter. The pollutant gases are removed by catalytic
activity in the catalyst coating. Monolithic catalytic converter substrates are shown
in the picture above.
Coating processes for catalytic converters present several challenges that
have been tackled in the visual analysis lab. Catalytic converter manufacturers

23

complained that quality control of catalyst coat thicknesses is difficult. In addition

the coating liquid often clogs several of the catalytic converter channels. Usually,
the monoliths are sprayed with a non-viscous solution containing dissolved
catalyst. Sometimes the monoliths are coated by dipping into a catalyst enriched
slurry and then blowing out the slurry with air. The air clears the channels leaving
a layer of deposited slurry solids on the channel walls. A solid coat of catalyst,
called the washcoat, is left after the liquid components dries out. A third method is
to suck the slurry through the monoliths by lowering one end of the monolith into a
catalyst slurry and applying a vacuum at the other end of the monolith. This
vacuum coating method has been the focus of our research and is illustrated below.

DIP COATING:
The ceramic monolith was then coated with the metal catalyst via dipping
technique. In this process ceramic monolith was immersed into prepared catalyst
slurry for the duration of 50 minutes. Then the coated ceramic was removed from
catalyst slurry to be blowered using air at the speed of 10 l/min until the unwanted
residual catalyst was evaded from the surface of the stainless steel wire mesh.
After blowered process, coated honeycomb structure was dried in an oven at
temperature 120C for 120 h before being calcined in a muffle furnace.
Calcination is a process in which a material is heated to a high temperature without
fusing, so that hydrates, carbonates, or other compounds are decomposed and the
volatile material is expelled. Calcinations take 60 hours at a temperature of 550C
with temperature ramping upon 100C/min and holding time of a 300 minutes.
After the calcinations process the ceramic monolith were arranged into straight bar
to become a substrate for use as a catalytic converter.

24

FIG 4.5 COATED HONEYCOMB STRUCTURE

COATING:
The coating of a catalytic converter can be considered as a chemical plant in
miniature, where toxic gases are converted into non toxic ones There are two
distinct parts to the coating. The first of these is known as the washcoat, the
purpose of which is to provide the maximum possible surface area for reactions to
take place. To extend the analogy of the chemical plant, the washcoat would be the
factory floor. If examined under a very powerful microscope, a good washcoat

25

appears extremely rough, a bit like sandpaper. The surface area of a washcoat is a
good indicator of how effective a catalytic converter will be, and a high quality
modern washcoat can provide amounts of surface area which are difficult to
comprehend for a non-chemist. For example, a washcoat providing less than 100
square metres of surface area per gram of weight would not meet the grade for
most OEM catalytic converters. Most washcoats consist primarily of alumina,
however ceria is also a common addition as are various chemicals known as rare
earths. Although, as mentioned above, the primary purpose of the washcoat is to
provide a large surface area, the ingredients of the washcoat also play an important
part in the chemical reactions which take place on its surface.
The second stage of the coating is the application of precious metals to the
washcoat, usually from the platinum group. These metals play a critical role in the
oxidation and reduction reactions which the catalytic converter is designed to
promote. Oxidation reactions are normally promoted by platinum, palladium or a
mixture of the two, whilst rhodium is used to promote reduction reactions.

26

STAGE IV:
4.1.4 GAS WELDING PROCESS:

FIG 4.6: GAS WELDED CATALYTIC CONVERTER

It is a fusion welding in which strong gas flame is used to generate heat and raise
temperature of metal pieces localized at the place where joint is to be made. In this
welding metal pieces to be joined are heated. The metal thus melted starts flowing
along the edges where joint is to be made. A filler metal may also be added to the
flowing molten metal to fill up the cavity at the edges. Different combinations of
gases can be used to obtain a heating flame. The popular gas combinations are oxyhydrogen mixture, oxygen-acetylene, and etc. different mixing proportion of two
gases in a mixture can generate different types of flames with different
characteristics.
After coating process, coated honeycomb structure is placed inside the
casing. Then the casing is welded with the help of gas welding process.

27

CHAPTER -5
5.1 RESULTS AND DISCUSSIONS:
5.1.1 RESULTS REGARDING PGM COATED CATALYTIC
CONVERTER:
CO(%BY

HC (PPM)

VOL.)

CO 2 (% BY O 2 (%

VOL.)

VOL.)

TRIAL 1

1.13

121

13.5

26.04

TRIAL 2

1.15

230

13.6

26.95

TRIAL 3

1.50

280

14

29.05

TRIAL 4

1.89

130

13.8

28.20

TRIAL 5

2.28

143

14.89

28.56

Table 5.1 Results for PGM Catalyst

28

BY

300
250
200

CO

150

HC

100

CO2

50

O2

0
TRIAL 1

TRIAL 2

TRIAL 3

TRIAL 4

TRIAL 5

FIG 5.1: GRAPH FOR PGM CATALYST

Before coating, vehicle is initially tested with PGM coated catalytic
converter. The results are shown in above table and graph. The optimal level for
CO is 3% by volume. It remains under the optimal level. But it keep on increasing
from lower to higher level. HC also under optimal level. But CO2 and O2 increases
abruptly.

5.1.2 RESULTS REGARDING ZSM -5 COATED CATALYTIC

CONVERTER:
CO(%

BY HC (PPM)

VOL.)

CO 2 (% BY O 2 (%

VOL.)

VOL.)

TRIAL 1

0.16

148

20.98

TRIAL 2

0.36

232

14

30.01

TRIAL 3

0.25

280

0.9

28.65

TRIAL 4

0.51

214

0.5

23.03

TRIAL 5

0.82

275

0.8

22.98

TABLE 5.2: RESULTS FOR ZSM -5 CATALYST

29

BY

300
250
200
CO
150

HC
CO2

100

O2

50
0
TRIAL 1

TRIAL 2

TRIAL 3

TRIAL 4

TRIAL 5

FIG 5.2 : GRAPH FOR ZSM -5 CATALYST

After coated with zeolite ZSM -5, once again catalytic
converter is tested for emission and its results are listed above in the form of table
and graph. In the above result, CO decreases abruptly. But HC cannot be able to
reduced. On the other hand, CO2 and O2 decreased in volume.

30

CHAPTER -6
6.1 CONCLUSIONS:
The following conclusions may be drawn from the present study.
Zeolite ZSM -5 catalyst based catalytic converter has been
successfullydeveloped.
The CO conversion efciency of catalytic converters are 25% than current
coated catalytic converter.
The HC conversion efciency of OEM and wire mesh catalytic converters
are increased by 27%.

The CO2 conversion efficiency is 25% more than current catalyst coated
catalytic converter.

The O2 conversion efficiency is increased by 90%.

31

CHAPTER -7
References
1. Angelidis T N, Papadakis P G 1997 Partial regeneration of an aged
commercial automotive catalyst. J. Applied Catalysis B: Environmental 12:
193206
2. Alois F 1995 Active metal: Preparation characterization application,
Mulhein: VCH
3. AkulaV,MikeSS2004LowtemperaturereductiveretreatmentofAu/fe2O3
catalysts,tpr/tpostudies and behaviour in the watergas shift reaction. J.
Applied Catalysis A: General 258: 241249
4. Avila P, Montes M, Miro E E 2005 Monolithic reactors for environmental
applications. A review on preparation technologies. Chemical Engineering
Journal 109: 1136
5. Bode H, Maus W, Swars H 1996 How metal substrate are able to have an
inuence on converter efciency, Presented at 17th International Engine
Symposium,Vienna, 2526th April
6. Eric V S, Gary S S, Rafene A M, Craig M, Heiko M, Martijn D L, Cyril T C
1996 tpr study on the preparation of impregnated CO/siO2 catalysts. J.
Catalysis 162: 220229
EttireddyPR,RajenderSV2004Preparation,characterizationandactivityofAl2O
3-supportedV2O5 catalysts. J. Catalysis 221: 93101
7. Fuad M A 2006 Cobalt Oxide/Titanium Dioxide (CoO/TiO2) catalyst
deposited onto wire mesh substrate as catalytic converter for natural gas
vehicle, Mech. Eng. Soc. Thesis, UiTM, Malaysia

32

8. Forzatti P, Lietti L 1999 Catalyst deactivation. Catalysis Today 52: 165181

Haber J 1991 Manual on catalyst characterization. J. Pure and Applied
Chemical 63: 9, 12271246
9. Heywood J B 1989 Internal combustion engine fundamentals, (New York:
McGraw-Hill)
10.Joy Industries 2007 Cobalt oxide catalyst for ammonia oxidation reduces
catalyst cost up to 75%, source: www.joyindustries.com/cobaltoxide.htm.(7/5/2007) KasparJ,FornasieroP,GrazianiM1999UseofCeO2basedoxidesinthethree-waycatalysis.Catal- ysis Today 50: 285298
11.Kielhorn J, Melber C, Keller D, Mangelsdorf I 2002 PalladiumA review
of exposure and effects to human health. Int. J. Hyg. Environ. Health 205:
417432 Matsubara E 2007 Studies of fabrication of nano-structuered
materials, procd. of 10th Field Wise
Seminar,AUNSEEDNET,EngineeringMaterials,CurrentAdvancesandPotenti
alApplications, 56th June. The Gurneng Hotel, Penang, Malaysia
12.Masakazu Anpo 2000 Use of visible light.second generation titanium oxide
photocatalyst prepared by the application of an advanced metal ionimplantation method. Pure Appl. Chem. 72: 9, 17871792, @2000 IUPAC
13.Merget R, Rosner G 2001 Evaluation of the health risk of platinum group
metals emitted from auto- motive catalytic converters. The Science of Total
Environment 270: 165173 Morita A, Kuma R, Masaki S, Kobayashi M
2007 Titanium oxide, catalyst for exhaust gas treat- ment and method of
purifying exhaust gas, World Intellectual Property Organization, Source:
www.wipo.int/pctdb/en/wo.jsp?wo=2006132097 (7/5/2007)
NijhuisTA,BeersAEW,VergunstT,HoekI,KapteijnF,MoulijnJA2001Preparati
on of monolithic catalysts. Catalysis Rev. 43(4): 345380

33

14.OsawaM1998Roleofceriumzirconium mixed oxides as catalysts for car

pollution : Ashortreview. J. Alloys and Compound 27(5): 886890
15.Poulopoulos S G and Philippopoulos C J 2004 MTBE, Methane, ethylene
and regulated exhaust emissions from vehicles with deactivated catalytic
converters. Atmospheric Environment 38: 44954500
16.Richard Stone 1999 Introduction to internal combustion engine, Third
Edition, (UK: University of Oxford press)
RavindraK,BenceL,GriekenRV2004Platinumgroupelementsintheenvironme
ntandtheirhealth risk. The Science of Total Environment 318: 143
17.Umit S O, Mahesh W K, Gurkan K 1998 Characterization and temperatureprogrammed studies over Pd/TiO2 catalysts for no reduction with methane.
Catalysis Today 40: 314
18.US Patent 2007 Conversion of carbon monoxide using cobalt-based metal
oxide catalysts, source: www.patentstorm.us/patents/5502019.html
(7/5/2007)
19.WhitelyJD,MurrayF2003Anthropogenicplatinumgroupelement(Pt,PdandRh)
concentrationsin road dusts and roadside soils from Perth, Western
Australia. The Science of the Total Environment 317: 121135

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