A

SEMINAR REPORT
ON
DESIGN AND FABRICATION OF CATALYTIC
CONVERTOR

Submitted By:

Guided By:

Brijesh Desai

Dr. Femina Patel

12BCH034

Associate Professor

CHEMICAL ENGINEERING DEPARTMENT

INSTITUTE OF TECHNOLOGY
NIRMA UNIVERSITY

CERTIFICATE
This is to certify that Mr. Brijesh Desai (12BCH034), student of Chemical
Engineering, 6th semester, of Nirma University, has satisfactorily completed the
seminar on DESIGN AND FABRICATION OF CATALYTIC CONVERTER as
a partial fulfilment towards the degree of B. Tech. in Chemical Engineering.

Date:
Place: Nirma University, Ahmedabad

Femina patel

Dr. S. S. Patel

Associate professor

Head of Department

ACKNOWLEDGEMENT
As an integral part of our B.Tech graduation, it has been privilege to undergo a Seminar at
Chemical Engineering Department, Nirma University.
We are very much thankful to our Chemical Engineering Department for helping and providing
all the support and facilities required for my seminar requirement.
I would like to take this opportunity to specially express my humble gratitude to Dr. Femina
Patel, under whom I have done this seminar. Constant guidance and willingness to share her
vast knowledge made us understand this project and its manifestations in great depths and
helped us to complete the assigned task.
I sincerely thank to all the individuals whose efforts helped me to successfully complete this
project.

ABSTRACT
Air pollution generated by automobile vehicle is an issue of great concern because of harmful gases
like nitrogen oxides (NOx), carbon-monoxide (CO), unburned hydrocarbons (HC) and particulate
matters (PM) that are emitted by automobile exhaust. These pollutants affect adversely on
environment, human health, and air quality which had led to stringent regulations called emission
norms. For controlling of tail pipe emission from two/four wheelers we have been using three way
catalytic converter which is based on catalyst Pt-Pd-Rh however there has been some limitations.
Other alternative of noble metal for catalytic converter is Perovskite oxides (with general formula
ABO3 where A and B are rare earth, alkaline earth, alkali metal and transition metal cations
respectively) for automotive CO oxidation because of its high thermal stability at high temperature,
low cost, good mechanical stability and excellent redox properties.
In the designing of catalytic converter, to decide the volume of the reactor is crucial aspect. This is
done by considering it as Tubular reactor. The modelling of the catalytic converter has also been
done which give relation between length, thickness and diameter. The pressure drop for the model
has also been determined.

Index
Sr. No
1

Title
Engine Introduction
1.1

1.2

Page No
1

Internal Combustion Engine(ICE)

1.1.1

Type of Ignition

1.1.2

Engine cycle

External Combustion Engine

Air Pollution

Vehicle Emission

3.1

Exhaust emissions

3.2

Evaporative Emission

3.3

Crankcase Emission

Exhaust Pollutant

Emission Standards

Emission Control

6.1

Catalytic Converter

Parts of Catalytic Converter

7.1

7.2

7.3

10

Substrate

10

7.1.1

Ceramic Monolith

10

7.1.2

Metallic Monolith

11

Catalyst

12

7.2.1

Noble Catalyst

12

7.2.2

Perovskites catalyst

13

7.2.3

Steps for catalyst Preparation

16

Washcoat

16

Design of Catalytic Converter

17

Modelling of Catalytic Converter

18

Outlook

21

10

Reference

21

List of Tables
Sr. No

Title of Table

Page No

Emission from Vehicle

Indian Emission Standards (4-Wheel Vehicles)

Emission Standards for Light-Duty Vehicles

Comparison of Characteristics of Metallic and Ceramic Monolith 12

Catalyst Substrates

List of Figures
Sr. No

Title of Figure

Page No

Schematic Diagram of different emission from automobile

Different shell density and sizes of monolithic material

11

Metallic monolith

12

(a)Perovskite structure (CaTiO3) , (b) Structure of Perovskite 13

(ABO3)

Schematic diagram of concentration change over dx length along 18

the converter

1) Introduction to Engine
A combustion engine is a machine that produces energy (mechanical) by the combustion of
substance (water or a fuel).
Classification of engine is done into different categories based on:

The cycle type they use,

The layout of engine,

The use of energy source ,

The mechanism for cooling employed or

Its use or application [1].

There are two types of Engines based on their Layout.

1.1) Internal Combustion Engine

An internal combustion engine (ICE) is an engine in which the combustion of a fuel take place
with an oxidizer i.e air in a combustion chamber which is an integral part of the working fluid.
The high-temperature and pressure leads to expansion of gases that is produced by combustion
which apply direct force on specific parts of the engine. The transformation of chemical energy
into useful mechanical energy take place due to the displacement of component which provided
by this force [2].
There can be different classification of internal combustion engines which are:

1.1.1) Types of ignition

I.

Spark Ignition (SI)

The process of combustion in an SI engine will start in every cycle by a spark plug. The high
voltage electrical discharge between two electrodes is produced by spark plug which is
responsible for ignition of the air and fuel mixture (in a specific ratio) in the combustion
chamber around the plug. Before electric spark plug were invented, use of different type of
torch holes started the combustion process with the help of external flame.
II.

Compression Ignition (CI)

In CI engine, the combustion operation initiate with self-ignition of air and fuel mixture
because of high thermal condition in the combustion chamber produced by high compression
[3].

1.1.2) Engine cycle

I.

Four-stroke cycle:
1. Intake, suction or inductive:
2. Compression stroke:
3. Power stroke:
4. Exhaust removal: [4]

II.

Two-stroke cycle:[5]

1.2) External Combustion Engine

An external combustion engine (EC engine) is a heat engine where an (internal) working fluid
is heated by combustion in an external source, through the engine wall or a heat exchanger.
The fluid then, by expanding and acting on the mechanism of the engine, produces motion and
usable work [6].

2) Air Pollution
There are generally three way types pollution caused by human being
1. Stationary or point,
2. Mobile,
3. Indoor
Air pollution by mobile sources like automobiles which is major threat to air quality in urban
and industrial areas. About 50 millions of cars are manufactured every year, and around 700
million are used globally. In developing countries talking about rural area, air pollution from
open fires for use such as cooking and heating is a serious threat. The cause of stationary air
pollution are industries, power plants etc. Although in urban area of developed countries
controlling of the air quality has been done to some extent in this last two decades, in most of
the developing countries the condition are worse and had become a major threat to the health
and also to the welfare of people and the environment.
In our modern society, quality of life is measured by the amount of electricity consumption or
by the use of car. Generation of electricity and operation of vehicles uses a fossil fuel. The
global population of vehicle excluding motorcycles expanded from around 350 million in 1960
to about 671 million in the 2000. Emission of Nitrogen-oxides from motor vehicles causes acid
rain and photochemical smog, leads to ecological damages and respiratory diseases and also

has become one of the most important issues for environmental protection. Ozone layer
depletion are also the adverse effect of emissions from motor vehicle. The different vehicular
air pollutants can have effects at all the three levels-local (e.g., smoke affecting visibility,
ambient air, noise etc.), regional (such as smog, acidification) and global (i.e., global warming).
The vehicles are the prominent source of air pollutants and also account for a number of
external effects, such as noise congestion, road wear and tear, accidents and barrier effects.
According to the World Health Organization (WHO), annually about 4 to 8 % deaths that occur
worldwide are due to air pollution and of its constituents. The major pollutants that are emitted
from gasoline fuelled vehicles are HC, CO, NOx. Due to incomplete combustion taking place
in the engine, there are generated a number of harmful products due to incomplete combustion
[7].
At the normal engine operating conditions the exhaust gas emitted are
1 Carbon monoxide (CO, 0.5 vol. %);
2 Unburned hydrocarbons (HC, 350 vppm);
3 Nitrogen oxides (NOx, 900 vppm);
4 Hydrogen (H3, 0.17 vol. %);
5 Water (H3O, 10 vol. %);
6 Carbon dioxide (CO3, 10 vol. %);
7 Oxygen (O3, 0.5 vol. %).
8 HC, CO and NOx are the major exhaust pollutants.
The combustion efficiency is less than 100% which leads to HC and CO formation due to
improper gas mixing and also the wall quenching effects. The formation of NOx take place at
high temperatures (>300C) during the combustion process which results in NOx formation
due to thermal fixation of the N2 in the air. Because of the large number of vehicle, large
amounts of pollutant such as HC, CO and NOx are released in the atmosphere. The formation
of ground level ozone take place due to a chemical reaction between HC, NOx and sunlight. In
urban area, when these stagnant air masses linger so the pollutants are present at place for very
long duration. The reaction of pollutant with the sunlight transforms them into ground level
ozone. Ozone is a prime component of smog which is responsible for damage of vegetation
and reduces atmospheric visibility. Volatile organic compounds (VOCs) are main class of air
pollutants which are emitted from many industrial processes and due to transportation. One of
the best technology for the VOC reduction is catalytic combustion. A catalyst can oxidise the
VOCs at temperatures lower than that of thermal oxidation [8].

3) Vehicular Emissions
Types of vehicular emissions are:

3.1) Exhaust emissions:

In Exhaust emissions, pollutant are released from the tail pipe when the vehicle is started or
running. Thus the exhaust emissions are mainly divided into two categories - start up emissions
and running emissions.
Start-up emissions:
Emissions from the automobile when it is just started. Depending on the duration of vehicle
for which engine is turned off after its use, there can be hot or cold start. Cold start is when the
vehicle is started suddenly after a long duration of its use and, hot start is when the vehicle is
started without giving vehicle enough time to cool down after its previous use.
Running emissions:
Emissions from the vehicle when it is running. In this condition the vehicle is in a mode of hot
stabilization.

3.2) Evaporative emissions:

Evaporative emissions are Hydrocarbon vapors lost constantly and directly to the atmosphere
because of volatile nature of petrol. It takes place mainly from the fuel tank, fuel lines and
carburettor depending upon the fuel composition, operating temperature of engine and ambient
temperature. Through fuel evaporation the volatile organic compounds (VOC) escape in the
air. On hot days, losses due to evaporative emission accounts for a majority of the total
pollution due to VOC.
Running Losses
While the vehicle is running the vaporization of gasoline take place from the hot engine and
exhaust system.
Hot soak (Cooling Down) (Losses from the carburettor)
After the vehicle is turned off the engine remain hot for a period of time which causes
gasoline to evaporate after the car is parked i.e. while cooling down.
Diurnal Emissions (Emissions from Engine when it is cool or parked)

Gasoline evaporation occurs even when the vehicle is parked for long duration because of the
rise in the temperature during the day.
Refuelling
Evaporation of gasoline take place from the fuel tank while the tank is being filled.

3.3) Crankcase Emission (also called running loss emissions)

Crankcase emissions is the pollutant emitted directly in the atmosphere from an opening which
leads to the crankcase of a motor vehicle engine. Crankcase emissions are partially burned or
unburnt fuel components which under pressure escape from the combustion chamber, pass the
pistons and enter into the crankcase. This type of mixture is referred as blow-by. The main
constituent of this type of emission is Hydrocarbons. If it is not controlled, it may constitute
13-35 % of total emissions. Since, diesel engines compress only air, blow-by emission contain
very low levels of pollutants.

Figure 1: Schematic Diagram of different emission from automobile

Table 1: Emission from Vehicle

Source

Amount of Emission%
4-stroke

Crankcase blow 30
by

Remarks

2-stroke
0

Carburetted

air-fuel

combustion fuel

mixture

&

under pressure

escape combustion chamber past

engine piston and ring and enter

crank base to be discharged into
atmosphere through vents

Evaporative

30

Emissions

Exhaust

Fuel vapours lost to the atmosphere

from tanks and carburettor

60

97

Emissions

Exhaust

gases

emitted

with

pollutants through the tailpipe.

4) Exhaust Pollutants
The pollutants that are released from the exhaust system of the vehicle are called an exhaust
pollutants. They are produced because of fuel combustion in the engine of vehicle. These type
of pollutants have adverse effect on atmosphere and living things. The major types of pollutants
released from the exhaust are listed in the following sections:
Sulphur Oxides (SOx)
SO2 is produced by combustion of petroleum. It is a pungent, colourless and not flammable
gas. It causes respiratory problems, but is present in exhaust gas in very low concentrations.
The oxidation of SOx forms H2SO4 and thus leads to acid rains.
Nitrogen Oxides (NOx)
Combustion of fuel at high pressure and high temperature emits Nitrogen dioxide (NOx). It is
reddish brown gas. The formation of ground level Ozone take place due to NOx and also
responsible for acid rain.
Hydrocarbons (HC) and Volatile Organic Compounds (VOC)
Hydrocarbons formation take place due to the incomplete fuel combustion. The reaction with
the sunlight forms smog and also responsible for ground level Ozone formation. Volatile
organic compound are a special type of Hydrocarbons. They are classified into 2 groups
methane and non-methane. Prolonged exposure to these compounds like Benzene, Toluene and
Xylene (BTX) may cause Leukaemia.

Carbon Dioxide (CO2)

Proportion of CO2 indicates about complete combustion of the fuel. It does not directly affect
our health but it is a greenhouse gas which leads to global warming.
Carbon Monoxide (CO)
CO is a product formed due to the incomplete burning of fuel i.e. due to partially oxidation of
Carbon. CO is a colourless, odourless gas but it is toxic in nature. It reaches the blood stream
and form Carboxyhemoglobin which is responsible for reducing the flow of oxygen in blood.
Lead (Pb)
It is a malleable heavy metal. Lead in the fuel helps in preventing engine knock. Lead has
adverse effect on the nervous and reproductive systems. It is a neurotoxin which gets
accumulated in the soft tissues and bones.
Particulate Matter (PM)
They are tiny solid or liquid particles suspended in gas (soot or smoke). Particulate Matter in
very higher concentrations may cause heart diseases and lung cancer. [9]

5) Emission Standards
1 Bharat stage emission standards
2 European emission standards
5.1) Bharat stage emission standards
The first Indian emission regulations became effective in 1989. These idle emission regulations
were soon then replaced by mass emission limits for both gasoline vehicles (1991) and diesel
(1993) vehicles, which were gradually tightened during the 1990s. Since the year 2000, India
started adopting European emission and fuel regulations for four-wheeled light and heavy-duty
vehicles. Indias own emission regulations is still applicable to two- and three-wheelers.
The National Auto Fuel Policy, announced on October 6, 2003, envisioned a phased program
for introducing Euro 3 - 4 emission and fuel regulations by 2010. The implementation schedule
of EU emission standards in India is summarized in Table.
Table 2: Indian Emission Standards (4-Wheel Vehicles)
Standard

Reference

Date

Region

India 3000

Euro 1

2000

Nationwide

Bharat Stage II

Euro 3

2001

NCR*, Mumbai,

2003.04

NCR*, 11 Cities

2005.04

Nationwide

2005.04

NCR*, 11 Cities

2010.04

Nationwide

2010.04

NCR*, 13 Cities

Bharat Stage III

Bharat Stage IV

Euro 3

Euro 4

*National Capital Region Mumbai, Kolkata, Chennai, Bangalore, Hyderabad, Secunderabad,

Ahmedabad, Pune, Surat, Kanpur

The above standards apply to all new 4-wheel vehicles sold and registered in the respective regions.
In addition, the National Auto Fuel Policy 2003 introduced certain emission requirements for
interstate buses with routes originating or terminating in Delhi or the other mentioned cities.
For 3-wheelers, Bharat Stage II applied from April 1, 2005 and Stage III standards came into force in
April 1, 2010. The roll out of Bharat Stage IV limits nationwide was delayed by the challenge of
convincing fuel producers to make the necessary investments required to supply 50 ppm sulphur fuel
nationwide. Potential solutions that have been suggested include deregulation of diesel prices, an
environment compensation charge on diesel vehicles and an additional levy on diesel fuel.
Even in cities with Bharat Stage IV limits, there have been challenges ensuring the dominance of
compliant vehicles. Some of these challenges include: exemptions granted to some specialty vehicle
(e.g., taxis) manufacturers, registration of Bharat Stage III vehicles by vehicle owners outside of their
place residence due to loopholes in residential proof, registration of commercial vehicles outside of
the Bharat Stage IV zones and insufficient availability of some specialty vehicles (e.g., garbage
trucks) in Bharat Stage IV configurations.
In order to establish limits beyond Bharat Stage IV, the Indian Planning Commission established a
Committee in 2013 to draft an updated Auto Fuel Policy. The panel recommended that Bharat Stage
IV fuel be required nationwide from April 2017 followed by a further step up to the Bharat Stage V
in April 2030. Draft recommendations discussed prior to the reports release included a national
Bharat Phase IV+ stage (40 ppm sulphur) starting in 2017 and a national Bharat Stage V fuel standard
staring in 2031.
Attempts to set fuel economy standards started in 2007, but it were delayed due to inter-ministerial
conflicts and pressure from the automobile industry. In January 2014, India notified minimum fuel

efficiency norms for passenger vehicles that are sold in India. Two sets of standards were announced:
one set for fiscal years 3016-17 to 3030-31 and another for fiscal year 3031-33 onwards [10].
Table 3: Emission Standards for Light-Duty Vehicles, g/km
Norms

CO (g/kmhr)

HC (g/kmhr)

NOx(g/kmhr)

PM(g/kmhr)

1991Norms

14

3.5

18

1996 Norms

11.3

3.4

14.4

1.1

8.0

0.36

India stage 3000 4.5

norms
Bharat stage II

4.0

1.1

7.0

0.3

Bharat Stage-III

3.1

1.6

5.0

0.10

Bharat Stage-IV

1.5

0.96

3.5

0.03

6) Emission Control
The new advancement in Engine design has steadily increased the efficiency of engine,
increased precision in ignition timing and also electronic ignition, accuracy in fuel metering,
and computer based engine management system.
Advancement in engine and vehicle technology has continually reduced the toxicity of exhaust
leaving the engine, but these single headedly is insufficient to meet emissions goals. Therefore,
detoxification technology of the pollutant gases from exhaust is prime focus of emissions
control.
Different Emission Control Technique are
1. Air injection
2. Exhaust gas recirculation

3. Catalytic converter
6.1) Catalytic converter
A catalytic converter is a device which is used reduction of the emissions from an IC engine
which is recent trend in automobiles and vehicles. There is generation of toxic by-product when
there is not enough availability of oxygen for oxidation of the carbon fuel completely into
carbon dioxide and water. The catalyst used in catalytic converters provide the active site for
the oxidation reaction and reduction reaction of toxic by-products (like nitrogen oxides, carbon

monoxide and hydrocarbons) of fuel into less hazardous substances such as carbon dioxide,
nitrogen gas and water vapor.
I.

Oxidation:

Oxidation catalytic converter: HC + O2 CO2 + H2O

2CO + O2 2CO2
II.

Reduction:

Reduction catalytic converter: 2NO N2 + O2

7) Parts of Catalytic Converter

7.1) Substrate
It consists of a honeycomb like structures of ceramic or metal which contain catalysts for
reaction to take place on it. A large number of small straight or parallel channels are present in
a monolith block. The monoliths are made by extrusion. A monolith structure is made by
passing a predefined mixture of clay binders and additives through a sophisticated dye. The
material is dried and cut to the appropriate length and processed at high temperatures. The
diameter of monolithic structure is about 3 cm and can have different shapes according to the
requirement in which the diameter of the channels ranges from 0.5 to 10 mm. A catalytic active
layer can be applied on the walls of the channels in which chemical reactions will take place.
The contact area between the catalytic layer and the fluid is very large because of large number
of channels. The arrangement of channels in the structure is straight and parallel so that the
flow is not obstructed which will develop very less pressure drop.
7.1.1) Ceramic monolith
The ceramic material mainly used is porous cordierite (3MgO.3Al2O3.5SiO3) which is a low-thermal
expansion property. The raw materials like talc, alumina, aluminum hydroxide, silica and kaolin are
blended to form a paste. Thereafter process called extrusion is done and which is followed by calcination
to produce ceramic monoliths of varying sizes up to 180 mm in diameter and 375 mm long.

The number of cells vary from 3 to 95 per cm2, the most common until recently being 63
cells/cm3 equal to 400 cells per square inch (cpsi) for passenger car application. The cells are
mostly square but triangular and hexagonal shapes have been considered. The triangular cells
have about 30 % higher pressure drop compared to the square cells. On the other hand,
hexagonal cell have 10-13 % lower pressure drop relative to square cell substrate.

Figure 2: Different shell density and sizes of monolithic material

7.1.2) Metallic monolith

In metallic monoliths, alternate flat and corrugated thin foils of about 0.05 mm thickness made
of temperature resistant aluminum containing steel are wound in a spiral shape to form the
honeycomb structure.
First, Iron (Fe) powder, Aluminium (Al) powder and Chromium (Cr) powder, or powders of
alloys of these metals, with optional additions of Sn powder and Cu powder, are mixed to
prepare a metal powder mixture having a composition essentially consisting of, as analysed in
weight percent, 3.5 to 30% Al, 0 to 40% Cr and a balance of Fe with the sum At, Cr and Fe
constituting 90% or more of the total composition. In case of the extrusion, subsequently, the
metal powder mixture is blended into an organic binder, such as methyl cellulose or polyvinyl
alcohol, and water to produce a formable mixture and that mixture is then formed into a shape
of a desired honeycomb configuration by the extrusion.
When the metal powder mixture is blended into the organic binder and water, prior to the
addition of water, an antioxidant, such as oleic acid, may be added to the metal powder mixture.
Next, the shaped honeycomb body is sintered in a non-oxidizing atmosphere at a temperature
ranging between 1000 and 1450C. During the sintering in the non-oxidizing atmosphere
containing hydrogen, the organic binder is decomposed and thereby removed with Fe or the
like acting as a catalyst, and a good sintered body (a metal monolith) can therefore be obtained
[11].

Figure 3: Metallic monolith

Table 4 Comparison of Characteristics of Metallic and Ceramic Monolith Catalyst Substrates
Characteristics

Metallic Monolith

Ceramic Monolith

Wall thickness, mmc

0.03-0.04

0.06-0.30

Range of cell density/cm3

16-186

16-186

Thermal Conductivity, W/mK

14-33

0.1-0.8

Specific Heat capacity, kJ/kg. K

0.4-0.5

0.75-1.05

Density, g/cm3

7.4

3.3-3.7

Geometric Data

Physical Data

7.2) Catalyst
7.2.1) Noble metal catalyst
The recent technology of simultaneously conversion of all three pollutants into innocuous
materials is the three way catalysis. The automotive catalysts in catalytic converter contain
precious metals palladium (Pd), platinum (Pt) and rhodium (Rh) which is widely recognized
for the conversion of three pollutant-emissions, such as carbon monoxide(CO) into CO2 ,
nitrogen oxides(NOx) to nitrogen and unburned hydrocarbons (HC) into CO2 and water in
engine exhaust gases (Cars tail pipe) . The basic function of the catalyst in this case is to
perform the above reaction in the vehicle exhaust at lower temperature than a thermal processes
[12].
Limitation

The deactivation of the metal in the catalyst because of the harsh conditions experienced in the
exhaust stream with temperatures up to 1000 C leads to a reduction in surface area and hence
is responsible for reduction in catalytic activity. The conventional means to meet tight engine
legislative emissions control targets is simply to increase the amount of PGM in the auto
catalyst. Also because of maintaining catalyst performance over the typical lifetime of
80,000km means that excess of metal has to be used as the performance of the catalyst drops
off over time. In addition rising PGM demand and costs are incentives towards achieving lower
metal loadings and higher activity. The compounds of the Mare generally considered highly
toxic while the Pd and Rh are carcinogenic in nature. Due to the fact that the PGM are produced
due to the abrasion of automotive catalyst wash coat. Because of this the road traffic is main
source for metallic as well as organic pollutant-emissions which affect the environment. The
catalytic converters is damaged by several mechanisms e.g. thermal deterioration and
poisoning. Thermal deterioration take place due to the exposure of the catalyst to high
temperature conditions. This is responsible for sintering of the PGM, also for loss of support
surface area and phase transformation. Poisoning is responsible for loss of activity generally
due to blockage of the pores or even by direct blockage of the active sites themselves.

7.2.2) Perovskites catalyst

The general chemical formula for perovskite compounds is ABO3 where A and B are two
cations and O is an anion that bonds to both. The A atoms are larger than the B atoms. A
ion (A coordinated by 12 oxygen) can be rare earth, alkaline earth, alkali and other large ions
such as Pb+2, Bi+3 that fits in to the dodecahedral site. The B ion in which B surrounded by six
oxygen in octahedral coordination) can be 3d, 4d and 5d transition metal ions [13].

(a)

(b)

Figure 4: (a) Perovskite structure (CaTiO3) , (b) Structure of Perovskite (ABO3)

The perovskite-type oxides will have catalytic property basically depend on the nature of A
and B ions and on their valence state. The A site ions are catalytically inactive. The nature of
these ions affect the stabilnormalyity of the perovskite phase. Catalytic activity is determined
by the B cation. Oxygen vacancies can be formed. The oxidation activity of perovskites has
been ascribed to their ionic conductivity, to oxygen mobility within their lattice, to their
reducibility and to their oxygen sorption properties. Indeed, two possible mechanisms, a
superficial and an intrafacial one are proposed for oxidation reduction over these catalysts. The
former mechanism rises from the interaction of surface oxygen with reactants and it is operative
at low temperature (< 400 0C). The latter is effective at higher temperature (> 400 0C) and
involves a Mars Van Krevelen redox cycle. In it, bulk oxygen migrates towards the surface
becoming available for the oxidation of the adsorbed substrate and it is quickly replaced by
oxygen coming from the gaseous phase. The mobility of O2- ions within the crystalline
framework determines the mechanism of the catalytic reaction. The released oxygen species
can be divided into two categories depending on temperature (1) oxygen: low temperature
superficial species, weakly chemisorbed on the surface of the perovskite, desorbed in the 300
600 C range and related to surface oxygen vacancies (2) oxygen: high temperature interfacial
one, less easy to desorbs and therefore more bound to the perovskite structure, desorbed above
600 C and related to the bulk nature of the catalyst. (Table 1).Generally speaking, A-site
replacement mainly affects the amount of sorbed oxygen whereas B-site replacement
influences the nature of sorbed oxygen. Therefore, such isostructural substitution would
produce modifications of the perovskites catalytic behaviour. [14]
Synthesis Method for Perovskite
1. Combustion Synthesis Method
2. Citrate Method
3. Sol-Gel
4. Co-Precipitation
5. Reactive Grinding method
Solution Combustion Synthesis (SCS)
To produce any metal oxide by combustion synthesis, an aqueous solution of metal nitrates
(oxidisers) and the appropriate amount of urea (fuel) is brought to the boil; shortly thereafter
the mixture ignites and the fast self-sustaining redox reaction takes off which generates a large
amount of gaseous products in a very short period of time which leads to a spongy catalyst
morphology and also form rough interfaces for the catalyst powder agglomerates which helps

in maximizing the number of contact points between catalyst and carbon (soot) and promoting
carbon combustion and consequently, NO reduction. In recent years, this technique has been
used to produce homogeneous, very fine, crystalline powders without the intermediate
decomposition and/or calcining steps which other conventional synthesis routes would require.
Powders prepared via SCS generally have higher specific surface areas as well as pure phases
and the desired chemical compositions. However, the main drawback of this method is that
hazardous or polluting compounds are emitted during the synthesis (mainly NH3 or NOx).
Citrate complexation
Nitrates of constituent metals of the required perovskite were dissolved in water and mixed
with an aqueous solution of citric acid (molar ratio of citric acid to total metals 1:l). Water was
evaporated from the mixed solution using a rotary evaporator at 330-340 K until a sol was
obtained. The sol was further dehydrated at the same temperature under vacuum for 5 h. Citrate
method normally produces solids with a higher degree of crystalline. Citrate method is most
effective route to create higher surface areas25.
Sol gel methods
The precursor in a sol-gel preparation can either be a metal salt/alkoxide dissolved in an
appropriate solvent (organic solvent) or a stable colloidal suspension of preformed sols.
Commonly, gels are obtained by a hydrolysis step followed by a condensation reaction. The
destabilization of a sol into a gel which mainly occurs by modifying the pH of the dispersion
can also be performed. Sol gel technique is one of the most efficient methods since it permits
a better control of stoichiometry, high reactivity, controlled dimensions and nanoparticles.
Co-precipitation
Synthesis of perovskites is by co precipitation from soluble precursors of the constituent metals
in suitable solvent and then coprecipitated as a gel by adding an acid/base or another reagent
to cause the precipitation. These can be readily converted to oxides by heating. Precipitation
has three stages: supersaturation, nucleation and growth. An amorphous or crystalline
precipitate or a gel is obtained which is aged, filtered, washed thoroughly until salt free. This
is then followed by further steps: drying, shaping, calcination and activation. Various
characterization techniques confirmed that the co-precipitation method produces lower
crystallinity and higher surface area than the citrate method. In addition, the final material
obtained from the alkali coprecipitation route suffers from the contamination of alkaline metals
as well as the formation of large amount of environmental wastes (e.g., salts from hydrolysis
and wash water).
Reactive grinding

A reactive grinding (high-energy mechanical synthesis) allowing to attain a pure perosvkites

phase at room temperature without the thermal treatment. Mechanical impact during the
process reduces the precursors crystallite size to nano scale provides a homogeneous mixture
and enhances the solid state diffusion. The synthesis is performed in a closed environment
without generating any waste.

7.2.3) Steps for Catalyst Preparation

1. First of all, the salt precursors for the targeted catalyst have been taken in an amount which
is stoichiometric ally balanced.
2. Pre-treatment like calcinations for a decided period of time is given in muffle furnace. To
remove hydrogen compound from salt precursors. This pre-treatment is not compulsory for
each catalyst.
3. Then the salt precursors are mixed and kept into jar of the ball mill to provide high energy
ball milling. The following conditions are maintained for milling.
4. This will lead to mechanochemical synthesis among salts, exothermic reaction will take
place and catalyst will be formed.
5. Then the calcinations of catalyst are done for 11hr at 600 C.

7.3) Washcoat
A thin layer of inorganic oxides known as wash coat is applied to the cells in monolith structure
to increase effective surface area for dispersion of active catalyst that increase its contact with
the reacting gases. The wash coat has pores of varying sizes ranging from 20 to 100 . The
ceramic monoliths generally have some wall porosity or surface roughness that results in good
adhesion of wash coat. The washcoat constitutes about 5 to 15 % of the weight of ceramic
monolith. Its thickness typically varies in the range 10-30 m on the walls and 60-150 m on
the corners of the square cells which reduces the open flow area of the catalyst. Ceramic and
metallic monoliths have a geometrical surface area of 2.0-4.0 m2/l of substrate volume. Wash
coat increase surface area of the catalyst substrate to 10000-40000 m2/l of monolith volume.
The wash coat components support the catalyst function and to improve resistance of catalyst
to thermal de-activation processes.
A Wash coat composition comprises of a soluble Wash coat salt species (a nitrate, a halide, a
sulfate, a sulfite, a nitrite, a phosphate, a carbonate, an oxalate, a carboxylate), a polar organic

solvent (ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, glyoxal, dialdehyde)
and an insoluble particulate material (iron oxide, Zinc oxide, tin oxide, ceria, titania, alumina, silica,
spinal, perovskite, or a combination).

7) Designing of reactor
In the designing of catalytic Converter the sizing of reactor is very important. The cell density &
the porosity will decide the back pressure generated in the reactor. The conversion will depend
upon the length of the reactor which in decided by the volume.

Consider the catalytic reactor as a plug flow reactor. Since pollutant conversion in the reactor
is a function of the catalyst loading, reactor length, and catalyst concentration, an integral
reactor principle was employed to evaluate significant changes in the pollutant reduction in the
reactor.

Where, V is the volume of reactor,

FA0 is the molar flow rate of the reactant,
XA is the fraction conversion,
rA is the reaction rate.
In a steady state Plug flow reactor with constant density system:

The performance equation can be given as:

And

The reactor volume can be calculated from:

From the value of internal diameter the reactor surface area can be calculated

The length of the reactor can be calculated from: L = VR /A

The space time was evaluated as the ratio of reactor volume to that of volumetric flow rate [15]
= VR / V0

8) Modelling of Reactor
Consider the conversion efficiency for the case of a catalytic converter operating in the mass
transfer limited regime under steady state conditions and a typical monolith channel as shown
in Fig. 1. Under such conditions conversion efficiency can be obtained using the Sherwood
number (Sh), a fundamental non-dimensional parameter for mass transfer.

Figure 5: Schematic diagram of concentration change over dx length along the converter.
Treating the flow as one-dimensional and neglecting axial diffusion then a simple mass balance
can be performed on a channel element of length dx by equating the net advection into the
element with mass transfer to the channel walls,
(UAC) x - (UAC) x + dx = h*P dx [C(x) C wall]

Hence
C(x) = C0 Expo (- h*P*x / U*A)
Here it is assumed that the temperatures are sufficiently high for the surface reaction rates to
be much faster than the mass transfer rate to the channel walls and hence wall concentrations
can be assumed to be negligibly small. Defining a channel hydraulic diameter, d 4A=P, then
with the mass transfer coefficient h defined as
h = Sh*Dm / d
The concentration at the channel exit is
C (L) = C0 Expo (- 4*L*Sh*Dm /U*d2)
And we can define a conversion efficiency as,

Once the flow field is known or assumed then Eq. (5) gives the conversion efficiency directly.
A similar approach can be found in work of Comfort [4], Karvounis and Assanis [6] and Jeong
and Kim.
Consider a monolith comprised of numerous such channels. It is convenient to define a
monolith superficial velocity, Us that assumes all the porous medium is fluid, i.e. there is
negligible wall thickness, w. Without loss of generality it is convenient to consider the case
for channels of square section, the shape normally associated with ceramic monoliths. For
this case for a substrate porosity, and cell density, n we have

If a uniform conversion efficiency is required across the monolith then according to Eqs. (5)
and (6) we must have for all channels

This suggests that for a given flow distribution there is an infinite number of combinations of
monolith parameters that can be chosen to give a uniform conversion efficiency across the
monolith. For example if the monolith length and wall thickness are fixed and constant then
the channel hydraulic diameter, d is given by

Alternatively if the channel hydraulic diameter and wall thickness are fixed and constant (hence
monolith porosity is constant), then the monolith length is given by

In both cases d and L will vary across the monolith because in general Us will vary but the
conversion efficiency for all channels is constant i.e. optimum use of the monolith is ensured.
This assumes of course that the distribution of Us is known a priori.
The flow distribution across the monolith is governed by the upstream geometry and monolith
resistance, this being a function of Us and monolith dimensions. Hence an iterative design
approach is needed. Such an iterative solution is in principle possible using CFD. As mentioned
earlier the monolith normally is treated as a porous medium. The flow in the monolith is made
unidirectional by applying large transverse resistances whereas in the flow direction the
pressure loss is normally described by the HagenPoisieulle relationship for fully developed
laminar flow; the maximum channel Re being typically in the range 4001500. Hence within
the channel the pressure loss can be described as,

Where K = 28:454 for cells of square cross-sectional area. Eq. (10) neglects other losses
associated with the developing boundary layer and entrance effects [28]. These can be included
but for the sake of simplicity and without loss of generality Eq. (10) will be considered here.
By way of example if we are given values of c , L and w then Eqs. (8) And (10) give

Alternatively for given values of c, d and w Eqs. (9) and (10) give

Utilising Eqs. (11) and (12) for the flow resistance will therefore provide iterative solutions to
the velocity distribution Us across the substrate ensuring uniform conversion is achieved within
each channel. For the first case the channel hydraulic diameter d is subsequently obtained from
Eq. (8) and for the latter case the channel length L is obtained by Eq. (9). [16]

9) Outlook

Concern about Environmental, ecological and health has result in increasingly stringent
emissions regulations of pollutant emissions from vehicle engines. Among all the types of
technologies developed so far, use of catalytic converters is the best way to control auto exhaust
emission. Three-way catalyst with stoichiometric engine control systems remain the state of
art method for simultaneously controlling hydrocarbon, CO and NOx emissions from vehicle.
The economical reasons, limited resources of platinum group (noble) metal and some operating
limitations of platinum group metal based catalytic converters have motivated the investigation
of alternative catalyst materials.

10)Reference
[1] Willard W. Pulkrabek, Engineering Fundamentals of the Internal Combustion Engine, page
no 5-9.
[2]"History of Technology: Internal Combustion engines". Encyclopedia Britannica.
Britannica.com. Retrieved 2012-03-20.
[3] http://cecs.wright.edu/~mawasha/Chapter%201%20Class%20Notes.pdf
[4] Stone, Richard, Introduction to Internal Combustion Engines (2nd ed.). Macmillan. ISBN
0-333-55083-8, 1992
[5] Nunney, Malcom J. Light and Heavy Vehicle Technology (4th ed.). Elsevier ButterworthHeinemann. ISBN 978-0-7506-8037-0, 2007
[6] External combustion - Definition from the Merriam-Webster Online Dictionary
[7] B. P. Pundir, Engine emissions and air pollution, in: B. P. Pundir, Engine emissions
pollutant Formation and Advances in Control Technology, Narosa Publishinghouse, New
Delhi, Chapter No 1, page no 1-10
[8] R. Heck, R. Farrauto, Automobile exhaust catalysts, Applied Catalysis A: General 221,
page no 443-457, 2001.

[9]http://arrc.ebscohost.com/ebsco_static/repairtips/8852CH15_Crankase_Emission.htm

[10]Jan Kapar, Paolo Fornasiero, Neal Hickey, Automotive catalytic converters: current
status and some perspectives, Catalysis Today 77, Page no 419449, 2003

[11] Dr. Tom V. Mathew, IIT Bombay, Fuel Consumption and Emission Studies,
Transportation Systems Engineering, chap 43 February 19, 2014

[12] Carlos Moreno-Castilla * and Agustn F. Prez-Cadenas, Carbon-Based Honeycomb

Monoliths for Environmental Gas-Phase Applications, Materials, Page no 3, 2010.

[13] Lan TAO, Elizabeth Garnsey, David Probert and Tom Ridgman, Innovation as response
to emissions legislation: Revisiting the automative catalytic converter, page no 3, February
2009

[14] Femina Patel and Sanjay Patel, Recent Trends in Catalyst Development For Diesel Engine
Exhaust Emission Control, Journal of Environmental Research And Development Vol. 6, page
no. 4, April-June 2012

[15] Soji Adeyinka *, J U Okoli & Yousuo Digincni, Design and fabrication of catalytic reactor
for treating automobile exhaust, Indian Journal of Chemical Technology Volume II, page no
560-564, July 2004.

[16] S.F. Benjamin *, Z. Liu, C.A. Roberts, Automotive catalyst design for uniform conversion
efficiency, Applied Mathematical Modelling 28, page no 559572, 27 October 2003.