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CATALYTIC CONVERTER

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ABSTRACT
Growth in population and growth in number of vehicles every year
have combined together to give dramatic increase in both water and air
pollution problems. The automotive vehicles have been a significant
contributor to air pollution on total mass basis. According to one survey it
has been shown that transportation contributes about 42% (by wt.) of the
maor pollutants. !otor vehicles alone contribute about "#%. Transportation
contributes about $%% of the man made hydrocarbons (&')( a little over
)%% of the total carbon mono*o+ide (',) emission and about 4%% of the
nitrogen o+ide (-,+).
!aor pollutants from automobiles are unburned hydrocarbon
(./&')( o+ides of nitrogen( carbon mono+ide( lead compounds( and o+ides
of sulphur. The air pollution due to these pollutants affects adversely
materials( animals and human life. 0t reduces visibility to a large e+tent
causing traffic ha1ards. The vegetarian and plants are affected badly by
sulphur dio+ide( photo chemical smog and lead.

POLUTANTS PORDUCED BY ENGINES
0n order to reduce emissions( modern engines carefully control the
amount of fuel they burn. They try to 2eep the air*to*fuel ratio very close to
the stoichiometric point( which is the ideal ratio of air to fuel. Theoretically(
at this ratio( all of the fuel will be burned using all of the o+ygen in the air.
3or gasoline( the stoichiometric ratio is about 44.564( meaning that for each
2
pound of gasoline( 44.5 pounds of air will be burned. The fuel mi+ture
actually varies from the ideal ratio 7uite a bit during driving. 8ometimes the
mi+ture can be lean (an air*to*fuel ratio higher than 44.5)( and other times
the mi+ture can be rich (an air*to*fuel ratio lower than 44.5).
AUTOMOBILE EMISSIONS
Tailpipe emissions
9vaporative emissions
:ife cycle emissions
LITERATURE REVIE O! PREVIOUS OR"
8tudy of e+haust emissions and its control has been a matter of
concern from a long period for the engineers. The operating variables affect
the auto engine e+haust. The main variables for emitting pollution are &'(
', and -,+. ;reviously the auto engineers control the pollution emission
by following ways.
'ontrolling Air*3uel ratio
'ontrolling 9ngine 8peed
;roper 8par2 Timing
9+haust /ac2 ;ressure
<alve ,verlap
0nta2e !anifold ;ressure= <acuum
'ombustion 'hamber >eposit /uild .p
8urface Temperature
8urface to <olume ?atio
3
8tro2e to /ore ?atio
'ompression ?atio
9ffect ,f 'oolant Temperature
PROBLEM !ORMULLATION #ADVANCE OR"$
A lot of research wor2 has been done since 4#4%@s to chec2 the
menace of pollution by automobiles. There are many techni7ues to control
the e+haust pollution through automobiles e.g.
9+haust Gas ?ecirculation
Thermal ?eactor
!odification in 'ombustion 8ystem to Achieve 'omplete
'ombustion
0nection 8ystem
0gnition 8ystem
'arburetor
After /urner
9vaporative 9missions and 'ontrol
'ran2case 9missions and 'ontrol
-ow a day@s use of catal%tic con&erter dominates all other techni7ues.
'atalytic converter is used in the tail pipe of the e+haust system so that the
level of obno+ious emissions from the engine is reduced before they are let
out to the atmosphere.
To evaluate the performance and design of catalytic converter is made
which predicts the catalytic converter performance. Ae can optimi1e
catalytic converter design by adusting different parameters.
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'&A;T9?*4
INTRODUCTION
>eterioration of air 7uality is a maor environmental problem in many
large urban centers in both developed and developing countries. Although
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urban air 7uality in developed countries has been controlled to some e+tent
during the past two decades( in most of the developing countries it is
worsening and becoming a maor threat to the health and welfare of people
and the environment. 0n our modern society( 7uality of life is greatly
measured by the amount of consumption of electricity or by the use of car.
9lectricity generation and operation of vehicles mostly use fossil fuel. As
these fuels are burnt( huge 7uantity of lethal chemicals and poisonous
particulate matter are released as a part of emission into the surrounding
atmosphere due to incomplete combustion causing serious air pollution(
affecting public health. The contribution of motor vehicles to air pollution
was first recogni1ed by ;rof. &a1en 8mit who discovered that the two
invisible vehicular emissions namely hydrocarbons and o+ides of nitrogen
were responsible for the famous :os Angeles Bphotochemical smog@. These
gases interact with one another and other components of the atmosphere to
generate several harmful compounds vi1. carcinogens. The auto e+haust also
affects our valuable cultural heritage( historical places= monuments=
architecture and the environment. The number of vehicles in 0ndia has
increased from 4.C) million in 4#54 to "2 million in 4##) and about $"
million in 2%%%. !eteorological and topographical conditions affect
dispersion and transport of these pollutants in ambient air.
The growth in population and growth in energy consumption per
person have combined together to give dramatic increase in both water and
air pollution problems. The man2ind can survive without food and water for
few days( seldom the survival e+ists without air. Among several sources of
pollution( vehicles used in transportation sectors have a substantial share in
increasing atmospheric pollution.
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0t has been estimated that about )% D 5%% air pollution is from motor
vehicles. Almost all these are powered from 0.'. engines which use fossil
fuel such as gasoline or diesel oil. The increases in two and three wheelers
are aggregated the problem further. 0n an average motor vehicle with no
emission control device (4( ") the estimated values of annual production of
these pollutants is about 55% 2g. of carbon mono+ideE 24% 2g. of unburned
hydrocarbons and 4% 2g. of nitrogen o+ides. This 7uantity increased
proportionately with the no. of vehicles.
'(' E!!ECT O! POLLUTANTS ON ENVIRONMENT
<ehicles e7uipment with petrol or diesel engines emit considerable
amount of carbon mono+ide and unburned hydro carbonsE ,+ides of
nitrogen( compounds of lead o+ides of sulphur etc. The air pollution due to
these pollutants effects adversely on materials( animals and human life .0t
reduces visibility to a large e+tent causing traffic ha1ards. The vegetation
and plants are affected badly by sulphur dio+ide( photo chemical smog and
lead.
'() E!!ECTS O! AIR POLLUTANTS ON *UMAN *EALT*
Air pollutants emitted by motor vehicles have a number of adverse
effects on human health and ecology. >iseases such as silicosis(
pneumoconiosis( coniosis( allergy( asthma( inflammatory lung diseases(
infections and cases of mycoto+icosis and neurological or vascular disorders
have been associated with e+posure to pollutants and bio aerosols (bacteria(
fungi and their by*products). 9+posure by inhalation directly affects
respiratory( nervous and cardiovascular systems of humans( resulting in
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impaired pulmonary functions( sic2ness and even death. ;ollution hampers
the body normal immune system and conse7uently secondary diseases 2ill
the subect. ;ollution is a hidden enemy of civili1ation. There are no specific
drugs for the diseases cause by the pollution. ;ollutants thus give rise to
enormous health costs( in addition to the general discomfort and poor 7uality
of life in urban area.
Partic+late matters cause breathing and pulmonary disorders li2e
asthma( bronchitis( lowering of the general immune system( cancer and long
term irreparable damage to the lungs. CO binds with hemoglobin to form
carbo+yhemoglobin (',&b) which reduces the blood@s carrying capacity to
transport ,
2
to the tissues. SO
)
is 2nown to cause decreased lung functions
and a variety of respiratory diseases and increased ris2 of mortality and
morbidity. Adverse effects include coughing( phlegm( chest discomfort and
bronchitis. Nitro,en o-i.es/-,
2
is lin2ed with increased airway resistance
in asthmatics and decreased pulmonary function. -,
2
has been associated
with respiratory illness in children (cough( runny nose( and sore throat).
,ccupational e+posure to -,
2
range from inflammation of the mucous
membrane of the tracheobronchial tree to bronchitis( bronchopneumonia and
acute pulmonary edema. Lea. prevents hemoglobin synthesis in red blood
cells in bone marrow( impairs liver and 2idney function and causes
neurological damage. ;A& are 2nown as carcinogenic. O0one/adverse
health effects include changes in pulmonary function( eye( nose and throat
irritation( coughing( throat dryness( thoracic pain( increased mucous
production( chest tightness( lassitude( malaise and nausea.
Chloro1l+orocar2ons/e+posure to increased .<*/ radiation is suspected to
increase the ris2 of s2in cancer and eye illness especially cataract and to
adversely affect the immune system. Ben0ene 3 about $%% of inhaled
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ben1ene is adsorbed. ;art of the absorbed ben1ene is e+haled by respiration
and eliminated through the urinary tract. /en1ene is accumulated in the fat
tissue and bone marrow. /en1ene has to+ic and carcinogenic effects. The
to+ic effects are associated with central nervous system( hematological and
immunological systems. &igher e+posure can damage the respiratory
tract( lung tissue and bone marrow and cause death. 'arcinogenic effects
include leu2emia.
Pol%aromatic *%.rocar2ons 3 ;A& absorbed in the lungs and
intestines and metaboli1ed in the human body( are mutagenic and
carcinogenic. Al.eh%.es/are absorbed in the respiratory and
gastrointestinal tracts and metaboli1ed. Adverse health effects of &',&
include eye and nose irritation( irritation of mucous membranes and
alteration in respiration( coughing nausea and shortness of breath. Lea.
#P2$ / Tetraethyl lead was added to gasoline to increase the fuels octane
number( which improves the anti2noc2 characteristics of the fuel in spar2*
ignition engines.
'(4 POLLUTANTS EMISSIONS !ROM MOTOR VE*ICLES
9mission from vehicles especially automobiles contribute
significantly two third of air pollution in the urban area. !ain sources of
emission from automobiles are6
i$ Volatile Or,anic Com5o+n.s #VOCs$ 6 E&a5orati&e Emissions/ are &'
vapors lost constantly and directly to the atmosphere due to volatile nature
of petrol( mainly from the fuel line@s( fuel tan2 and carburetor depending
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upon fuel composition( engine operating temperature and ambient
temperature. :osses from the carburetor( called &ot 8oa2 9missions( occur
when a hot engine is stopped. 0t should be noted that out of total emissions(
which are much more in case of petrol than diesel( 2%*"2% of the total
emissions are due to evaporation losses( of which the &'s happen to be the
chief constituents. These gases are also 2nown as hydrocarbons and defined
as FvolatileF because of their ability to evaporate 7uic2ly and easily into the
air. They react with nitrogen o+ides in the presence of sunlight to produce
ground level o1one( a principle component of smog.
ii$ Cran7case Emission #also calle. r+nnin, loss emissions$ 3 are unburnt
or partially burned fuel components that( under pressure( escape from the
combustion chamber( pass the pistons and enter the cran2case. This mi+ture
is called blow*by. The main constituent of blow*by emission is &'s. 0f
uncontrolled( it may constitute 4"D2$% of total emissions. 8ince( diesel
engines compress only air( blow*by contain very low levels of pollutants.
iii$ E-ha+st Emission/ Automotive e+haust is the maor source constituting
about )%% of the total emission. Automobile e+haust consists wide range of
pollutants from simple to carcinogenic substances such as (4) &ydrocarbons
(.nburnt)( (2) 'arbon mono+ide( (") ,+ides of nitrogen (-,+)( (4) :ead
o+ides( ($) ;articulate matters e.g. lead( carbon( al2aline earth compounds(
iron o+ide( tar( oil( mist ()) Traces of aldehydes( esters( ethers( sulphur
dio+ide( pero+ides( 2etones ben1ene ('
)
&
)
)( 4( " butadiene( ;oly Aromatic
&ydrocarbons (;A&)( metal dust( asbestos fiber( dio+in( furan( ammonia(
organic acids ( chlorofluorocarbons ('3's) etc. .
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&ydrocarbons and ', appears in the e+haust gas products of
incomplete combustion. ,+ides of nitrogen result from the reaction of
nitrogen and o+ygen contained in the combustion air at high temperature
prevailing during combustion. 3urther( many of these primary pollutants
react with each other to form secondary pollutants. 'hief among these are
&'( ',( -,+ when mi+ed with atmospheric water vapors in presence of
sunlight form o1one and variety of comple+ organic gases and resultant
particulates 2nown as ;hotochemical 8mog (8harma( and Agnihotri( 4##2).
Partic+late Matter #PM$ includes particles of soot( ash( and dirt that are
released from car e+haust. ;articles are measured by their diameter and with
respect to smogE two si1es are of the most concern * ;!4% and ;!2.$.
;articulate matter and ground level o1one combine to ma2e up smog.
8ulphur >io+ide (8,2) gas contributes to smog formation( but is
2nown better for combining with water molecules to form sulphuric acid and
producing acid rain. A comparative sulphur content in diesel fuel in different
countries and pollution arise from different parts of the automobiles are
given in Table*4.
Table 46 !a+imum ;ermitted 8ulphur 'ontent in Automotive >iesel 3uel
E(C( Co+ntries 8 Mass
..G. %."
3rance %."
Germany %.2
0taly %."
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Others
'anada %.$
Hapan %.$
8wit1erland %.2
8outh Gorea 4.%
.8A %.$
In.ia 9(:
'(; EMISSION !ROM GASOLINE VE*ICLE
Gasoline* powered engines are of two types D 4 stro2es and 2 stro2es.
The e+haust consists of ',( &'( -,+( 8,
2
and partial o+ides of aldehydes(
besides particulate matter( lead salts account for the larger chun2 of all
pollution from gasoline*run vehicles.
The 2 stro2e engine re7uires 2*T oil for lubrication of engine. 8ince the
burning 7uality of mineral based lubricating oil is very poor( maor fraction
either remain unburned or burns partially and comes out through e+haust and
responsible for smo2e emissions.
TA/:9*2 9missions from Gasoline <ehicles
S(N( So+rce Amo+nt o1 Emissions #8$
;/stro7e )/stro7e
4 'ran2case blow by 2% *
2 9vaporative
9missions
2% "
" 9+haust 9missions )% #5
Table*" 9+haust 9mission from 0ndian :ight >uty Gasoline <ehicle
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The average 0->0A- light*duty gasoline vehicle annually emits
appro+imately6
;:99 7, o1 CO)
)99 7, o1 CO
)9 7, o1 VOCs
)) 7, o1 NO<
' 7, o1 SO<
9(': 7, o1 PM'9
9(': 7, o1 PM)(:
(based on data from the year 2%%%)
'(: EMISSION !ROM DIESEL VE*ICLE
>ue to low volatility( evaporative emissions are non*significant.
Though the concentration of ', and unburnt &' in the diesel e+haust are
rather low( they are compensated by high concentration of -,+. There are
smo2e particles and o+ygenated &'( including aldehydes and odour*
producing compounds.
'(= MA>OR POLLUTANTS
!aor pollutants from automobiles are6
(a) .nburned hydro carbons. (./&').
(b) ,+ides of nitrogen (-,+).
(c) 'arbon mono o+ides.
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(d) :ead compounds.
(e) ,+ides of sulphur.

(a) &ydro carbon e+haust emissions arise from three sourcesE
(i) Aall 7uenching(
(ii) 0ncomplete combustion of charge.
(iii) 9+haust scavenging as in a two cycle engines.
(b) 3ormation of nitric o+ide ta2es place within the combustion chamber
at the pea2 combustion temperature and remains there during e+pansion and
e+haust stro2e in non e7uilibrium amount. Ahen this -itric o+ide comes in
contact with atmospheric o+ygen( other compounds of nitrogen may be
formed.
I 'arbon mono+ide is generated from the automobiles largely by old and
petrol vehicles( due to in complete combustion of organic matters. 0t has no
smeltE inactivates hemoglobin and can be very harmful because it shows no
physiological symptom or uncomforted. &uman e+posure to this for longer
than eight hours at a concentration of about 42% ;;! should not be allowed
for more than one hour.
(d) Among anti 2noc2 additives T9: (Tetra ethyl lead ('2&$)4 ;b) is well
2nown. The effect of adding T9: is to reduce a non volatile combustion
product which tends to accumulate on the spar2 plug and cause the engine to
misfire. Therefore T9: is always blended with ethylene dibromide and
ethylene dichloride so that the lead compounds formed during combustion
are sufficiently volatile and are discharged through e+haust to atmosphere.
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(e) 8ulphur is present in the crude oil itself. >uring refining large amount
of sulphur is separated from the fuel. 8till there remains some of its amount
in the fuel. 0t forms o+ide of sulphur during combustion. These ,+ides of
sulphur from e+haust go to atmosphere. This sulphur o+ide may be
combined with sulphuric acid (&28,4)E a very corrosive secondary
pollutant.
C*APTER/)
AUTOMOTIVE ENGINE TYPES ? AUTOMOTIVE POLLUTION
S5ar7/i,nition an. Diesel en,ines are the two most common
engines. ,ther types of engines are ?otary (Aan2el) 9ngines( Gas*Turbine
(/rayton) 9ngines( 8team (?an2ine) 9ngines( 8tirling) 9ngines( 9lectric and
&ybrid <ehicles.
8pa
r2*ignition gasoline engines have either a )/Stro7e (the cycle is completed
in 2*stro2es of the piston) or ;/Stro7e .esi,n (the cycle is completed in 4*
stro2es( 8uction J'ompression J9+pansion or ;ower and J 9+haust
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8tro2es of the piston). 2*stro2e engines are cheaper( lighter and can produce
greater power output per unit of displacement( so they are widely used in
motorcycles( scooters and mopeds and small power e7uipment. 0t emits 2%*
$%% of their fuel unburned in the e+haust( resulting in high emissions and
poor fuel economy. All gasoline engines currently used in automobiles and
larger vehicles use the 4*8tro2e design. Advanced 2*8tro2e engines under
development would achieve lower emissions and fuel consumption than 4*
8tro2e engines.
)(' MODE O! VE*ICLE OPERATION AND EMISSION RATES
The vehicle operation is divisible into 4 modes or driving cycles6 #i$
I.le 6 Start Mo.e / when the engine of vehicle has been started. 0t is yet
stationary. At this stage there is high level of &' and ', and very low level
of -,
K
( #ii$ Acceleration/ the emission of &' and ', come down with rise
in -,
K
levels( #iii$ Cr+ise6Stea.% Mo.e/steady speed produces relatively
low concentration of &' and ', but high concentration of -,
K
and #i&$
Deceleration (a) free and while (b) applying bra2e* slow speed contributes
to more pollutants.
)() TYPES O! !UELS
;ollutant emissions from motor vehicles are determined by the
vehicle@s engine type and the fuel it uses. 0deal fuel must have certain
physical( chemical and combustion properties( such as high energy density(
good combustion 7ualities( high thermal stability( and low deposit forming
tendencies( compatibility with engine hardware( good fire safety( low
to+icity( low pollution( easy transferability and on*board vehicle storage.
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'ommonly use fuels are gasoline and diesel. Gasoline is a mi+ture of
hydrocarbon compounds which have been distilled from petroleum. 8ulphur
is a constituent in oilE low sulfur oil is in great demand as a fuel because the
8,
2
emission is reduced. :ow sulphur oil is called L8weetM.
Alternative fuels considered for vehicular use are natural gas (in
compressed or li7uefied form( Nat+ral ,as contains the lighter aliphatic
compounds( largely methane( '&
4
. A typical gas would be C%*#%% '&
4
( $
to 4% % ethane and the rest other compounds)( li7uefied petroleum gas
(:;G)( methanol (made from natural gas( coal or biomass)( ethanol (made
from grain or sugar) vegetable oils( hydrogen( synthetic li7uid fuels derived
from the hydrogenation of coal and various blends such as gasohol.
)(4 AIR POLLUTANTS !ROM MOTOR VE*ICLES
The maor pollutants emitted from ,asoline 1+ele. &ehicles are ',(
&'( -,+ and ;b while pollutants from .iesel/1+ele. &ehicles are particulate
matter (including smo2e)( -,
K
( 8,
2
( ;olyaromatic &ydrocarbons ;A&.
The composition of automotive and diesel e+hausts is characteri1ed
by greater amounts of carbon mono+ide and hydrocarbons than that of
emissions from other fuel burning processes. 3actors for automotive and
diesel e+haust emission( in pounds per 4(%%% gallons of fuel consumed
(Giver( 4#52)( are given in Table*4(
Table*46 9mission 3actors for Gasoline 9ngines and >iesel 9ngines (lb=4%%%
gal of 3uel$
S( No( Poll+tants Gasoline
En,ines
Diesel En,ines
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4 Partic+lates 44 44%
2 ,+ides of 8ulphur # 4%
" ,+ides of -itrogen 44" 222
4 'arbon mono+ide 2#4% )%
$ &ydrocarbons $24 4C%
) Aldehydes 4 4%
5 ,rganic acids 4 "4
C Ammonia 2 *****
# /en1o(a) pyrene %." g=4%%% gal %.4 g=4%%% gal
Car2on mono-i.e #CO$ / 'olorless and odorless gas( slightly denser
than air. ?esidence time and turbulence in the combustion chamber( flame
temperature and e+cess ,
2
affect ', formation. 'onversion of ', to ',
2
in
the atmosphere is slow and ta2es 2 to $ months. 0n developing countries the
transport sector account for $"% of ', emissions and the residential and
commercial sectors( 4)%.
*%.rocar2on Com5o+n.s #*C$ / 'ompounds consisting of carbon
and hydrogen and include a variety of other volatile organic compounds
(<,'s). !ost &'s are not directly harmful to health at concentrations found
in the ambient air. Through chemical reactions in the troposphere( however
they play an important role in forming -,
2
and ,
"
which are health and
environmental ha1ards. Among the various &'( methane ('&
4
) does not
participate in these reactions. ?emaining &'( non methane hydrocarbons
(-!&') are reactive in forming secondary air pollutants. -!&' are photo
chemically reactive.
Ben0ene an. Pol%aromatic *%.rocar2ons #PA*$ * !otor vehicles
emit to+ic &' including ben1ene( aldehydes and polyaromatic hydrocarbons
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(;A&). About C$ to #%% ben1ene emissions come from e+haust and the
remainder comes directly from gasoline evaporation and through distribution
losses. Toluene and +ylene &' compounds are present in the gasoline
whereas aldehydes( 4( " butadiene are not present in gasoline( diesel fuel(
ethanol or methanol but are present in their e+haust emissions as partial
combustion products.
-ote6 ;A& are emitted at a higher rate in e+haust of diesel*fueled vehicles
than gasoline Dfueled vehicles.
Nitro,en o-i.es #NO
K
$ / includes nitric o+ide (-,)( nitrous o+ide
( -
2
,)( nitrogen dio+ide (-,
2
)( dinitrogen trio+ide (-
2
,
"
) and nitrogen
pento+ide (-
2
,
$
). -, and -,
2
collectively represented as -,
K
( are the
main nitrogen o+ides emitted by vehicles. About #%% of these emissions are
in the form of -,. -, is produced in the vehicle engine by combustion of
nitrogen at high temperatures. -,
2
formed by o+idation of -,( has a
reddish brown color and pungent odour.
0n the atmosphere( -,2 involved in a series of reactions in the
presence of .< radiation that produce photochemical smog( reducing
visibility. 0t may also react with moisture to form nitric acid (&-,
"
)
aerosols. 0n the lower atmosphere (troposphere)( -,
2
forms ,
"
by reacting
with &'. 0n the upper atmosphere( it reacts with chlorine mono+ide to form
chlorine nitrates. 0n developing countries( the transport sector accounts for
4#% of -,
K
emissions and the power sector( 2$%E the industrial sector(
44%E the residential and commercial sectors( 4%% and other sources $%.
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S+l1+r .io-i.e #SO
2
$ / is a stable( nonflammable( none+plosive(
colorless gas. 0n the atmosphere( 8,
K
may be converted to sulfur trio+ide
(8,
"
) by reacting with ,
2
. 8,
2
and 8,
"
react with moisture in air to form
sulfurous (&
2
8,
"
) and sulfuric (&
2
8,
4
) acids may precipitate to earth as acid
rain. 8ulphates may also be produced through reaction of these sulfur
compounds with metals present in particulate matter.
O0one #O
4
$ / in the lower (troposphere) layer( ground level o1one (G:,) is
formed by the reaction of <,'s and -,
K
with ambient ,
2
in the presence of
sunlight and high temperatures. G:, is a maor constituent of smog in urban
areas and motor vehicles are the main emission source of its precursors. The
reactions that form G:, also produce small 7uantities of other organic and
inorganic compounds such as pero+yacetyl nitrate (;A-) and nitric acid.
G:, concentrations depend on the absolute and relative concentrations of
its precursors and the intensity of solar radiation( which e+hibits diurnal and
seasonal variations. Thermal inversions increase G:, concentrations.
Partic+late matter #PM$ / consists of fine solids and li7uid droplets
other than pure water that are dispersed in air. Total suspended particulates
are particles with an aerodynamic diameter of N5% m. ;! with an
aerodynamic diameter of 4% m 2nown as suspended inhalable particulate
matter= ?espirable 8uspended ;articulate !atter (?8;!) or ;!
4%
( remains
in the atmosphere for longer periods because of its low settling velocity.
;!
4%
can penetrate deeply into the respiratory tract and cause respiratory
illness in humans. ;! with an aerodynamic diameter of 2.$*4% m or less is
defined as fine particles (;!
2.$
)( while the larger ;! is called coarse
particles. -early all ;! emitted by motor vehicles consists of fine particles
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and a large fraction of these particles has an aerodynamic diameter less than
4m.
;!
2.$
can also be formed in the atmosphere as aerosols from chemical
reactions that involve gases such as 8,
2
( -,
K
and <,'. 8ulfates( which are
commonly generated by conversion from primary sulfur emissions( ma2e up
the largest fraction of ;!
2.$
by mass. ;!
2.$
can also form as a result of
solidification of volatile metals salts as crystals following cooling of hot
e+haust gases from vehicles in ambient air. Gasoline fueled vehicles have
lower ;! emission rates than dieselDfueled vehicles. ;! emissions from
gasoline fueled vehicles result from unburned lubricating oil and ash*
forming fuel and oil additives. ;! emitted by diesel*fueled vehicles consists
of soot formed during combustion( heavy &' condensed or adsorbed on the
soot and sulfates. These emissions contain ;A&. Aith the advancement of
emission control measures in engines( however( the contribution of soot has
been reduced considerably.
Blac7 smo7e( associated with the soot portion of ;! emitted by
diesel*fueled vehicles( is caused by ,
2
deficiency during the full combustion
or e+pansion phase. /lue( gray and white smo2es are caused by the
condensed &' in the e+haust of diesel*fueled vehicles. /lue or gray smo2e*
results from vapori1ed lubricating oil and white smo2e occurs during engine
start*up in cold weather. >iesel fuel additives such as /a( 'a and !g reduce
smo2e emissions but increase ;! sulfate emissions. These additives may
also increase ;A& emissions..
21
Chloro1l+orocar2ons #C!Cs$ / The source of '3' emissions from
motor vehicles is the 3reon gases used in air conditioners. '3' emitted into
the atmosphere rise to the stratosphere layer within 4% years and are
estimated to remain there for 4%% years. '3' molecules struc2 by .<
radiation release chlorine atoms( which destroy ,
"
by forming chlorine
mono+ide. 3urthermore( when a free ,
2
atom reacts with a chlorine
molecule( an ,
2
molecule is formed and a chlorine atom is released to
destroy more ,
"
.
C*APTER/4
CONTROL TEC*NOLOGIES !OR POLLUTION EMISSION
#LITERATURE REVIE O! PREVIOUS OR"$
8tudy of e+haust emissions and its control has been a matter of
concern from a long period for the engineers. The operating variables affect
the auto engine e+haust.
4(' E!!ECT O! OPERATING AND DESIGN VARIABLE ON *C ?
CO EMISSION
4('(' Air/!+el Ratio
3or a fuel 7uality( concentrations of many of these pollutants
are influenced by such factors as the air*fuel ratio in the cylinder at the time
of combustion( ignition timing( combustion chamber geometry( engine
parameters (e.g. 8peed( load and engines temperatures) and use of emission
22
control devices. <ehicles with electronic fuel inection engines maintain an
air*fuel ratio of about 44.56 4 (i.e. burning of 4 lb of fuel about 44.5 lbs of air
is needed( which is the stoichiometric= ideal ratio for the air*gasoline
mi+ture) to achieve complete combustion.
:ean mi+ture (&igher ?atios) produces less &' O ', emissions
while ?ich mi+ture (:ower ?atios) produces more ', O &' and low values
of -,+ emissions from unburned or partially burned fuel. The air=fuel ratio
is adusted ta2ing into consideration the emission and efficiency of an
engine. 0t is seen that most of the gasoline operated engines are adusted
within the air=fuel ratio of 4264). The air=fuel ratio and ignition timing are
readily adustable( both in design specifications and field tune up
adustments.
4('() En,ine S5ee.
9mission concentration is mar2edly reduced at higher engine speed.
;rimarily increase in engine speed improves the combustion process within
the cylinder by increasing turbulent mi+ing and eddy diffusion. This
promotes after o+idation of 7uenched layer. 0n addition increased e+haust
port turbulence at higher speeds promote e+haust system o+idation reactions
through deter mi+ing.
4('(4 S5ar7 Timin,
0t has been found that at a constant power of 4" /&; and 4$%% rpm( a
retard of 4%P from the manufacturers recommended setting of "%P //>'
reduced &' emissions by 4%% ;;!( but increased fuel consumption of 4%%.
23
The 4%% ;;! change for 4%P retard suggests the importance of precise spar2
timing and minimum distributor tolerance.
4('(; E-ha+st Bac7 Press+re
0ncreasing e+haust gases in the cylinder at the end of the cycle. 0f this
increase in residual does not increase the percentage dilution of the fresh
charge to a level where the combustion process is adversely affected( the &'
emission concentration will be lowered. The reduction arises from leaving
the tail end of the e+haust( which is rich in unburned hydrocarbons in the
cylinder. This tail is subse7uently burned in ne+t cycle.
4('(: Val&e O&erla5
0t has similar effects as that of bac2 pressure case. The charge is
further diluted with the residual gases. 8light valve overlap (about 2P)
provided minimum emission. Thus a slight amount of residual tail did lower
the average &' emission value. &owever a further increase in residual led to
an incomplete combustion and a &' emission increase.
4('(= Inta7e Mani1ol. Press+re
At a fi+ed mi+ture ratio and speed with best power timing there is no
effect of engine horsepower on hydrocarbon or carbon mono o+ide emission.
&owever because carburetor and distribute settings are variable in a vehicle(
there is a change in emission concentration as the throttle is varied at a
constant speed.
4('(@ Com2+stion Cham2er De5osit B+il. U5
24
!aor source of combustion chamber deposit is T9:( fuel additive
used to suppress the combustion 2noc2. >eposits act to increases. >eposits
also act as a sponge to trap raw fuel which remains unburned and adds to
e+haust hydrocarbons. >eposits build up also increases compression ratio
which in turn increases emission.
4('(A S+r1ace Tem5erat+re
'ombustion chamber surface temperature affects the ./&' emission
by changing the thic2ness of the combustion chamber 7uench layer and the
degree of after reaction. Aent Aorth ()) studied the effect of such changes
on hydrocarbon emissions of %."$ to %.$C ;;! he+ane per one degree
3ahrenheit (f) rise in combustion chamber surface temperature. 0n one test
an increase of 4%%P3 decreased emissions by "5%
4('(B S+r1ace to Vol+me Ratio
0t is desirable to minimi1e the surface area of the combustion chamber
because hydrocarbons emissions arise primarily from 7uenching at the
chamber mi+ture( a thin layer of &' is left on the wall surface. &ence by
decreasing the surface area for the same volume of the combustion chamber
we can reduce this emission.
4('('9 Stro7e to Bore Ratio
9ngine with small bore born and large stro2e have lower surface to
volume ratio. /ut this modification is opposed due to increased frictional
losses in case of long stro2e and practice is for short stro2e for reduced
friction( increased power and economy.
25
4('('' Com5ression Ratio
A large reduction in surface to volume ratio can be affected by
decreasing compression ratio. This increases the clearance volume greatly
with little increase in surface area. &owever( reduced compression ratio
results in lower thermal efficiency and reduced engine power. A decrease in
compression ratio reduces hydrocarbon emissions a second way when '.?.
reduces( thermal efficiency is lowered and as a re result e+haust gas
temperature is increased which improves e+haust system after reactions.
4() E!!ECT O! OPERATING AND DESIGN VARIABLE ON NO-
EMISSION
4()(' EC+i&alence Ratio
The e7uivalence ratio affects both the gas temperature and the
available o+ygen during combustion. Theoretically an increase in the
e7uivalence ratio from 4 to 4.4 results in an increase in the ma+imum cycle
temperature of 4%%P3 while o2 concentration occurs at an e7uivalence ratio
of %.#. The ma+imum cycle temperature with this lean mi+ture is lower that
with a richer mi+ture( but the available o+ygen concentration is much higher.
4()() S5ar7 timin,
0ncrease in spar2 advance at any load and speed results in an increase
in the no concentration.

26
4()(4 Inta7e Mani1ol. Vac++m
0ncrease in manifold vacuum decreases load and temperature and an
increase the mass of the residual gases( due to this ignition delay is increased
and flame speed is reduced. This results in increase in the time of
combustion. 0f the spar2 timing is 2ept constant the increase in manifold
vacuum would cause the greater part of the combustion process to occur
during the e+pansion stro2e. This would result in decrease of ma+imum
temperature of cycle and a corresponding decrease in -o concentration in
e+haust.
4()(;En,ine s5ee.
An increase in engine speed has a little effect on ignition delay(
results in an increase in the flame speed due to turbulence and reduces heat
losses=cycle. This tends to raise compress and combustion temperature and
pressure. 0t spar2 timing is held constant a greater portion of this combustion
tends to occur during e+pansion where temperature and pressure are
comparatively low. This is slowest for burning mi+ture ratio 4#64. 3or richer
mi+ture( which burn faster( the effect of reduced heat losses at higher speed
predominates. This implies that an increase in the rate of no formation due to
reduced heat losses opposed by a reduction in the rate of no formation due to
late burning. 3or rich mi+tures where combustion and -, formation are( the
former effect predominates. 3or lean mi+tures where combustion and no
formation are rapid( the former effect predominates. 3or lean mi+tures where
combustion and no formation are flow the later effect predominates.
27
4()(: E11ect o1 Coolant Tem5erat+re
An increase in coolant temperature results in a reduction in the heat
lost to the cylinder walls and an increase in ma+imum gas temperature. This
results in an increase in -o concentration and vice versa.
4()(= *+mi.it%
An increase in the mi+ture humidity is mainly due to the drop in
ma+imum flame temperature which reduces -o formation( !oore (5) has
calculated that 4% (by weight) of water vapour reduced a hydrogen*air
ethylene air flame temperature by ")P3. This reduced the initial rate of -o
production by about 2$%.
C*APTER/;
CONTROL TEC*NOLOGIES !OR POLLUTION EMISSION
#ADVANCE OR"$
0f we adust above design and operating variables we can minimi1e
9+haust emission pollution but we are not able to do so and to maintain the
e7uilibrium along different variables. The following techni7ues have been
used to reduce the e+haust emission6
;(' E-ha+st Gas Recirc+lation
A portion of the e+haust gas is recirculated to the cylinder inta2e
charge. This reduces the pea2 combustion temperature( since the inert gases
absorb a large 7uantity of heat. This also reduces the 7uantity of o+ygen
available for combustion. The e+haust gas for recirculation is directly ta2en
from the stove area through an orificeE 0t passes through the butterfly control
28
valve for regulation of the rate and ducted down to the throttle shaft by
means of appropriate lin2age and the amount of valve opening is recycle
e+haust is normally shut off during full throttle acceleration to prevent loss
of power when ma+imum performance is needed. There will be a little effect
on -o+ emission even if the above arrangement is not made because -on
concentrations in idle and full throttle are already very low. ?eduction of the
pea2 combustion temperature by 9G? reduces the formation of -o+.
;() Thermal reactors
A thermal reactor is a chamber in the e+haust system designed to
provide sufficient residence time to allow appreciable homogeneous
o+idation of 'o and hydrocarbon to occur. 0n order to improve co conversion
efficiency( the e+haust temperature is increased by spar2 retard. This
however( results in fuel economy loss. Thermal reactor consist of two
enlarged e+haust manifold which allow greater residence time for burning of
&' and ', with o+ygen in the air( which is pumped. A cylindrical reactor
with a tangential entry from the e+haust manifold is attached to the engine.
8econdary air pumps inect fresh air into the reactor to 2eep a flame
constantly burning and thereby assuring complete combustion.
;(4 Mo.i1ication in Com2+stion S%stem to Achie&e Com5lete
Com2+stion
The undesirable e+haust emission of vehicle is formed mainly within
the combustion process. >ue to improper vapori1ation of fuel in inlet
29
manifold incomplete combustion results which leads to liberation of 'o and
&' modification such as heating the inlet air(4)( enhances the vapori1ation
of li7uid gasoline and improve mi+ture distribution among the cylinder
resulting in a better. 'ombustion which reduce &c and 'o.
;(; InDection S%stem
The obective of the inection system is to atomi1e and distribute the
fuel throughout the air in the cylinder while maintaining prescribed fuel*air
rations. To accomplish these tas2s a number of functional element might be
re7uired within the system.
(a) ;umping elements6 to move the fuel from fuel tan2 to cylinder.
(b) !etering element6 to measure and supply the fuel at the rate
demanded by the speed and load.
(c) !etering control6 to adust the rate of metering elements for changes
in load and speed of the engine.
(d) !i+ture control6 to adust the ratio of fuel rate to air rate as demanded
by the load and speed.
(e) >istributing elements6 to divide the metered furl e7ually among the
cylinders.
(f) Timing control to compensate for changes in temperature and
pressure of either air or fuel or engine that affects the elements of the
system.
(g) Ambient control6 to compensate for changes in tem. And pressure of
either air or fuel or engine that affects the element of system.
30
(h) !i+ing 9lement6 to atomi1e that fuel and mi+ with air to from a
homogeneous mi+ture.
These changes ensure precise fuel metering in accordance with changing
engine re7uirements at low and high loads.
;(: I,nition S%stem
0gnition system modification is carried out for burning leaner air
fuel mi+ture. :ean mi+tures have higher brea2down voltage than do slightly
rich mi+tures. Good ignition depends upon the following reasons.
(a) :ength of air gap of the spar2 plug the greater the gap( the larger is
the re7uired brea2down voltage.
(b) Geometry of the gap6 ;ointed electrodes re7uire less brea2down
voltage.
(c) The temperature of the electrodes and enclosed air fuel mi+ture6 high
temperature allow lower brea2down voltage
(d) The density of mi+ture6 higher density re7uires high brea2down
voltage.
(e) The lea2age resistance of the insulator6 carbon and metallic o+ides
from electrically conductive coatings on the insulator which thus
shunt the secondary winding and reduce the ma+imum voltage that
the secondary can impress across the spar2 gap.
(f) The rate of increase of the voltage at the gap6 if the ignition system
builds up the voltage at a rapid rate( the effect lea2age will be
minimi1ed and a Grater spar2ing voltage is available.
(g) The presence of ioni1ed gases in the gap6 Good ignition system also
depends on following point.
31
A combustible mi+ture must present between the electrodes. 3or this
reason( a spar2 plug location near the inta2e valve is desirable(
although opposed by the necessity to locate the plug near the hot
e+haust valve to avoid 2noc2.
A large gap increases the probability of regular firing( especially at
parts loads( when stratification from e+haust gas dilution is present.
A high mi+ture density allows a greater amount of energy to be
liberated and probability of ignition is increased.
0gnition is best secured with slightly rich mi+tures( since a greater
release of energy is obtained.
The position of the plug and the position of the electrodes relative to
the flow conditions in the chamber.
;(= Car2+retor
!ain wor2 of carburetor is to meter( atomi1e( vapori1e and mi+ the
fuel with air. 0f carburetor modifications are such that to ensure precise fuel
metering in accordance with changing engine re7uirements at low and high
loads.
;(@ A1ter B+rner
The after burners designed to o+idi1e ./&' and ',E includes a pre*
combustion chamber where secondary air and fuel are ignited by a spar2 to
provide thermal energy for the reaction.
32
;(A E&a5orati&e Emissions an. Control
>iurnal and &ot soa2 emissions have been controlled by venting the
fuel tan2 to the atmosphere through a canister of activated carbon. The
volatile nature of gasoline can be minimi1ed by 2eeping gasoline ?eid <apor
;ressure of 4% psi. Gasoline with an ?<; of 44 psi will produce about twice
the evaporative emissions of gasoline with an ?<; of C.5 psi.
;(B Cran7case Emissions an. Control
'ran2case emission controls involve closing the cran2case vent port
and venting the cran2case to the air inta2e system via a chec2 valve. 0n
newer model cran2case blowDby are controlled by recycling to the engine
through the inta2e system.
;('9 Catal%tic con&erter
The principal of catalytic converter is to control the emission levels
of various pollutants by changing chemical characteristics of the e+haust
gases.
9+cept catalytic converter above method re7uire additional changes
in the engine design. 0n the e+haust gas recirculation method( is basically to
reduce the concentration of only one specie i.e. -o+. and may increase the
concentration of other constituents. Thermal reactors need additional
combustion chamber and spar2 ignition systems which ma2e it more
e+pensive. This may also increase the combustion of fuel.
33
0n modern practice catalytic converter has been effectively used
because it has some additional benefits e.g.
-o additional fuel is necessary to initiate or sustain reaction.
Temperature inside the catalyst 1one is lower( which reduces the
problem of construction material.
8ystem is self initiating at e+haust gas temperature and does not need
spar2 plug or other device.
8ystem operates even at low level of &' and ',.
C*APTER/:
CATALYTIC CONVERTER
:(' *istorical Bac7,ro+n.
Air pollution problems became serious in 4#4%s and many nations
too2 a serious view of it and some legislation was introduced since then in
4#)C most of the automobile. !anufacturers started introducing some from
of emission control devices( such as catalytic converters. There were studied
e+tensively in 4#$5*)4 and again appeared in 4##%s when it was recogni1ed
to get large reductions in pollutants from the e+haust. <arious materials such
as platinum or its group metals have been used for reduction of pollutants.
/esides of them o+ides of base metals( such as copper( nic2el( chromium
34
and magnise were also used as o+idi1ing catalyst( which had shown
significant reduction in pollutants.
/ase metal alloys such as copper*nic2el( and copper*Qin2 were
successfully used as a catalyst. These alloys along with noble metals
supported on alumina formed a dual catalyst system the reducing catalyst for
reducing nitrogen o+ides has been 2ept in first half of the converter and the
second half is pac2ed with o+idation catalyst. This would give out some
o+ygen for o+idation reactions in the second half( so as to improve the
reduction mechanism.
Three way catalyst systems generally 2nown as T.A.'. have been
come into operation and are being widely used. A three way catalyst system
is employed to promote the o+idation and reduction reactions
simultaneously. The converter contains a catalytic element in a cylindrical
bloc2 with a large number of channels forming a honey comb structure. The
active material( platinum and pollodinum( platinum and rhodium in different
combinations are dispersed over the outer surface of alumina. Ahen the
e+haust gases pass over the honey comb structure they would be in contact
with the catalyst and would get o+idi1ed and reduced simultaneously.
Gandhi /lum berg et al&ansel /aruah &ammerle and many others
evaluated the three way catalyst system under different operating conditions
and the performance of a T.A.'. catalytic converter has been found very
encouraging for reduction of pollutants( improved fuel economy and a
negligible loss of engine power.
0t has also been felt that duel catalyst system would be better than
T.A.8. for certain operations. Ahether it is a three way catalyst or a dual
catalyst system the catalyst used are made of noble metals li2e platinum(
35
palladium and rhodium which are very e+pensive and application to
automobile industry in the country would mean additional cost.
'hing &.wu and &ammerle then presented a solution for the
development of a low cost stable T.A.'( 8ystem. This consists of cheaper
palladium in one half and platinum and rhodium in second half to give an
improved performance of converter at a comparative cheaper cost. The
operation of three way catalyst re7uires a very close control of air fuel ratio
in the vicinity of the stoichiometric air* fuel ratio. This re7uires sophisticated
electronically operated closed loop feed bac2 control. T.A.'. system gets
poisoned by lead( phosphorous and sulphur dio+ide which are also present in
e+haust gases. This deactivates the catalyst and re7uires a replacement cost.
Therefore( the necessity of a low cost thermally stable catalyst preferably
from indigenous sources for the reduction of the pollutants having same
activation period as that of other noble metals. /ase metal o+ides such as
copper o+ide( iron o+ide( chromium o+ide( and magnese o+ide can easily be
used for reduction. 'opper and -i alloy
2nown as !onel( is available in sheet form and could be easily which is
indigenously available can also be used as a catalyst. This has got a tendency
to promote o+idation and reduction of the pollutants. 3or an automobile
industry( the primary consideration of selecting a catalyst is its cost
effectiveness and availability of material. A newly (4##") searched
compound B9conogreen@ has been used as catalytic converter and it is given
pollution control chec2 certificate.
Galen et al. investigated the alternatives to the ?hodium. Aith
Aorld*wide growth of the automotive emissions control mar2et( concerns
about future cost and availability of catalytic metals( particularly ?hodium(
have also grown. These factors have led to an increased interest in catalyst
36
formulations which might allow reduced ?h usage or the complete removal
of ?h from the catalyst without compromising the performance of the
emission control system. They had tested a set of catalyst to e+amine ?u( 0r(
and ;d as alternative to ?h( either alone or in combination with ;t. They
found that addition of ;d (or ?h) always improves the activity of ;t=;d
system over ;t=?h formulation.
;orter B>oyle et al. have studied the performance characteristics of
o+idation catalyst in heavy duty application and reviewed the optimi1ation
process re7uired to match the system to the application. They reviewed the
recent research by 8vens2a emissions Te2ni2 A / and ?ecardo to investigate
the potential and performance characteristics of catalysts for the application
together with a critical e+amination of the matching process re7uire to
optimi1e the engine and catalyst as a system. They concluded a sound
udgment to meet the 4##4 standards of emissions from automobiles.
8uresh T. Gulati published a paper on the development and successful
application of ceramic catalytic converters for controlling automotive
e+haust emission. They designed the high surface area to meet both
performances( durability re7uirement. They followed a step by step design
process for each of the converter components. The initial design stage
focuses on understanding automa2ers re7uirements and optimi1ing
component design commensurate with them. The intermediate stage
0nvolves laboratory testing of converter component in simulated
environment and ensuring component compatibility from durability point of
view. The final design stage addresses the critical tests on converter
assembly to ensure performance and field durability. They also e+amined the
necessary trade*offs and associated design modification and evaluates their
impacts on warranty cost on system failure. They focused on integrated
37
design approach for failure free operation of catalytic converter over the
vehicles li2e them. &urley et al. studied about electrically heated catalyst to
meet stringent 'alifornia and federal 4##"=#4 emission standards. They
focused specific attention on the cold start characteristics of the vehicles
emission system. 8pecially that of the catalyst. 3rom test data it is evident
that maor portion of the total & ' and 'o emission occur within the first
two minutes of the driving cycle. ,f The use of an electrically heated
catalyst (9&') is shown to be advantageous in lowering cold start emissions
during this portion of the drive cycle. They showed the effect on emissions
from the stand point of 9&' location( catalyst volume( and engine
calibration in an overall emission improvements have been at a premium( i.e.
lower fuel economy( additional vehicle weight( power consumption( and yet
to be totally accessed 9&' durability.
!artin . &eimrich added some improvement in the &urley@s efforts
for electrically heated catalyst. 0n his 8tudy he inected air ahead of an
electrically heated catalyst during cold start operation. &e continuously
recorded raw e+haust emissions. Analysis was used to determine air
inection calibration and o+idation reduction trade offs. 0mproved control of
non methane hydrocarbons (-!&')( ben1ene( and carbon mono o+ide (co)
emission control was maintained by the use of carefully controlled air
inection flow rate and schedule. They determined that heating an
automobile e+haust emission catalyst prior to cold start operation may not be
sufficient in itself. 8upplemented o+ygen may be re7uired for improved
emission control.
>ouglas H. ball and ?obert Gattac2 gave a theory about the diesel
e+haust catalysis using an o+idation flow*through type catalyst to reduce
particulate emission. They discussed about converter design( catalyst support
38
materials and the use of nodle metals for light and heavy duty applications.
They performed e+periments to determine the sulphur storage and release
characteristics of alumina and silica catalyst support materials and the ability
of platinum and palladium to o+idi1e so2 to sulfate particulate.
!itsure et algave a techni7ue to reduce -o+ in diesel engine e+haust.
'opier iron e+changed 1 sm*$ 1eolite catalyst( which reduces nitrogen
o+ides (-o+) in the presence of o+ygen and hydrocarbons( was applied to
actual diesel engine e+haust. 'opper ion e+changed 1sm*$ 1eolite effectively
reduced -o+ by 2$% in normal engine operation and by C%% when
hydrocarbons in the e+haust were increased. Aater in the e+haust gas
decreased the -,+ reduction efficiency but o+ygen and sulphur appeared to
have only a small effect. !a+imum -,+ reduction was observed at 4%%Pc
irrespective of hydrocarbon species.
!asaa2i Ta2iguchi et al. gave a techni7ue to reduce the -,+ from
diesel engines with -&" as reducing agent -&" is one of the most useful
compounds that react with -,+ selectively on a catalyst( such as v2o$* Ti
o2( under o+ygen containing e+haust gas. &owever ammonia can not be
stored because of its to+icity for the small power generation in populated
areas or for the diesel vehicles. This system is constructed from the
hydrogen generation by fuel reformer( the -&" synthesi1er( 8'? catalyst for
-,+ reduction and the gas inection system of reformed gas into the
cylinder.
?. /ec2mann et ale+plained the wor2ing and use of a precious metal
based( flow*through type diesel o+idation catalyst. &e paid much attention to
the durability of the diesel o+idation catalyst and especially to the influence
of poisoning elements on the catalytic activity. 8tarting from 4#C4 an
increasing number of diesel passenger cars in 9urope have been e7uipped
39
with this type of precious metal based catalyst. The main function of this
flow*through type catalyst( containing precious metal( are the conversion of
the gaseous pollutants carbon mono*o+ide and hydrocarbon as well as the
o+idation of hydro carbon components absorbed on the soot. Therefore it is
possible to reduce the amount of particulates emitted by the diesel o+idation
catalyst in such a way that it selectively cataly1es the o+idation of carbon
containing components at the low e+haust gas temperature typical for diesel
engine at partial load operation( and that it does not o+idi1e sulphur dio+ide
or nitrogen o+ides in the range of high e+haust gas temperature occurring at
full load.
!a2oto &oriache studied the effects of flow*through type of o+idation
catalysts on the particulates reduction of 4##%@s diesel engines. The
reduction behavior of diesel particulate and so 3 by flow through type
o+idation catalysts was investigated under steady and dynamic engine
conditions using a current fuel (8.'ontentE%."C% by wt.). 9ach catalyst gave
4%*#%%( soluble organic fraction (8,3) reduction at e+haust gas temperature
between 4%%P' to $%%P'. 8,3 is absorbed on catalyst surface at lower
temperature and is decomposed at the higher temperature ;T only load
catalyst which has high 8,2 o+idation ability resulted in a low total
particulate reduction due to high sulfate formation at higher temperature
even when low sulphur fuel was used.
;aul Qeien2a did research wor2 on reduction of diesel e+haust
emissions by using o+idation catalysts. ?esearch describes the result wor2
concerning the investigation and optimi1ation of o+idation catalysts for
diesel engines( especially for passenger cars and light duty truc2s.
40
:() UNLEADED PETROL CAN NOT PLUG POLLUTION
IT*IOUT CATALYTIC CONVERTER
A 'atalytic converter ('') is placed inside the tailpipe through which
deadly e+haust gases containing unburnt fuel( ',( -,+ and air are emitted.
The function of the '' is to convert these gases into ',
2
( water and -
2
.
.nleaded petrol if used with catalytic converters could chec2 pollution.
.nleaded petrol has a low density and therefore( it evaporates fast.
'urrently( it is compulsory for all automobiles plying on roads in .8
and Hapan to have catalytic converters as they use unleaded petrol. 0n 0ndia(
the government has made catalytic converters mandatory for registration of
new cars. /ut what about old cars whose engine can get damaged due to
prolonged use and two*wheelers and three wheelers which account for )%%
of vehicular pollutionR
:(4 PROBLEMS IN USE O! CATALYTIC CONVERTER
-obel metals li2e platinum( rhodium and palladium re7uired to ma2e
good catalytic converters is also not available in 0ndia. To increase the
efficiency of fuel( ben1ene is added to petrol. 0n leaded petrol( the ben1ene
content was $% which have been brought down to "% in unleaded petrol.
0nterestingly( the permissible euro limits are ust 4% for ben1ene.
:(; TYPES O! CATALYTIC CONVERTER
The catalytic converter is one of the most effective emission control
devices available. Two types of catalytic converters are commonly used in
automotive engines.
41
TEo/Ea% catal%tic con&erters #O-i.ation$ / used in diesel* fueled
vehicles can reduce ', emission by C%% and a large portion of &'
present in particulate matter emissions.
Three/Ea% Catal%tic Con&erters #O-i.ation3Re.+ction$/ installed
on gasoline fueled vehicles can reduce ', and &' emissions by
about #%% and -,
K
emission by 5%% from uncontrolled levels.
Lean nitro,en/o-i.e Catal%st/ is a new type of catalytic converter
which reduces -,
K
emissions in lean conditions where a three*way
catalyst is ineffective.
:(;(' A TO/AY CATALYTIC CONVERTER *AS
TOSIMULTANEOUS TAS"F
4. o+idationof carbon mono+ide to carbon dio+ide6 2', S ,
2
T 2',
2

2. ,+idation of unburnt hydrocarbons (unburnt and partially*burnt fuel)
to carbon dio+ide and water6 2'
+
&
y
S (2+Sy=2),
2
T 2+',
2
S y&
2
,
This type of catalytic converter is widely used on diesel engines to reduce
hydrocarbon and carbon mono+ide emissions. They were also used on spar2
ignition (gasoline) engines in .8A mar2et automobiles up until 4#C4( when
they were replaced by three*way converters due to regulatory changes
re7uiring reductions on -,
+
emissions.
?eduction of the -,
+
emissions re7uires an additional step. ;latinum
catalysis can be used. 0nstead of catalysis( a true reactant U diesel fuel or
42
ammonia pyroly1ed in situ from ureaU can be used to reduce the -,
+
into
nitrogen.
'uriously( the regulations regarding hydrocarbons vary according to the
engine regulated( as well as the urisdiction. 0n some cases( Fnon*methane
hydrocarbonsF are regulated( while in other cases( Ftotal hydrocarbonsF are
regulated. Technology for one application (to meet a non*methane
hydrocarbon standard) may not be suitable for use in an application that has
to meet a total hydrocarbon standard. !ethane is not to+ic( but is more
difficult to brea2 down in a catalytic converter( so in effect a Fnon*methane
hydrocarbonF standard can be considered to be looser. 8ince methane is a
greenhouse gas( interest is rising in how to eliminate emissions of it.
:(;()T*REE/AY CATALYTIC CONVERTERS #O<IDATION/
REDUCTION$
9nsuring good 7uality air is essential for the protection of public
health. Governments worldwide have adopted a range of increasingly
demanding measures to curb air pollution with a particular focus on the
emissions from motor vehicles. An important part of this strategy has been
the development of the three*way catalytic converter to remove e+haust
pollutants such as carbon mono+ide( unburnt hydrocarbons and nitrogen
o+ides. This unit ta2es an in*depth loo2 at the construction of this converter
for petrol*driven vehicles and investigates the catalytic chemistry ta2ing
place at the molecular level. 0t is assumed that you already have a scientific
bac2ground.
43
The three*way catalytic converter
:(;()(' COMPOSITION
The current three*way catalyst( shown schematically in 3igure 4( is
generally a multicomponent material( containing the precious metals
rhodium( platinum and (to a lesser e+tent) palladium( ceria ('e,
2
)( V*
alumina (Al
2
,
"
)( and other metal o+ides. 0t typically consists of a ceramic
monolith of cordierite (2!g.2Al
2
,
"
. $8i,
2
) with strong porous walls
enclosing an array of parallel channels. A typical monolith has )4 channel
openings per cm
2
(4%% per in
2
)( This design allows a high rate of flow of
e+haust gases 'ordierite is used because it can withstand the high
temperatures in the e+haust( and the high rate of thermal e+pansion
encountered when the engine first starts D typically( the e+haust gas
temperature can reach several hundred degrees in less than a minute.
!etallic monoliths are also used( particularly for small converters( but these
are more e+pensive.
44
3igure 4. 8chematic diagram of the three*way catalytic converter.
To achieve a large surface area for catalysis( the internal surfaces of
the monolith are covered with a thin coating ("%D$% Wm) of a highly porous
material( 2nown as the Eashcoat (3igure 2). The total surface area is now
e7uivalent to that of about two or three football pitches. The washcoat
generally consists of alumina (5%DC$%) with a large surface area( with
o+ides( such as /a,( added as structural promoters (stabili1ers to maintain
surface area) and others( for e+ample 'e,
2
( as chemical promoters. This
system becomes the support for the precious metal components (;t( ;d and
?h). These metals constitute only a small fraction (4D2%) of the total mass
of the washcoat( but they are present in a highly dispersed form. They are
generally applied by deposition from solution( although they may instead be
introduced during formation of the washcoat itself. 9+act catalyst
45
formulations are( as one might e+pect( closely guarded secrets. 8ome
compositions use all three metalsE others use ?h together with only one of
the other two( typically ;t( as in the present generation of ;t*?h converters
used in the .G( in which ;t constitutes C%D#%% of the total precious metal
mass
3igure 2. 9lectron micrograph of a cross section of a ceramic monolith coated with an
alumina washcoat
:(;()() CATALYST PER!ORMANCE
3igure " shows the difference in the emission levels for ',( <,' and
-,
x
for a vehicle( with and without a three*way catalytic converter. 0t is
evident that the catalytic converter reduces the emissions of all three classes
of pollutants 7uite dramatically over a wide range of speeds. /efore we
discuss the data in any detail( a few words about how they were obtained are
in order.
46
!i,+re 4 9mission levels for ',( <,' and -,x for petrol*engine vehicles as a function
of speed( with (green) and without (blac2) a three*way catalytic converter.
3ederal and 9uropean Test ;rocedures are used to test emissions from
a complete Bfinished@ converter and engine together( to ensure that a new car
model( for instance( will meet the current emissions legislation. 8ome sort of
smaller*scale testing is obviously re7uired in the laboratory. 0n the research
and development of automotive catalysts( activity testing fulfils the function
of screening and comparing novel and modified catalysts( and e+amining
their performance under different conditions. The process of screening must
provide a reliable means of identifying materials that will perform as active(
selective and durable catalysts under automotive conditions. The approach
usually ta2en is to measure conversion of the pollutants as a function of
47
temperature( using a simulated e+haust*gas mi+ture flowing through a bed of
powdered catalyst6 the flow*rate has to be high enough to mimic the
Bthrough*put@ or s5ace &elocit% of a catalytic converter (typically a contact
time for the gases with the catalyst of 52 milliseconds is used). The test is
then repeated using a different simulated e+haust*gas to represent a different
engine mode. Ageing studies are performed by e+posing the catalyst to
different and often e+treme conditions( for varying lengths of time.
!i,+re ; Activity of a three*way catalyst for the simultaneous conversion of ',
(blac2)( -,x (solid green) and the hydrocarbon propene ('"&)) (dotted green)
3igure 4 shows a typical graph of catalytic performance over the
normal range of operating temperature( 4%%D)%% P'. .ntil the incoming
gases have heated the catalyst to around 2$%D"%% P'( the activity of the
catalyst is low. This temperature( at which the efficiency of the catalyst
rapidly increases( is 2nown as the li,ht/o11 tem5erat+re. .ntil this
temperature is reached( the catalyst is not wor2ing at full efficiency( and so
',( -,
x
and hydrocarbons will all be emitted from the e+haust pipe in
48
significant amounts. This problem is 2nown as col. start. 0deally the light*
off temperature should be as low as possible.
:(;()(4 E-ha+st Emission Characteristics
Before we consider how the three-way catalyst functions in any
detail, it is important to understand how the emissions of CO, HC and
NO
x
, from the engine depend on the ratio of air (A) to fuel (F) the
air/fuel ratio (or A/F ratio) !he si"nificance of this will #ecome
clear when we see that the ratio at which the three-way catalytic
con$erter operates is crucial for its success
Ta2ing octane ('
C
&
4C
) to be the only constituent of fuel( and assuming
that air is 2%% ,
2
by volume( estimate the stoichiometric A=3 ratio (mass
ratio) re7uired for total combustion to occur. At this stage neglect the effect
of -, as an o+idant. 'omment on the difference between the value you
obtain and the e+perimental value of 44.564 (.se the following relative
atomic masses6 '( 42.%4E &( 4.%4E ,( 4).%%E -( 44.%4.)
The stoichiometric e7uation for the complete combustion of octane
can be written as follows6
'
C
&
4C
S 42
4
=
2
,
2
X C',
2
S #&
2
,
8o combustion of 4 mol of octane will re7uire 42.$ mol of o+ygen.
Assuming air to be appro+imately 2%% ,
2
and C%% -
2
(by volume)( the
mass o1 air re7uired will be 42.$ ("2.%% S 4 Y 2C.%2) g X 4C%4 g.
49
The mass o1 ' mol of octane is (C Y 42.%4 S 4C Y 4.%4) g X 444.2) g.
Thus( the A=3 mass ratio for complete combustion is6
A=3 X 4C%4=444.2)
X 4$.C64
!i,+re : The effect of changing air=fuel ratio on the levels of -,x (solid green)( ',
(blac2) and &' (dotted green) produced in the en,ine. The diagram also shows
7ualitatively how the engine power output changes with the A=3 ratio.
This is as close as you would e+pect to the e+perimental value of
44.564( because we have used a very simplified system. Ae had not included
-, as an o+idant or the other hydrocarbons( ', or &
2
as reductants( and we
have used octane( not the real mi+ of hydrocarbons in petrol.
A general relationship between levels of ',( &' and -,
x
released
from the engine and the A=3 ratio is shown in 3igure $. At A=3 ratios
50
somewhat a2o&e stoichiometric (44.564) D that is( when the engine is
operating under 1+el/lean( net o+idi1ing conditions D low levels of &' and
', are produced in the engine( and there is a pea2 in -,
x
concentration. At
higher A=3 values( -,
x
falls( but the hydrocarbon concentration increases as
the engine begins to misfire.
!i,+re = Activity of a three*way catalyst for the simultaneous conversion of -,x (solid
green)( ', (blac2) and &' (dotted green) as a function of the air=fuel ratio. The shaded
area defines the window for conversions of C%% and above for all three pollutants. (-ote
that( for clarity( the A=3 ratios are e+pressed as the amount of air per unit of fuel( e.g. 44.5
instead of 44.56 4. Ae shall use this notation for the rest of this unit.)
Ahen the e+haust gas is close to its stoichiometrically balanced
composition( at an A=3 ratio of about 44.564( the concentrations of o+idi1ing
gases (-, and ,
2
) and reducing gases (&' and ',) are matchedE in theory(
it should then be possible to achieve complete conversion to produce only
',
2
( &
2
, and -
2
. This is( of course( the obective of the three*way catalytic
converter( and so( ideally( it should be operated in a narrow band( or
51
Ein.oE( close to the stoichiometric ratio( within which it will promote
sim+ltaneo+sl% the nearly complete reduction of -,
x
to -
2
and the nearly
complete o+idation of ', and &' to ',
2
and &
2
,. 3igure ) shows the
catalyst conversion efficiency for all three classes of pollutants as a function
of A=3 ratio( with the dotted lines defining the window for conversions of
C%% and above.
.sing the information given in 3igures $ and )( e+plain the changes
in conversion efficiency seen for all three pollutants when the A=3 value is
(a) greater than the window for optimum conversion( and (b) less than the
window for optimum conversion.
(a) 3igure $ shows that over the narrow range of A=3 ratios covered in
3igure ) the amounts of ', and &' emitted form the engine decrease as
A=3 increases. As there is a simultaneous increase in the total amount of
o+idants (air S -,
-
)( the overall conversion of ', and &' increases to
approach effective completion at the stoichiometric ratio( and then remains
constant in the net o+idi1ing conditions beyond that point. The sharp fall in
-,
x
conversion for A=3 values approaching and above stoichiometric is
understandable in terms of the virtual elimination of reductions in this
region. /ecause the system is unable to remove all of the -,
x
( we would
e+pect to see an increase in -,
x
emissions from the e+haust. The three*way
catalytic converter is therefore unsuitable for engines that run lean.
(b) At A=3 ratios below the window value there is less -,
x
and more
&' and ', present in the mi+ture e+pelled from the engine (3igure $). All
the -,
x
present will react over the catalyst( so the -,
x
conversion will still
is high (as seen in 3igure )). &owever( we see a decrease in catalyst
52
efficiency for destroying &' and ',( as there are insufficient o+idants
present for complete conversion. Ae would therefore e+pect to see an
increase in the &' and ', levels emitted from the e+haust.
,bviously in both cases( in the absence of the three*way converter the levels
of ',( &' and -,
x
emitted for the e+haust would be much higher.
9ngine control systems have been developed to include an o+ygen
sensor (or lambda( Z( sensor as it is sometimes called)( and an electronic
module to regulate the A=3 ratio( so that the e+haust composition is 2ept
within the window for optimum conversion. &owever( because there are
time delays in the A=3 correction( the ratio cycles very rapidly between
slightly fuel*rich and slightly fuel*lean( oscillating about the
stoichiometrically balanced composition (44.5 [ %.") at a typical fre7uency
of 4 cycle per second. !inimi1ing the amplitude of the oscillation increases
the effectiveness of the converter.
:(;()(; The Chemical Reactions
Intro.+ction
%ince its de$elopment, the three-way catalyst has #een e&posed
to the full spectrum of techni'ues a$aila#le for the characteri(ation of
catalytic materials !he data pro$ided can #e correlated with the
results of acti$ity tests and )inetic measurements, which pro$ide
information on the performance of the catalyst !his re$eals that
althou"h the catalyst functions as a composite material, it can #e
di$ided into distinct "roups of catalytic centers that pro$ide se$eral
53
different types of site, acti$e for one or more of the many different
reactions !he participation of a particular type of site at any "i$en
moment will depend on the conditions e&perienced #y the catalyst*
for e&ample, whether the "ases are a net reducin", stoichiometric, or
o&idi(in" mi&ture
+easurements of intrinsic )inetics are usually carried out on
simple "as mi&tures to allow acti$ation ener"ies and reaction orders
to #e calculated for specific reactions !he data can often contri#ute
to an understandin" of the mechanisms #y which the surface
reactions occur !hey are also used to create reaction models that will
predict the performance of the catalyst under $arious anticipated
conditions
!he o$erall reaction scheme is complicated, with many
contri#utin" processes !he strate"y of the three-way catalyst is to
simultaneously remo$e CO, HC and NO
x
, and our treatment will
accordin"ly #e di$ided into three su#sections !he desired reactions
can #e e&pressed in simple terms as follows,
Remo&al o1 CO
', o+idation6
Aater*gas shift (AG8) reaction6
54
?emoval of hydrocarbons
&ydrocarbon o+idation6
3or e+ample6
8team reforming6
?emoval of -, (plus ', or &' (not shown))
', S -, redo+ reaction6
,r with hydrogen6
Any number of these reactions may be occurring simultaneously as
the A=3 ratio goes through its cycle about the stoichiometric composition.
The following subsections will loo2 more closely at the removal of each of
the pollutants under various conditions( and will also e+amine the role of the
catalyst components.
The supported commercial catalyst is the one most difficult to study
because of its comple+ity( with a large number of different components D ;t(
?h( Al
2
,
"
( 'e,
2
( /a,( etc. D present in one catalyst. 0t is therefore often
55
simpler to study model systems( such as ;t=Al
2
,
"
or ?h='e,
2
( and if certain
surface*science techni7ues are to be used( the Bcatalyst@ under study has to be
even simpler D a particular face of a metal single crystal. These studies( often
performed under ultrahigh vacuum (.&<)( are far removed from the real
catalyst system and the conditions it e+periences. &ence( it cannot be
assumed automatically that the results will be directly relevant to what is
actually happening in a converter fitted to an operational vehicle.
Remo&al o1 CO
.nder fuel*lean conditions (e+cess ,
2
)( the o+idation of ', has been
studied over a very large range of single crystals and model noble metal
catalysts( one of the most intensively investigated e+amples being the
;d(444) surface. Although this metal is not a component of the current three*
way catalyst used in the .G( it is worth considering the results in some
detail for a number of reasons. The reaction on metals such as ;t is in many
ways similar to that on ;d and( in any case( palladium is already being
incorporated into future generations of catalytic converter( particularly for
the .8 mar2et. !ost notable( however( is the fact that this is one of the few
cases in which surface*science techni7ues have successfully revealed the
details of a Breal*world@ catalytic mechanism. 8pecifically( we will see how
surface studies of the adsorption of ', and o+ygen on ;d (444) D both
individually and together D have led to the current understanding of the
mechanism of ', o+idation.
56
:99> results for the adsorption of ', on ;d (444)( obtained at room
temperature and below( have been interpreted in terms of the structural
models shown in 3igure 5. ,ne of the significant observations from this
wor2 is the readiness with which one arrangement of ', on the surface
evolves into another. Thus at a surface fractional coverage of \ X
4
=
"
(3igure
5a)( the ', occupies a hollow site where it can bind to three ;d atoms. As \
is increased to
4
=
2
(3igure 5b)( ', moves out of the hollow to a bridging site(
where it binds to two ;d atoms. 3inally( at \ X
2
=
"
(3igure 5c)( a he+agonal
structure forms( in which half of the ', molecules reoccupy hollow sites(
while the remainder bind to single ;d atoms at terminal sites. The readiness
with which the ', molecules can reposition themselves suggests that the
activation energy for surface migration in the chemisorbed state is low( and
that ', is a highly mobile species under catalytic conditions.
,+ygen adsorbs dissociatively on ;d (444)( and the , atoms are found
to be less mobile on the surface than ', molecules. The structure of the
chemisorbed layer at ma+imum coverage is shown in 3igure C.
Figure 7 %tructural models for the adsorption of CO on -d(...) at a surface fractional co$era"e of
(a) /
.
01* (#) /
.
02* and (c) /
2
01
0dentify the adsorbate structure shown in 3igure C in terms of the (mYn)
notation( and determine the fractional surface coverage( \( of o+ygen atoms.
57
Figure 8 !he surface structure of O atoms adsor#ed on -d(...) at ma&imum surface co$era"e
The unit meshes of the substrate (4 Y 4) structure and of the adsorbate
structure are shown in 3igure CA. 9vidently( the latter is (2 Y 2) in the (m Y
n) notation( so the full description of this structure should be ;d (444) (2 Y
2)D,.
3or adsorption on a single crystal surface( the fractional surface coverage is
given by
\ X += (m Y n)
Ahere x is the number of adsorbate species within the (m Y n)
adsorbate unit mesh. 0n this case (3igure CA)( , atoms occur only at the
corners of the mesh( so the latter contains a total of (4 Y
4
=
4
) X 4 atom. &ence
\ X 4= (2 Y 2) X
4
=
4
58
3igure CA the surface structure of , atoms adsorbed on ;d (444) at ma+imum surface
coverage( showing the substrate unit mesh and the adsorbate unit meshes.
Ae might now assume that when ', and ,
2
are adsorbed together
during the o+idation reaction( the properties of the system will be a simple
combination of those of the two molecules adsorbed separately. The surface
layer would then consist of mobile ', (ma+imum coverage( \ X
2
=
"
) within a
fi+ed lattice of , atoms (ma+imum coverage( \ X
4
=
4
). The fact that this is not
the case( as we shall see below( demonstrates an important point. /ecause of
mutual interactions( the behavior of two (or more) co*adsorbed species very
often differs from their behavior when adsorbed separately.
0n the case of ', and ,
2
( the order in which adsorption is carried out
is significant. 0f ', is adsorbed first( to a coverage greater than one*third of
a monolayer (\ X
4
=
"
)( subse7uent o+ygen adsorption is completely bloc2ed.
Aith lower coverages of ',( dissociative o+ygen adsorption does occurE but
the two species form separate domains on the surface (3igure #a). ,+idation
59
will then ta2e place only at the boundaries between domains( and so it will
be relatively slow.
3igure # 8chematic representation of domains of ', (ad) and , (ad) on ;d (444). (a)
8eparate domains (', adsorbed first)E (b) mi+ed domains (,2 adsorbed first).
Ahen o+ygen is adsorbed first to its ma+imum coverage( \ X
4
=
4
(
subse7uent ', adsorption occurs readily and compresses the , atoms into
domains in which the local coverage reaches \ X
4
=
"
. At first( the adsorbed
', is found in separate areas (as when ', is adsorbed first)( but as more is
added mi+ed domains form( containing both ', and ,( each at a local
coverage of \ X
4
=
2
(3igure #b).
These mi+ed domains bring ', (ad) and , (ad) into intimate contact(
with the , atoms at twice the surface concentration possible in the absence
of ',. Thus( the stoichiometry is now that re7uired for the o+idation
reaction. !oreover( an electronegative , atom will withdraw charge from
the surface. 0n turn( the surface will withdraw charge from neighboring ;dD
', bonds( wea2ening them and so ma2ing the ', more readily available
for reaction. The net result is that the mi+ed domain is highly reactive and
generates ',
2
at temperatures far below room temperature.
&aving thus established that( on ;d (444)( rapid ', o+idation can
occur by way of a :angmuirD&inshelwood type process (a surface reaction
60
between two adsorbed species)( we are almost in a position to propose a
detailed mechanism. 3irst( however( we must consider the possibility of an
alternative 9leyD?ideal type mechanism( in which the rate*limiting step
involves reaction between an adsorbed species and a molecule in the gas
phase. 0n this case( there are two such possibilities6
Ae can ma2e a decision about reaction # on the basis of the
information provided in 3igure 4%. A ;d(444) surface presaturated with a
7uarter of a monolayer of , atoms was e+posed to a beam of gaseous ',(
and the surface coverages and the o+idation rate were monitored with time.
3igure 4% shows that the rate became significant only after a population of
', had built up on the surface( and it reached a ma+imum when the
coverages of , and ', were appro+imately e7ual. This is clear evidence for
a :angmuirD&inshelwood process. 0f reaction # had been operative( the rate
would have been high initially( and would have fallen continuously as the
o+ygen layer was consumed by the reaction.
61
3igure 4% 'hanges in the rate of ',2 formation from ', and in the surface density of
o+ygen and ', on ;d(444). The surface was precovered with a 7uarter of a monolayer of
o+ygen atoms at time 1ero( and then e+posed to a constant stream of ', at a pressure of
5.#Y4%
]44
atm.
Given the research effort that was involved( the mechanism finally
proposed for ', o+idation on ;d(444) is deceptively simple6
Although the e+act nature of the surface intermediates is still not
2nown( the depth of understanding of the catalytic mechanism is 7uite an
accomplishment. /ut ust how relevant are these surface studies to the
practical catalysis ta2ing place in the converterR
62
0ndeed( 3igure 42 shows that in the case of rhodium there is e+cellent
agreement between the rates of ', o+idation over a ?h(444) single crystal
surface and over a ?h=Al
2
,
"
catalyst.
3igure 42 'omparison of the rates for ', o+idation measured over ?h(444) (blac2) and
over %.%4 mass % ?h=Al2," (green) at p(',)Xp(,2)X%.%4 atm( as a function of
temperature
63
Althou"h the se'uence of elementary steps is 'uite simple, the
o$erall )inetics of the CO o&idation reaction is not !he non-
uniformity of the surface, and the se"re"ation of the reactants in
surface domains, complicates the detailed modellin" of the )inetics
!he e&ception is the special case of low surface co$era"es of CO and O
atoms, when they are found to #e randomly distri#uted o$er the
surface and so satisfy one of the criteria for applica#ility of the
3an"muir isotherm 4nder these circumstances, 3an"muir
Hinshelwood )inetics can #e applied
Fi"ure .1 shows the comparati$e performance of sin"le-metal
catalysts for the o&idation of CO at a fi&ed temperature 5$idently, all
three of the platinum "roups metals present in automoti$e catalysts
are acti$e for CO o&idation 6n addition, results ha$e shown that 7h
may impro$e low-temperature acti$ity 6n the current (.889) three-
way catalyst used in the 4:, in which -t constitutes ;<8<= of the
no#le metal composition and 7h the remainder, it is the -t that is
mainly responsible for ', o+idation. .nder stoichiometric or slightly fuel*
rich (reducing) conditions( where there is insufficient o+ygen present to
o+idise all of the ',( conversion can also occur by one of the following
routes6
64
3igure 4" 'omparison of catalytic activity for ', o+idation at 4%% P' for ;t( ;d and ?h
at different A=3 ratios
<ia the ', S -, redo+ reaction (reaction )). This will be
discussed in detail in section 4.4(
via the water*gas shift reaction (e7uation 2)( because &
2
,
is present in the e+haust gases as a product of
combustion6
The water*gas shift reaction is cataly1ed by ;t and=or ?h( with ceria
acting as an e+cellent promoter. ;t='e,
2
DAl
2
,
"
and ;t*?h='e,
2
DAl
2
,
"
are
particularly active combinations for the removal of ', under slightly fuel*
rich conditions. The hydrogen produced in this reaction will react( in
preference to ',( with any o+ygen present. &ence( although the water*gas
shift reaction removes ',( it also inhibits ', o+idation by producing
hydrogen( which will remove any ,
2
present6
65
Remo&al o1 h%.rocar2ons
3igure 44 shows a comparative study for hydrocarbon o+idation over
single*metal catalysts6 it can be seen that ?h( ;d and ;t all give high
conversions for A=3 ratios at and above stoichiometric. Again (as in the case
of ',)( in the current (4##)) .G three*way catalytic converter( ;t is the
main component responsible for o+idation of the hydrocarbons. ,n noble
metal surfaces( al2ane adsorption is dissociative( whereas unsaturated and
aromatic hydrocarbons adsorb either dissociatively or associatively as *
comple+es. The subse7uent o+idation process is thought to be considerably
more complicated than the o+idation of ',( and we shall not consider it in
any detail.

Ahen the engine e+haust gas composition is reducing (fuel*rich)(
hydrocarbons compete effectively with ', for o+ygen( and they can also
react with water vapour to produce ', and &
2
D a reaction 2nown as steam
reforming6
66
3igure 44 'omparison of catalytic activity for &' o+idation at 4%% P' for ;t( ;d and ?h
at different A=3 ratios
This is cataly1ed by ?h and=or ;t with ceria and( as in the case of the
water*gas shift reactionE the combination ;tD?h='e,
2
DAl
2
,
"
is particularly
active. As we noted earlier( the &
2
produced may react preferentially with
any ,
2
present( thus reducing the amount of o+ygen available to react with
hydrocarbons and ',. 0n addition( the ', produced adds to the burden of
carbon mono+ide to be removed.
Remo&al o1 NO
:aboratory e+periments have shown that( under the conditions in the
catalytic converter( the decomposition of -, to ,
2
and -
2
over noble metal
catalysts is too slow to be significant. Ahen the A=3 ratio is stoichiometric
67
(or below stoichiometric)( -, can be removed by reduction with ', and=or
hydrocarbons. 3or simplicity we shall consider only reduction with ',( as
with the o+idation reaction( the situation with hydrocarbons is considerably
more complicated.
0n principle( a variety of products can be formed( specifically6
0n addition( &
2
produced from the water*gas shift or steam reforming
reactions can reduce -, to -
2
( -
2
, or -&
"
6
The -,
x
activities of ?h( ;t and ;d are shown in 3igure 4$. 0t is
evident that ?h has the highest activity( particularly under net reducing
conditions (low A=3). 8o why is ?h superiorR To answer this 7uestion( we
need to consider the mechanism of the reaction.
68
3igure 4$ 'omparison of catalytic activity for -,x reduction at 4%% P' over ?h( ;t and
;d at different A=3 ratios.
The catalytic reduction of -, by ', and=or &
2
over a variety of
surfaces has been the subect of a great deal of research. Application of
various surface*science techni7ues has provided some understanding of the
elementary steps involved( but the e+act mechanism is still controversial.
,ne view is that the first step is the dissociative chemisorption of -,. (^ou
should note that although we describe this as dissociative chemisorption
strictly it does not meet the definition( as -, is in fact first adsorbed
associatively and then dissociates on the surface.) The , atoms produced are
then removed by the reducing agents ', or &
2
. The - atoms can combine to
give -
2
( react with chemisorbed -, to give -
2
, (particularly important at
low temperatures)( or react with chemisorbed & atoms to form -&
"
. These
and other processes that may be involved are listed below.
69
Adsorption
>issociation
-, (ad) -(ad) S ,(ad)
0n the following steps we have assumed( for simplicity( that all
products are desorbed as 7uic2ly as they are produced. ^ou should
recogni1e( however( that adsorbed species( no matter how transient( will be
formed initially.
8urface reactions and desorption
?eactions with hydrogen
70
3igure 4) compares the rate of the -,D', reaction over an ?h (444) single
crystal with that over a ?h=Al
2
,
"
*supported catalyst.
3igure 4) 'omparison of the rates for the -,D', reaction measured over
?h(444) (blac2) and over %.%4 mass % ?h=Al
2
,
"
(green) at
p(',)Xp(-,)X%.%4 atm( as a function of temperature
This seems to be the case( particularly at higher temperatures. At
lower temperatures( the concentration of -, (ad) increases and reactions 22
and 2" would then be e+pected to contribute to - atom removal.
71
The elementary steps 24D2" all re7uire surface mobility of - atoms
(to encounter either -, (ad) or other adsorbed - atoms). Although this
process may occur on surfaces that are e+tensive on the atomic scale( such as
those of single crystals or large supported crystallites( it has been argued that
such mobility will be insignificant on or between the small highly dispersed
particles of ?h in the automotive catalyst. Therefore( we might e+pect the
rate*limiting steps and the observed 2inetics in the cases of ?h(444) and
supported ?h to be different. The Arrhenius*type plots in 3igure 4) confirm
that this is so6 over ?h=Al
2
,
"
( the reaction has higher activation energy (the
plot in 3igure 4) has a larger gradient) and a lower rate (at a given
temperature) than over ?h (444).
Ahat then is the rate*limiting step with the supported catalystR ,ne
suggestion is -, dissociation (reaction 4#) but there is a more radical
alternative( involving a different overall mechanism. 0nfrared spectra for -,
adsorbed on ?h=Al
2
,
"
(3igure 45) show bands at 4 54" cm
]4
and 4 C2$ cm
]4
(
which have been ta2en as evidence of a dinitrosyl species( ,X-D-X,(
formed by reaction 2)6
This step provides a means( other than diffusion of - (ad)( of
accomplishing the most important tas2 in the reduction of -,( namely the
pairing of two nitrogen atoms on the surface. ,nce formed( the dinitrosyl
species is thought to lose its two o+ygen atoms by way of an -
2
,
intermediateE for e+ample6
72
3igure 45 0nfrared spectra( recorded at "%% G( for -, adsorbed on ?h=Al2," as a function
of -, coverage( increasing from spectrum A to spectrum >. The bands at 4 54" cm
]4
and
4 C2$ cm
]4
have been assigned to the dinitrosyl species ,X-D-X,.
To summaries Ahichever mechanism is correct D -, pairing to form
a dinitrosyl species( or -, dissociation followed by -*atom combination
and -
2
desorption D both re7uire catalytic sites that can not only bind -,
but also donate charge to the adsorbate. 0n the first case( this charge would
be used to coordinate the two -, molecules. 0n the second case( it would be
73
transferred into the partially vacant 2 _ antibonding orbital of -, (3igure
4C)( wea2ening the -D, bond and hence facilitating dissociation.
,n e+amining the electronic structures of the noble metals( that of
rhodium is found to be particularly suitable for facilitating charge transfer to
adsorbed -,( with the uppermost occupied electron levels of the metal at
higher energy than the partially vacant 2 _ antibonding orbital of -,
(3igure 4C). 3or ;t (and also ;d)( however( the situation is reversed. <acant
metal levels lie at energies below that of -, 2 _( so charge will drain from
this orbital to the surface( strengthening the -D, bond.
This picture provides an appealingly simple e+planation for the
observation that rhodium is the most active of the noble metals for -,
x
removal( particularly under*net reducing conditions (3igure 4$). 0n fact( not
only do ;t and ;d show lower activities( they are also less selective( with ;t(
for e+ample( promoting ammonia formation (reaction 45). ?hodium is
therefore the essential ingredient in the automotive catalyst for -,
x
control.
/ecause it is so active( the amount re7uired is small D about %.4 mass % of
the catalyst( or %.4D%.2 g( highly dispersed over the surface D but even so(
catalytic converters account for around #%% of world rhodium demand (see
/o+ 4).
74
3igure 4C (a) The partial orbital energy*level diagram of molecular -,. (b) 8chematic
energy*level diagram showing the highest occupied level of ?h and the lowest vacant
level of ;t( in relation to the 2_ molecular orbital of -,.
Postscri5t
0t is important to remember that the reactions discussed in sections
4.2D4.4( and often studied separately( occur simultaneously in the presence
of all the other e+haust constituents. This may have an effect on the
efficiency of the individual reactions. 3or e+ample( 2inetic e+periments have
demonstrated that -, has a strong inhibiting effect on the rate of the
reaction of ', with ,
2
6 3igure 4# illustrates the point for a ?h=Al
2
,
"
catalyst.
3igure 4# The temperature dependence of ', conversion rates over %.%4 mass %
?h=Al2," in ',D,2( ',D-,D,2 and ',D-, mi+tures The concentration of each of the
reactants was %.$ vol % in all cases.
75
The role o1 CeO)
3igure 2% shows the effect on performance of adding 'e,
2
to a ;t catalyst
for three*way catalytic conversion.
3igure 2% The effects of adding 'e,2 to a ;t catalyst in terms of the simultaneous
conversion of ',( &' and -,x. The green lines show the conversions for the ;t catalyst
with 'e,2 and the blac2 lines those without.
Thus( ceria( which is added with the alumina in the washcoat( is an
essential ingredient of the three*way catalyst. 0t plays a number of roles6
46 'eria is a structural promoter( stabilising the precious metals and alumina
against sintering and particle growth. 3igure 24 emphasises this point.
76
3igure 24 The variation of dispersion stability as a function of ageing temperature( with
(green) and without (blac2) the addition of 'e,2 to %.# mass % ;t=Al2,"
'eria also stabilises the V*Al
2
,
"
used in the support( inhibiting a phase
change to *Al
2
,
"
( which has a lower surface area. (:anthanum o+ide and=or
barium o+ide are also often added as stabili1ers to help maintain the surface
area of V*Al
2
,
"
.)
26 'eria is 2nown to be able to pic2 up and store o+ygen from the gas phase
under fuel*lean operating conditions (e+cess o+ygen) D thus promoting the
reduction of -, to -
2
D and to release it under fuel*rich conditions (e+cess
fuel)( for reaction with ',( &
2
or hydrocarbons. Thus( it effectively dampens
the variations in the A=3 ratio as the e+haust gas mi+ture cycles about
stoichiometry( thereby helping to 2eep operation within the desired window
for optimum conversion over the catalyst.
"6 As we have seen in section 4.2( the ceria also enhances the water*gas shift
activity of ;tD?h three*way catalysts( and hence promotes ', removal via
the following reaction under fuel*rich conditions6
77
The point is illustrated by the results shown in Table 4 for ', conversion
under fuel*rich conditions. 0ncreasing the ceria content of the catalyst in the
absence of water has no effect( but when water is present the water*gas shift
reaction becomes increasingly important. (Addition of ceria also leads to an
improvement in activity for steam reforming.)
Table 1 CO conversion for a 1.08 mass % Pt-Rh
a
catalyst on -Al
2
O

!ith 1."# $.0 an% 8.0 mass % Ce levels# &n%er f&el-rich


con%itions# !ith an% !itho&t !ater 'resent. (
a
Pt 0.) mass % an%
Rh 0.18 mass %.*
CO conversion+%
,ith -2O ,itho&t -2O
1.5 mass %
Ce
54 49
4.0 mass %
Ce
64 49
8.0 mass %
Ce
70 49
>6 9nhanced conversions of ',( '
"
&
)
and -, at low temperatures have also
been observed for ;t='e,
2
catalysts that have undergone a reducing
pretreatment. This is believed to be due to an interaction between ;t and
'e,
2
induced by the reduction( causing an increase in the number and
activity of the active sites.
'hemical reactions6 summary
4. 8urface studies of the adsorption of ', and ,
2
on single
crystals and model catalysts have led to the development
of a possible mechanism for the o+idation of ',.
78
>issociatively adsorbed , atoms undergo a surface
reaction with adsorbed ',( to form ',
2
.
2. .nder slightly fuel*rich conditions( where there is
insufficient o+ygen present for complete o+idation( ',
can be removed by the water*gas shift reaction( using
water produced in the combustion process in the engine.
This is promoted by ceria.
". &ydrocarbons can be removed by o+idation or by
reaction with water (a process 2nown as steam
reforming).
4. /oth ', and hydrocarbons can be removed by reaction
with -, under stoichiometric or fuel*rich conditions.
The -,*', redo+ reaction is believed to proceed either
by dissociation of -,(ad) followed by - atom
combination( or by pairing of -,(ad) to give a dinitrosyl
species( followed by dissociation. Ahatever the detailed
mechanism( ?h is particularly active for this reaction( and
as such is currently an essential ingredient of the three*
way catalyst.
$. 'eria plays a number of important roles in the three*way
catalyst6 it is a structural promoter( stabilising both the
noble metals and the support against particle growth and
sinteringE it is an o+ygen*storage component( storing
o+ygen under fuel*lean conditions( and releasing it under
fuel*rich conditionsE it is a promoter for the water*gas
shift and steam reforming reactions and it can enhance
79
the low*temperature activity of the catalyst after certain
types of pretreatment
Ahat are the maor roles proposed for the different components of the
;t*?h='e,
2
DAl
2
,
"
three*way catalystR
The maor roles proposed for the different components of the ;t*?h='e,
2
D
Al
2
,
"
three*way catalyst can be summarised as follows6
Platin+m
', o+idation
&' o+idation
steam reforming and water*gas shift reactions (with
'e,
2
)
Rho.i+m
',D-, redo+ reaction
steam reforming and water*gas shift reactions (with
'e,
2
)
Ceria
o+ygen storage
structural promoter maintaining both metal and
support surface areas
80
chemical promoter for the water*gas shift and steam
reforming reactions
enhancement in low*temperature activity of ;t after
reducing pretreatment
0n 3igures 4"( 44 and 4$( ;d in its fresh state is seen to be superior to
;t for the conversion of all three pollutants. 'onsidering the properties we
re7uire of a catalyst( what possible reason can you suggest for the current
widespread use of ;t in three*way catalysts( rather than ;dR
;d is in fact cheaper than ;t (/o+ 4)( so the reason for using ;t is not an
economic one. The principal properties we re7uire of a catalyst are activity(
selectivity and stability. /ecause we have seen that the first two of these are
at least as good for ;d as for ;t( this should lead us to consider the third(
stability. 0n fact( as we shall discover in section $."( ;d has a high
susceptibility to poisons( especially lead and sulfur. 0n addition( it sinters in
reducing atmospheres( and can also form an alloy with ?h( reducing the
activity of the latter.
:(;()(: Catal%st Deterioration
Intro.+ction
0n the .G( three*way catalysts must currently (4##)) meet emission
standards for a life of $%(%%% milesE however( research efforts and legislation
are set to double this re7uirement in the very near future to the current .8
standard of 4%%(%%% miles. The catalysts do deactivate with use. 0ndeed the
ability to withstand mild deactivation is built into the design of the catalyst(
and into the entire emission control system in the vehicle. This is done by
81
setting up vehicles at efficiencies well above the legal re7uirements at low
mileage( so that as the catalyst slowly deactivates( it will still meet the
emission standards.
&owever( the catalyst may be e+posed to conditions that result in
more severe deactivation above and beyond that which is Ballowed for@ in its
lifetime. The maor causes of deterioration are thermal damage (due to
e+posure of the catalyst to high temperatures)( and poisoning by
contaminants in the e+haust (notably phosphorus( lead and sulfur). ?esearch
aimed at detecting deterioration and trying to understand its nature( has
included post*mortem e+aminations of used catalysts( and simulated ageing
studies( in which the catalyst is e+posed to high temperatures or catalyst
poisons.
Thermal e11ects
9+haust catalysts usually operate in the temperature range 4$%D)%%
P'( but they can e+perience temperatures of up to 4%%% P'. The conditions
that can produce such high temperatures include repeated misfire (resulting
in the o+idation of large amounts of unburned fuel over the catalyst) and
high driving speeds. 0n addition( very high temperatures may be e+perienced
if the catalyst is Bclose coupled@ to the engine( which is one of the possible
solutions to the cold*start problem. Although commercial catalysts are
designed to withstand occasional high*temperature operation prolonged and
repeated e+posure to temperatures in e+cess of C%% P'( especially under
o+idi1ing conditions( have a number of serious effects.
82
&igh temperatures may affect all the components of the catalyst. The
noble metal particles may sinter (recall 3igure 24 in section 4.))( resulting in
a decrease in the fraction of the metal available for catalytic reactions. 8uch
sintering particularly affects the low*temperature activity of the catalyst. 0t
can be countered to some e+tent by the addition of ceria as a structural
promoter( which also stabilises the alumina support against sintering.
&owever( the ceria may itself undergo crystallite growth at elevated
temperatures. This can be inhibited by the addition of barium and 1irconium(
as shown by the comparison in 3igure 226 it is apparent that barium and
1irconium help to stabili1e the catalytic activity.
Figure 22 'omparison of catalytic activity for a ;tD?h='e,2 catalyst with (green) and
without (blac2) the addition of /a and Qr( after ageing at A=3X4).$ at #$% P' for 4%
hours.
At very high temperatures the support may itself sinter or even
undergo a phase change( affecting the total surface area. !echanical loss of
catalyst support material may also occur in cases where the washcoat shrin2s
83
and crac2s( causing it to separate from the monolith (3igure 2"a). Again( the
problem can be overcome by incorporating so called Bphase stabili1ers@ D
e+amples include barium and lanthanum D into the washcoat (3igure 2"b).
At e+cessively high temperatures the ceramic monolith may even melt(
forming additional channels that may allow the e+haust gases to pass
through the converter without contacting the catalyst.
3igure 2" ,ptical micrographs of a washcoat after e+posure to high temperatures. 0n (a)
sintering has caused severe shrin2age( whereas in (b) the addition of Bphase stabilisers@
has prevented shrin2age crac2ing.
&igh temperatures can also promote damaging interactions between
the noble metals( resulting in the formation of a less active alloy( or between
a noble metal and base metals in the washcoat support. 0n particular( it has
been established that ?h begins to penetrate the surface of V*Al
2
,
"
at
temperatures greater than )%%P ' by a solid state reaction between ?h
2
,
"
and V*Al
2
,
"
. This subsurface penetration and loss of active ?h can be
slowed down if the reactivity of the support is minimi1ed by first supporting
the ?h on 1irconium( Qr,
2
( and then incorporating the resulting powder into
the V*Al
2
,
"
washcoat. 3igure 24 shows the dramatic effect this can have on
the catalytic activity of a ?h=V*Al
2
,
"
catalyst. .nfortunately( the
incorporation of ?h=Qr,
2
into three*way catalysts re7uires comple+
manufacturing methods( which are not yet suitable for high*speed
production. An alternative approach has been suggested by wor2 that
84
indicates that the ?h=Al
2
,
"
interaction may occur preferentially at the grain
boundaries of the support. 'eria can be incorporated as a stabili1er into the
alumina in an attempt to preferentially bloc2 this interaction.
!i,+re ); 8chematic comparison of the catalytic activity of (a) ?h=V*Al2," and (b)
`?h=Qr,2a=V*Al2," after thermal treatment at 4 4%% P' in air for 4 h. The activity of the
Qr,2*supported catalyst (b) remains virtually intact after the calcinations( whereas that of
the standard ?h=V*Al2," catalyst (a) is seriously diminished.
The E11ect o1 Poisons
Lea.
The use of catalytic converters was one of the maor contributors to
the phasing*in of unleaded petrol. :ead in petrol is a severe poison for the
catalyst( and there have been many stories( particularly in the early days of
the converter( of people disabling the catalyst by misfiling. 3igure 2$ shows
how the activity of a typical three*way catalyst is impaired during( and
following( intermittent operation with leaded fuel (%.2) g l
]4
) during 4$(%%%
miles of vehicle operation. The efficiency of a control vehicle (unleaded
petrol only) was virtually unchanged at #4% for hydrocarbons( #$% for ',
and ))% for -,
x
. 3ollowing the misfiling( the ',*conversion efficiency
(3igure 2$a) decreased( but subse7uently recovered to an acceptable level.
85
/y contrast( the conversion efficiencies for the hydrocarbons (3igure 2$b)(
and especially -,
x
(3igure 2$c)( did not recover to passable values( and
hence did not meet the emission regulations current at the time (4#C)).
3igure 2$ 9ffect of intermittent use of leaded petrol (blac2 points) on catalyst efficiency
(for a typical three*way catalyst) for the conversion of (a) ', (b) &' and (c) -,x.
,f the various noble metal components( ;d is the most sensitive to lead
poisoning. 0ts activity decreases when there are ust trace amounts in the
fuel. ?h is slightly less susceptible( and ;t is by far the most resistant. 'lues
to the mechanism of lead poisoning have come from model systems( which
are amenable to detailed surface analysis
86
3igure 2) 9lectron probe elemental maps of ;t=V*Al2," after e+posure to ;b for 24 hours
at 5%% P'. 9lectron probe microanalysis (9;!A) is based on the emission of
Bcharacteristic@ K*ray photons following the ioni1ation of atoms by high*energy electrons.
9;!A allows 7uantitative determination of the composition of solids with a resolution of
the order of 4 Wm. The whiter the area on the map( the higher the concentration of the
element under study. The K*ray spectrophotometer is a common attachment on scanning
and transmission electron microscopes.
This deposition of lead specifically onto the noble metal is believed to
occur because the molecules that Bcarry@ the lead out of the engine( probably
halides or o+yhalides( decompose on the noble metal( leaving the lead on the
surface.
The fact that ;t is more resistant to lead poisoning than ?h or ;d is
largely due to an indirect effect. The small amount of sulfur also present in
fuel can act as a scavenger for lead. ;rovided that the sulfur is in its
he+avalent o+idation state (8
<0
)( in the form of 8,
"
( it can combine with lead
o+ide to form a stable lead sulfate( which( although a poison itself( is not
site*specific. ,nly ;t( however( is a good catalyst for the o+idation of 8,
2
(produced from sulfur in the combustion reaction( and present in the e+haust
mi+ture) to 8,
"
6 indeed( it is used for this purpose in the industrial
production of sulfuric acid.
87
Phos5hor+s
;hosphorus is recogni1ed as a potential poison for automotive
catalysts. The phosphorus level in fuel is generally very low (2Y4%
]$
g l
]4
)(
but it is present in higher concentrations in engine oils (4.2 g l
]4
).
;hosphorus derived from the engine oil is believed to react with the alumina
support( and also to reduce the activity of the noble metal component. This
deactivation is particularly important for ;d( with which phosphorus may
form an alloy. At the time of writing( phosphorus levels in engine oil are
becoming an issue( and oils with reduced levels are appearing on the mar2et.
S+l1+r
.eactivation
The presence of sulfur in the e+haust gas mi+ture causes a reduction
in the activity of the three*way catalyst( particularly for the water*gas shift
and steam reforming reactions D processes that are important mechanisms
for the removal of ', and hydrocarbons under fuel*rich conditions. 8ulfur
also decreases the efficiency of -,
x
removal. The deleterious effect of
e+posure to 8,
2
on the catalytic activity of a commercial monolithic catalyst
(;tD?h='e,
2
DAl
2
,
"
) is evident in 3igure 25. -otice( however( that the
conversion efficiency recovers 7uite rapidly once the sulfur has been
removed from the gas stream. This is significant because it suggests that a
change in the sulfur content of fuel (average 2%C mg l
]4
in the .G)( could
achieve a reduction in emissions from vehicles currently in use.
88
The general resistance of ;t and ?h to sulfur poisoning( and their
ability to recover from it( were two of the factors in the original decision in
the 4#5%s to use noble metals rather than the less active( but cheaper( base*
metal o+idation catalysts. (0n terms of the more stringent legislation now in
force( let alone that which will apply in the future( it is unli2ely that base*
metal activity (or durability) would be sufficient to meet emission control
re7uirements( even if all the sulfur in fuel were to be removed.) ;d is more
susceptible to long*term damage( and it is this susceptibility to poisoning
that limits its use in the .G at the moment. ;d*only catalysts are( however(
under development for the .8 mar2et D where there are stricter controls over
the contaminant levels in fuel.
8ome understanding of the mechanism of catalyst deactivation by
sulfur has been obtained by e+amining the effects of 8,
2
on the surface area
of metals The physical adsorption of -
2
can be used to determine the Btotal@
surface area of a catalyst. The capacity of a supported metal catalyst to
chemisorb ', can be used as a measure of the free metal surface area. 0t is
typically e+pressed as the ratio ',=!( where ', is the amount of ',
chemisorbed by a fi+ed mass of catalyst (proportional to the number of
surface metal atoms)( and M is the metal content of the catalyst (proportional
to the total number of metal atoms). The higher the value of ',=!( the
higher the surface area of the metal. Table 2 gives values of the ',
chemisorption capacity of a ;tD?h='e,
2
DAl
2
,
"
model catalyst after ageing
in a fuel*rich mi+ture( in the presence and absence of 8,
2
.
89
Table 2 /ffect of f&el-rich a0ein0 on the metal-s&rface area
(e1'resse% as CO/M* for a Pt2Rh+CeO
2
2Al
2
O

catalyst# in the
'resence an% absence of 3O
2
. The val&e of CO/M for a fresh
sam'le is 0.4).
A0ein0 tem'erat&re+5C CO/M after a0ein0
6n the 'resence of 3O2 6n the absence of 3O2
400 0.20 0.78
550 0.12 0.69
700 0.10 0.39
/ecause the effects are not permanent( this sulfur species is
presumably relatively wea2ly adsorbed. As a result it is desorbed( and the
activity of the catalyst is regenerated( when the gas*surface e7uilibrium is
shifted in favour of the gas*phase by removal of 8,
2
from the gaseous
mi+ture (3igure 25).
The production of hydrogen sulfide
?ecently( there has been a great deal of interest in the interactions of
sulfur with the three*way catalyst( not so much because of its impact on
activity( but rather because of a smelly side*effect. 9ver since catalytic
converters were introduced( the odour of hydrogen sulfide (&
2
8)( described
as Bsmelling li2e rotten eggs@( has been an issue. This is particularly
noticeable when a car in front accelerates after idling (at traffic lights or a
roundabout( say) or decelerates sharply after cruising. After combustion in
the engine( sulfur in the fuel is released to the e+haust gases as 8,
2
. .nder
fuel*rich (reducing) conditions( this is converted into &
2
8 over ;t( the
suggested mechanism involving the formation of the metal sulfide as a
90
reaction intermediate. 0t has been found( however( that the amounts of &
2
8
generated when engine conditions become fuel*rich( following prolonged
running under fuel*lean (or o+idising) conditions( are larger than e+pected.
The catalyst can apparently Bstore@ sulfur under lean conditions and release it
under rich conditions.
The noble metals do not retain any sulfur under these conditions.
&owever( adsorption studies with both model catalysts and the commercial
(fully formulated) catalyst have shown that sulfur storage under lean
conditions can occur by interaction of 8,
2
with both 'e,
2
and Al
2
,
"
in the
support. .nder typical conditions( 'e,
2
provides the preferred adsorption
sites( and the sulfur storage by the catalyst has been found to increase with
increasing 'e content. K;8 studies (some results of which are collected in
Table ") have been used to study the nature of the species involved.
Table " K;8 data recorded for various cerium and sulfur compounds.
8ample &istory /inding energy=e<
'e "d 8 2p
'e,
2
$$% P'( air CC4.5 D
CeO2 20 C, SO2 881.6 168.0
CeO2 550 C, SO2 882.8 168.8
Ce(NO3)3.6H2O 883.3
S
VI
como!"#s 168.5168.9
S
IV
como!"#s 166.3167.9
91
&ence( interpretation of the K;8 data suggests that( at room
temperature( 8,
2
is adsorbed on 'e,
2
( possibly to form a sulfite species
(that is( a species containing 8
0<
). At $$% P' the 'e
0<
o+ide( 'e,
2
( appears to
participate in a redo+ reaction with 8,
2
E the sulfur is o+idised to 8
<0
and the
cerium is reduced to 'e
000
( possibly resulting in the formation of cerium(000)
sulfate( 'e
2
(8,
4
)
"
.
The sulfate=sulfite species formed under fuel*lean conditions with the
cerium and aluminium in the support decompose in fuel*rich conditions to
release the 8,
2
=8,
"
species( which are then converted into &
2
8 over the
noble metal component of the catalyst. 'atalysts that do not contain noble
metals do not produce &
2
8.
Although it has been 2nown for some time that automobile e+haust
catalysts can produce &
2
8 in fuel*rich e+haust streams( there has been an
increase in the levels emitted in recent years. This is believed to be a
conse7uence of the considerable improvements made in catalyst activity
over the years. &owever( during one study into this effect( it was noted that
&
2
8 emissions from Bengine*aged@ catalysts( that is( those that had been Bon
the road@ for $%(%%% miles( were much lower than those from the fresh
catalyst. 0n addition( the &
2
8 Bspi2es@ when going from lean to rich
conditions were found to be much smaller on the engine*aged catalyst.
9+amination of an aged catalyst revealed traces of the usual poisons(
including 8 and ;b from the fuel( and phosphorus (and 1inc) from the engine
oil. This suggested that at least one of these components can reduce the
storage of sulfur by the ;tD?h='e,
2
DAl
2
,
"
system. ;hosphorus appears to
be a li2ely candidate( because it has been found that phosphorus*doped ;tD
92
?h='e,
2
DAl
2
,
"
catalysts e+hibit a lower capacity for adsorption of 8,
2
than
an undoped reference catalyst. This suggests that the phosphorus is
somehow Binterfering@ with the component of the catalyst that adsorbs the
8,
2
D the ceria. 0ndeed( it has been proposed that a 'eD;D, species
(possibly 'e;,
4
) is formed( which is more stable than( and hence inhibits
the formation of( a 'eD8D, species (for e+ample( 'e
2
(8,
4
)
"
). This would
have the effect of reducing the storage capabilities of the ceria( and hence of
reducing the si1e of the &
2
8 spi2e on going from lean to rich conditions.
To summaries 0n view of the discussion above( it would seem that
several different strategies could be used to reduce &
2
8 emissions6 (i)
decreasing the 'e surface area (however( this will have detrimental effects
on the catalyst activity)E (ii) improving the A=3 controlE (iii) reducing the
sulfur content of the fuelE (iv) including an &
2
8 scavenger in the catalyst (in
the .8A nic2el is used( but in 9urope this is prohibited because of concern
that it could lead to the formation and release of carcinogenic nic2el
carbonyl).
'atalyst deterioration6 summary
4. An ability to withstand mild deactivation is built into the
design of the catalytic converter. &owever( severe
deactivation could prevent the system from meeting
emissions legislation.
2. The maor causes of deactivation are thermal damage and
poisoning.
". &igh temperatures may cause sintering of the metals
and=or the supportE this can be prevented to some e+tent
by the addition of ceria as a structural promoter.
93
>amaging interactions between the noble metals( or with
the support( can also occur at high temperatures. The
interaction between ?h
2
,
"
and V*Al
2
,
"
can be slowed
down by first supporting the ?h
2
,
"
on Qr,
2
.
4. :ead is a severe poison( particularly for ;d( and is
believed to associate with the noble metal.
$. ;hosphorus from engine oil can contaminate the catalyst
and cause deactivation.
). 8ulfur present in fuel has two maor undesirable effects.
0t can cause deactivation of the catalyst( and it also leads
to generation of &
2
8.
5. 8ulfur is o+idised to 8,
2
( which is believed to bloc2 sites
on the metal surface( forming a wea2ly adsorbed species
that is desorbed when the sulfur is removed from the gas
stream.
C. 8ulfur can also be stored under fuel*lean conditions by
Al
2
,
"
( and especially 'e,
2
( in the support( and released
as &
2
8 under fuel*rich conditions. The sulfur is believed
to be stored as 'e
2
(8,
4
)
"
. ,n going to fuel*rich
conditions( this species decomposes( releasing 8,
2
(
which is converted into &
2
8 over the noble metal. 0t has
been found that adsorption of 8,
2
( and hence the storage
capabilities of a ;tD?h='e,
2
DAl
2
,
"
catalyst( are reduced
in the presence of phosphorus. The preferential formation
of a 'eD;D, species (possibly 'e;,
4
) inhibiting
formation of the 'eD8D, species ('e
2
(8,
4
)
"
) has been
proposed.
94
?efer bac2 to the ',=! values listed in the final column of Table 2.
&ow would you e+plain the variation in these ',=! values with increasing
ageing temperatureR
The decrease in the value of ',=! observed as the ageing
temperature increases indicates that the free metal surface area of the
catalyst is decreasing with increasing temperature. This is li2ely to be due to
sintering of the noble*metal particles( and=or the support.
RE!ERENCES
95
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Throttle ,pening on !i+ture distribution in four 'ylinder 8par2
0gnition 9ngine@( !.Tech. Thesis( 00T >elhi( 4##).
$. 8ubrah manyum( T.;.( B8tudies on -itrogen ,+ides 9mission and
;erformance of a 8par2 0gnition 9ngine Aith 9G? .sing Gasoline
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). Aent Aorth( H.T.( B9ffect of 'ombustion 'hamber 8urface
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preprint no. 54%$C5( 4#54.
5. !oore( H. b BThe 9ffect of Atmospheric !oistures on -,
;roduction(@ paper presented in 8eoul meetingE combustion
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96
#. :ester( G.?. B8election of 'atalytic ?eduction of -d+@( 8A9 paper
5C%2%2( 4#5C.
4%. /ernstein( :.8.( :ang( ?.T.( :unt( ?.8.( !usser(G.8. and fedor( ?.H.(
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8A9 Trans 5"%$)5. 4#5".
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of three*way 'atalyst D part 00@( 8A9 paper 55%4#)( 4#55.
4$. Gandhi( &.8.( ;i2en( A.G.( 8helot( !( and >elosh( ?.G.( B9valuation
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C4%25"( 4#C4.
45. &ensel( H.G. 'o+( T.;.( -ugent( Thomas( BThe Application of TA'
system at a heavy >uty Gasoline 9ngine@s ;aper C4%%C$( 4#C4.
97