UNIT 6

CATALYST
Contents

The development of catalysts for petrol

engines

Structures and functions

The three-way catalyst

The honeycomb substrate

Controlling pollutants at cold start

Exhaust gas after-treatment for diesel

engines
The development of catalysts for petrol engines

The air-polluting effects of internal-combustion engines

were not recognized until the early 19!s"

#p until that time$ improvements in power output and

exhaust noise were the main areas of development"

The driving force for change originated in the first

measures to control air pollution$ which were
introduced in the smog-bound city of %os &ngeles$
#S&"

Controls for exhaust gases from motor vehicles were

introduced in 'apan and Europe soon afterwards"

These early measures were focused on carbon

monoxide (C)* and unburned hydrocarbon (+C*"

The use of oxidizing catalysts to convert +C and C)

has been mandated under exhaust gas regulations in
the #S& and 'apan since 19,-"

The main components of the early catalysts were base

metals such as Co$ Cu$ .e$ /i and Cr"

+owever$ these were found to degrade over time$ and

precious metal catalysts were introduced to address
problems of sulfur poisoning and metal evaporation"

#nleaded petrol was developed because it was found

that the lead in petrol coated the catalysts and made
them ineffective"
The development of catalysts for petrol engines

&n exhaust gas recirculation (E01* system was

introduced to decrease /)x emissions$ but catalysts
to remove /)x were not legally re2uired until 19,3"

1egulations introduced in 'apan (19,3* and the #S&

(1931* re2uired a further decrease in /)x
emissions$ and although the oxidizing catalyst
system addressed +C and C) re2uirements$ various
controls in the engine were necessary to decrease
/)x"

&s a result$ power output fell and fuel consumption

increased"
The development of catalysts for petrol engines

The first vehicle with a three-way catalyst was

mar4eted in 19,,$ although it was not introduced
for European cars until 1995" & system
combining a three-way catalyst with electronic
fuel in6ection (E.7* and oxygen sensors has now
become the standard in petrol engines for cars"
The three-way catalyst system reduces exhaust
emissions after warming up$ but recent
legislation on emissions now re2uires a further
decrease in pollutants$ and reducing emissions at
cold start is an important issue"
The development of catalysts for petrol engines
Functions of modern ehaust system
Structures and functions

.igure 1!"1 lists the tas4s for modern exhaust systems1

and the various functions needed to bring about
improved engine performance while 4eeping emissions
low"

The catalytic converter is an important component of

the exhaust system and efforts to comply with emission
regulations" The main pollutants are +C$ C)$ and /)x"

.igure 1!"8 illustrates the concentrations of these gases

against air9fuel ratio" The concentration of each
component varies with combustion$ air9fuel ratio$ E01
and ignition timing" +C derives from unburned fuel"

The concentration of +C decreases in lean combustion$ but inversely increases

in extremely lean combustion due to misfire"

The concentration of C) does not depend on engine load$ but does depend on
the air9fuel ratio"

The concentration of /)x is largely influenced by the air9fuel ratio and

combustion temperature$ and shows a maximum value at around an air9fuel
ratio of 1"

Catalysts are materials that cause chemical changes !ithout "eing a part
of the chemical reaction"

&ll exhaust gas must flow through the catalytic converter (.ig" 1!"5a*" The
catalysts clean the exhaust gas by converting the pollutants to harmless
substances$ causing the reaction:
C) ; +C ; /)x <C)8 ; +8) ; /8 inside the catalytic converter"
The result is an exhaust gas containing less +C$ C) and /)x"
Structures and functions

/ormally$ the complete unit is referred to as a catalytic

converter$"

This term should only be used to describe the catalytic

precious metals"

These are platinum (=t*$ rhodium (1h* and palladium

(=d*"

.igure 1!"5(b* schematically illustrates catalysts in a

ceramic monolith"

& honeycombed monolith of extruded ceramics or

wrapped metal foils is normally used as the carrier$ with
the catalysts applied in a wash-coat covering the
honeycomb substrate"
Structures and functions

.igure 1!"- illustrates the conversion characteristics of a three-way

catalyst during exhaust gas purification" =ollutants behave very
differently in the exhaust flow$ as demonstrated by the /)x conversion
in comparison to that of C) and +C"

& common optimum for conversion of all pollutants has to be

determined$ and this is 4nown as lambda (>*$ or the lambda window"

The highest conversion rate for all three components occurs in a small
range around > ? 1"

.or the catalytic converter to be most effective$ the air9fuel mixture must
have a stoichiometric ratio of 1@", : 1"

&n oxygen sensor in the exhaust flow$ the lambda sensor$ controls the
mixture electronically$ 4eeping it at the optimum state over all engine
loads"

The oxygen sensor consists of a solid electrolyte$ Ar)8$ which generates

electromotive force (Bs* proportional to the oxygen concentration"
Characteristics
Characteristics

Electromotive force of the sensor drastically decreases around the

stoichiometric air9fuel ratio$ > ? 1 (.ig" 1!"-*" This characteristic$ combined
with the E.7 system$ enables accurate fuel control"

Cithout the sensor$ E.7 and control electronics$ the three-way catalyst does
not wor4 well" .igure 1!" illustrates the feedbac4 control mechanism of the
sensor and fuel in6ector"

To meet future +C and C) limits and to improve fuel economy$

manufacturers are loo4ing forwards$ running air9fuel ratios near lambda ? 1
for full load engine conditions"
Characteristics
The three#!ay catalyst
$idation% reduction and three#!ay catalysts

&round 9!D of all chemicals are manufactured using

catalysts"

&rtificial catalysts are used in the manufacture of petrol$

plastics$ fertilizers$ medicines and synthetic fibers for
clothing" The word catalyst was first used by the
Swedish chemist '" Eerzelius and means Fto brea4 down"

& catalyst alters the speed of a chemical reaction but is

left unchanged once the reaction has finished" .or
example$ C) and )8 do not react together at room
temperature$ and a mixture of these gases may remain
stable for more than a thousand years if it is not heated"

+owever$ in the presence of a catalyst$ the mixture

rapidly changes to C)8"

Guring this reaction$ the gas molecules are adsorbed

onto the surface of the catalyst" This causes the bonding
in the C) and )8 molecules to relax$ resulting in the
atomic exchanges that form C)8 and generating heat"

The exhaust gas catalysts are functionally classified into

three types$ oxidizing$ reducing and three-way"

The oxidizing catalyst oxidizes +C and C) in an

oxygen-rich atmosphere"

The reducing catalyst reduces /)x even under oxygen-

rich atmospheres H Cu9Aeorite is a typical example"
The three#!ay catalyst

Iost catalysts used in petrol engines now are three-way

catalysts that convert +C and C) into C)
8 and +8) and reduce
/)x to /8"

The catalyst comprises an alumina powder carrying =t$ =d and 1h$ with auxiliary catalyst Ce)8"
=t and =d oxidize +C and C)$ and 1h reduces /)"

1h wor4s effectively even under low-oxygen conditions" Typically$ the chemical reactions assisted
by the components of three-way catalysts are:
C5+
3
; )
8
< C)
8
; +
8
) by =t and =d
C) ; )8 < C)8 by =t and =d$
/) ; C5+3 < /8 ; C)8 ; +8) by 1h
The three#!ay catalyst

Efficiency is influenced by several factors$ including surface

area of the catalyst and range of the lambda window" The
available surface area of precious metal particles is
maximized by using ultra small particles (1 nm* and
dispersing them on the porous alumina substrate (.ig"1!"5b*"
This basic technology was developed in the 19@!s$ when
catalysts were used to increase the octane value of petrol"

The three pollutants are drastically reduced under conditions

within the lambda window as shown in .ig" 1!"-" +owever$
small variations outside the lambda window increases
exhaust emissions" The wider the lambda window$ the wider
the range of air9fuel ratios that the catalyst can clean"
The three#!ay catalyst

To widen the lambda window$ Ce)

8 is added
as an auxiliary component" Ce)8 can store or supply oxygen via changes
in its crystal lattice" Ce has two atomic values$ Ce@; or Ce5;$ and the
valence number changes according to variations in the atmosphere$
binding or releasing oxygen"

8Ce
@;)8 < Ce
5;8)5 ; 198)8"

This property compensates for deviations in the air9fuel ratio away from
the stoichiometric ratio and therefore helps to maintain optimum
conditions for catalytic conversion of the exhaust gases"
The three#!ay catalyst
&eterioration of catalysts
There are three main causes for the deterioration of
catalysts:
1" =hysical failure due to thermal shoc4 or
mechanical vibration"
8" =oisoning by impurities such as =b$ = and S in
the petrol and engine oil" and
5" Thermal failures such as sintering$ where the
precious metal and Ce)
8 particles aggregate by diffusion and
therefore reduce available surface area$ and heating$ which decreases the micro-pores
in the alumina surface"
The three#!ay catalyst
The honeycom" su"strate
Ceramic

The monolithic honeycomb has replaced the pellet type as

the most commonly used structure for catalytic
converters" The ceramic monolith (.ig" 1!"@* has proved
to be an ideal carrier (substrate* for catalytic coatings
containing precious metals" The honeycomb substrate
must have the following properties:
J &ppropriate strength
J +igh heat and thermal shoc4 resistance
J %ow bac4-pressure
J &de2uate adhesive strength to bond catalytic materials
J %ac4 of chemical reactivity with the catalysts"

The starting materials for a ceramic honeycomb

are magnesium oxide$ alumina and silicon oxide$
which are extruded and ba4ed into cordierite
(8Ig) K 8&l
8)5 K -Si)8*"

.igure 1!",(a* illustrates the manufacturing process of ceramic honeycomb" 7t has an

optimal chemical resistance$ low thermal expansion$ high resistance to heat (melting
point L 1@!! MC* and can be recycled relatively easily"

The standard monolith has a structure of @!! or !! cpsi (cells9 inch

8*"

The fine honeycomb structure of the ceramic monolith calls for very careful
embedding$ or canning"

Special covers consisting of high-temperature resistant ceramic fibers are used (.ig"
1!"@*" These insulate$ protect and compensate for the different expansion coefficients
of the monolith and steel casing"
The honeycom" su"strate
'etal

&nother type of honeycomb is made of metal foil" .igure 1!"3 shows a

typical metal honeycomb" .igure 1!",(b* illustrates the manufacturing
process for a metallic honeycomb"

The cell is constructed from a special$ very thin and corrugated steel
(typically$ .e-8!DCr--&l-!"!-Ti-!"!3%n-!"!8C N /* foil"-$ Bacuum
brazing using a filler metal such as /i-19DCr-1!Si brazes the foil
honeycomb directly into the steel casing"

&nother type of honeycomb is made of metal foil" .igure 1!"3 shows a

typical metal honeycomb"

.igure 1!",(b* illustrates the manufacturing process for a metallic

honeycomb"

The cell is constructed from a special$ very thin and corrugated steel
(typically$ .e-8!DCr--&l-!"!-Ti-!"!3%n-!"!8C N /* foil"

Bacuum brazing using a filler metal such as /i-19DCr-1!Si brazes the foil
honeycomb directly into the steel casing"
The honeycom" su"strate

The filler metal has a low &l content$ so resistance to

oxidation deteriorates near the bond"

Chile the alumina protects the honeycomb from

corrosion$ it also obstructs bonding by diffusion at
high temperature"

& solid phase diffusion bonding method was

developed to avoid the need for filler metal"

The alumina film on the foil surface is removed by

evaporating aluminum atoms from the surface through
vacuum treatment at high temperature$ thus enabling
diffusion bonding without the use of filler metal"
The honeycom" su"strate
'anufacturing process of catalyst

The metal honeycomb has a thin wall (@! Om*$ and

therefore a lower bac4-pressure and a smaller construction
volume for an identical surface area compared with the
ceramic honeycomb"

+owever$ the metal honeycomb has several disadvantages$

including higher costs$ and higher radiation of heat and
structure-borne noise$ so additional insulation is re2uired"

& wash-coat containing the catalyst covers the honeycomb

substrate surface"

PQ&l8)5 containing some auxiliary components is

commonly used for the coating" 7t holds the precious metal
particles and operates as an auxiliary catalyst"
The honeycom" su"strate
.igure 1!",(d* shows the process of coating catalytic
metals on the honeycomb" The wash-coat should have the
following characteristics:

& large surface area to increase contact with the exhaust

gas

+igh heat resistance

Chemical stability against poisonous components

lac4 of chemical reactivity with catalytic components

&de2uate adhesive strength to bond to the substrate under

high temperatures and drastic temperature changes"
The honeycom" su"strate
Controlling pollutants at cold start

&dvances in emission control technology have succeeded

in removing 1!!D of the regulated components after
warming up"

+owever$ to decrease emissions further$ the focus must

now shift to emissions at cold start" The main cold start
problem relates to the activation of the catalyst at low
temperatures"

The catalytic converter is a chemical reactor and the

reaction rate mainly depends on the operating
temperature"The catalyst does not wor4 well in
temperatures below 5-! MC" .igure 1!"1! lists some
countermeasures"18 Two technologies aimed at enhancing
the activity of catalysts at cold start are discussed below"

(educing heat mass and "ac)#pressure

The stricter exhaust gas laws have raised demands on the

monolith$ re2uiring substrates with a larger surface area than
the conventional @!! or !! cpsi"

The geometrical surface area of a substrate is mainly

determined by cell density$ while the wall thic4ness has very
little influence"

.or an effective conversion rate$ a high cell density is

preferred" &t a constant wall thic4ness$ however$ the mass of
the substrate increases and the pressure drop increases due
to a reduction in the open frontal surface area"

The pressure drop obstructs the smooth flow of exhaust gas"

Controlling pollutants at cold start

& high cell density thus increases the exhaust gas pressure drop and
the thermal mass of the substrate" This can be partially compensated
for by reducing the cell wall thic4ness$ which in turn may influence
the strength and durability of the substrate" #ltra-thin walled ceramic
substrates with 9!! and 18!! cpsi and a wall thic4ness of between 8
and 8"- mil (the unit mil represents !"!!1 inch* have a high geometric
surface area and a low mass"

.igure 1!"11 shows the light-off time (the time to the catalytic
converterRs effective phase* for +C and C) conversion as a function
of cell density"
Controlling pollutants at cold start

Eoth heat up 2uic4ly and show good conversion

behavior" The 9!! cpsi98 mil substrate is
superior to the 18!! cpsi98 mil substrate with
regard to bac4pressure and mechanical strength"

Thin-walled substrates with a high cell density

have proven to be very effective for catalytic
converters" They are lighter than the standard
monolith$ have a larger internal surface area and
reach the catalytic converterRs wor4ing
temperature with a relatively low thermal input"
Controlling pollutants at cold start
The close#coupled catalytic converter

The exhaust gas reaches temperatures of up to 9!!

MC very 2uic4ly after cold start" To use this energy
to heat the catalyst$ the converter has to be placed
as close as possible to the engine" The exhaust gas
in the exhaust pipe loses most of its heat energy in
the first 1 m away from the engine"

7f the time between the catalytic converterRs

response and its effective phase is cut to around
one 2uarter$ the cleaning efficiency rises to almost
93D"
Controlling pollutants at cold start
Controlling pollutants at cold start
*haust gas after#treatment for diesel engines
&iesel particulate filters

Giesel engines are becoming more popular for cars in the

European mar4et$ and this is encouraged not only by high
performance combustion control but also by exhaust gas
after-treatment"

Easically$ diesels are lean combustion engines$ so /)x and

particulates must be after-treated" The use of diesel engines
in cars is expected to grow if particulates and /)x are well
controlled"

The relationship between the conversion efficiency of a

three-way catalyst and air9fuel ratio is shown in .ig" 1!"-"
=etrol engines reduce /)x$ +C and C) by controlling the
stoichiometric air9fuel ratio"

7t is difficult to maintain stoichiometric combustion in a diesel

engine$ and therefore /)x cannot be reduced"

=articulate matter from diesel engines mainly consists of carbon

microspheres (dry-soot* on which hydrocarbons$ soluble organic
fraction (S).* and sulfates from the fuel and lubricant condense"

The 2uantity and composition of the particles depends on the

combustion process$ 2uality of diesel fuel and efficiency of after-
treatment"

The soot is a solid and it is difficult to remove by catalysis" To

decrease soot$ fuel and air should be well mixed$ but the resulting
increased combustion temperature raises /)x"

To decrease /)x$ flame temperature is lowered using E01 or

delayed in6ection timing" (Exhaust gas recirculation has been
fitted to all light-duty diesels"*
*haust gas after#treatment for diesel engines

Eut this then results in an increase in soot and

S).$ so a balance must be achieved between
the amount of soot and the amount of /)x"

Barious technologies have been proposed to

remove particulates from the exhaust gas"
)xidation catalysts are fitted to all new
diesel-engined cars and will be fitted to light
duty truc4s"

These oxidize the S). and remove +C and

C)$ but cannot oxidize the soot"
*haust gas after#treatment for diesel engines

Capturing particulates in a filter (diesel

particulate filter G=.* is a solution"

The filter captures all particle sizes

emitted$ but the problem is then how to
eliminate the accumulated soot$ which
raises the bac4-pressure and could
potentially cause a malfunction of the
engine"

The soot must therefore be captured

and burned continuously in the filter"
Soot burns in the region of --! to !!
MC$ but diesel car exhaust reaches only
1-! MC in city traffic conditions" The
problem of soot burn-off is referred to
as regeneration"
*haust gas after#treatment for diesel engines

.igure 1!"18 shows a cutaway view of a typical G=. combined

with anxidizing catalyst"

The G=. has a different microstructure to the monolith for petrol

engines" .igure 1!"15 shows the mechanism"

The channels in the G=.1- ceramic monolith are bloc4ed at

alternate ends (.ig" 1!"1@*" To pass through the monolith$ the
exhaust gas is forced to flow through the channel walls$ which
retain particulate matter in the form of soot but allow gaseous
components to exit"

This type of filter is called a wall-flow filter"

*haust gas after#treatment for diesel engines
*haust gas after#treatment for diesel engines
(egenerative methods

1egenerative methods fall essentially into two groups as shown in

.ig" 1!"1-"

Thermal regeneration raises the soot temperature to the light-off

temperature by either electrical or burner heating$ and catalytic
regeneration chemically lowers the light-off temperature of soot"

7n thermal regeneration$ the heater raises the temperature to burn

away the soot"

The thermal management of the filter during regeneration

(temperature$ oxygen content and flow rate* must be carefully
matched to the re2uirements of the filter"

)wing to fuel economy penalties incurred in thermal regeneration$

these problems ma4e thermal regeneration less attractive
*haust gas after#treatment for diesel engines

Catalytic regeneration is the alternative method" Soot

burns in air at around --! MC$ while it will react with
/)8 below 5!! MC" 7n the continuously regenerating
trap (C1T*$ (5 in .ig" 1!"1-*$ the oxidizing catalyst
placed before the G=. changes /) to /)8" The
/)8 generated in this way continuously oxidizes and
removes =I1$13 through the reaction$
/)
8 ; C < /) ; C)"

The main obstacle to widespread introduction of the C1T is the effect of sulfur in fuel" The
adsorption of S)8 inhibits the adsorption of /)$ hence bloc4ing the formation of /)8" This
is common to all oxidation catalysis in diesel after-treatments" 7n this type of coated catalyst$
the amount of S in the fuel must be low to avoid poisoning the catalyst"
*haust gas after#treatment for diesel engines

*penda"le catalyst additive

The expendable cerium-based catalyst is added to the diesel fuel

using an on-board container and a dosing system" The catalyst lowers
the light-off temperature of soot to @-! MC" Combustion compensates
for the residual temperature gap of 5!!MC (from @-!MC to 1-! MC*"
Chen soot accumulation in the filter becomes excessive$ additional
fuel controlled by in6ection raises the temperature of the soot" The
rich exhaust gas from the engine also heats up the exhaust gas
through an oxidation catalyst positioned before the particulate filter"

This system uses Ce)8 as the additive" The G=. filter is cleaned
automatically every @!! to -!! 4m" & system that uses expendable
additives does not depend on the sulfur level in diesel fuel" Barious
organic compounds are also 4nown to have a catalytic effect for
oxidizing particulates"
*haust gas after#treatment for diesel engines

The deN$ catalyst

The exhaust gas emitted by diesel and lean-burn petrol engines is

comparatively rich in oxygen" This inherently facilitates the removal
of +C$ C) and =I through oxidizing reactions$ but not the removal
of /)x" Girect decomposition of /)x is too slow without a catalyst$
so mechanisms using chemical reduction have been proposed" .igure
1!"11, provides some typical de/)x mechanisms"

The /)x storage reduction type (1 in .ig" 1!"1* is the same as that
for the gasoline engine (.ig" 1!"9*" The main problem is how to
generate an instantaneous rich state" The catalyst also operates poorly
with high-sulfur fuels" Selective reduction uses controlled in6ection of
a reducing agent into the exhaust gas" Ge/)x assisted by +Cs (5 in
.ig" 1!"1* and urea (8 in .ig" 1!"1* are currently being researched
for diesel engines"
*haust gas after#treatment for diesel engines
*haust gas after#treatment for diesel engines

&mmonia is very effective at reducing /)x$ but is toxic"

&n alternative is to in6ect urea$ ((/+8*8C)*$ which

undergoes thermal decomposition and hydrolysis in the
exhaust stream to form ammonia"
(/+
8*8 C) < /+5 ; +/C)

The /) and /)8 reduction then proceeds with the assistance of a catalyst (e"g"$ B8)-9C)59
Ti)8*"
+/C) ; +8) < /+5 ; C)8
@/) ; @/+5 ; )8< @/8 ; +8) and
8/)8 ; @/+5 ; )8< 5/8 ; +8)

This process is called selective catalytic reduction (SC1*$ and re2uires a metering system for
in6ecting urea (as an a2ueous solution*" .uel consumption does not increase because this method
does not re2uire excessive combustion control"
*haust gas after#treatment for diesel engines

The science and

technology of materials in
automotive engines
by +iroshi Samagata

Automotive *ngineering
Light!eight% Functional%
and Novel 'aterials
by Erian Cantor"

Advance composite
materials for automotive
applications
by &hmed Elmara4bi
(eference +oo)s
=resentation =repared Ey:
Ir" +ardi4 Shah
=resentation =repared Ey:
Ir" +ardi4 Shah