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INSTITUTE OF TECHNOLOGY, NIRMA UNIVERSITY, AHMEDABAD 382 481, 08-10 DECEMBER, 2011 1

Review paper on Catalytic Converter for


Automotive Exhaust Emission
Julie M Pardiwala, Femina Patel, Sanjay Patel
pollutants like ozone, nitrogen dioxide & peroxyacyl nitrate
Abstract-- Air pollution generated from mobile sources is a which cause also global environmental problems [4].
problem of general interest. Vehicle population is projected to grow As the emission standards were tightened, more advanced
close to 1300 million by the year 2030. Due to incomplete combustion control strategies were applied that included modifications in
in the engine, there are a number of incomplete combustion products engine design and fuel system, control of engine parameters
CO, HC, NOx, particulate matters etc. These pollutants have negative and use of sophisticated exhaust after treatment devices [1]-
impact on air quality, environment and human health that leads in
stringent norms of pollutant emission. Numbers of alternative
[10].
technologies like improvement in engine design, fuel pretreatment, Reduction of toxic substances emission from combustion
use of alternative fuels, fuel additives, exhaust treatment or better engines can be achieved by primary (inside engine) measure
tuning of the combustion process etc. are being considered to reduce and secondary (outside engine) measures. As primary measures
the emission levels of the engine. Among all the types of technologies many different possibilities and technical methods of reducing
developed so far, use of catalytic converters based on platinum exhaust gas emission are used e.g. combustion of lean air fuel
(noble) group metal is the best way to control automotive exhaust mixture, multistage injection fuel, exhaust gas recirculation,
emissions. fuel gas after burning, loading of additional water into cylinder
This review paper discusses automotive exhaust emissions and its
volume [11],[12]. Nowadays secondary measures, in
impact, automotive exhaust emission control by platinum (noble)
group metal based catalyst in catalytic converter, history of catalytic
automotive exhaust aftertreatment processes a range of
convertor, types of catalytic convertor, limitation of catalytic advanced technology is applied based on oxidation and three-
convertor and also achievements of catalytic convertor. way catalyst adsorption storage and filtration process [13]. This
Keywords- Automotive emission, Catalytic Converter, Catalyst, enables reduction of the carbon monoxide (CO), hydrocarbons
Perovskite, Platinum group metal (HC), nitrogen oxide (NOx) and particulate emissions from a
gasoline or diesel engine to meet the demands of current and
I. INTRODUCTION future exhaust emission regulations [14]-[16].
This review paper discusses automotive exhaust emissions and

A ir pollution generated from mobile sources such as


automobiles contributes major air quality problems in rural
its impact, automotive exhaust emission control by platinum
(noble) group metal based catalyst in catalytic converter,
history of catalytic convertor, types of catalytic convertor,
as well as urban and industrialized areas in both developed and
developing countries. About 50 million cars are produced every limitation of catalytic convertor and also achievements of
year and over 700 million cars are used worldwide. Vehicle catalytic convertor.
population is projected to grow close to 1300 million by the year
2030 [1]. II. CATALYTIC CONVERTER
Most vehicular transportation relies on combustion of gasoline, The pollutants have negative impact on air quality,
diesel and jet fuels with large amount of emission of carbon environment and human health that leads in stringent norms of
monoxide (CO), unburned hydrocarbons (HC), nitrogen oxides pollutant emission. Numbers of alternative technologies like
(NOx) and particulates matter (PM) are especially concern improvement in engine design, fuel pretreatment, use of
[1],[2]. HC and CO occur because the combustion efficiency is alternative fuels, fuel additives, exhaust treatment or better
less than 100%. The NOx is formed during the very high tuning of the combustion process etc. are being considered to
temperatures (>1500 0C) of the combustion process resulting in reduce the emission levels of the engine. Out of various
thermal fixation of the nitrogen in the air which forms NOx. technologies available for automobile exhaust emission control
Typical exhaust gas composition at the normal engine a catalytic converter is found to best option to control CO, HC
operating conditions are: carbon monoxide (CO, 0.5 vol.%), and NOx emissions from petrol driven vehicles while diesel
unburned hydrocarbons (HC, 350 vppm), nitrogen oxides particulate filter and oxidation catalysts converter or diesel
(NOx, 900 vppm) hydrogen (H2, 0.17 vol.%), water (H2O, 10 oxidation catalyst have so far been the most potential option to
vol.%), carbon dioxide (CO2, 10 vol.%), oxygen (O2, 0.5 vol.%) control particulates emissions from diesel driven vehicle.
[3]-[10].Carbon monoxide is a noted poison that has an affinity A catalytic converter (CC) is placed inside the tailpipe through
for hemoglobin in the blood 210 times greater than the oxygen which deadly exhaust gases containing unburnt fuel, CO, NOx are
affinity prolonged exposure to levels above 9 ppm can lead to emitted [17]. The function of the catalytic convertor is to convert
reduce mental acuity for some individuals. HC and NOx lead to these gases into CO2, water, N2 and O2 and currently, it is
photochemical smog in presences of sunlight give secondary compulsory for all automobiles plying on roads in US and Japan
to have catalytic converters as they use unleaded petrol. In India,
2 INTERNATIONAL CONFERENCE ON CURRENT TRENDS IN TECHNOLOGY, NUiCONE 2011

the government has made catalytic converters mandatory for catalyst, the catalyst rips the nitrogen atom out of the molecule
registration of new cars [18]-[20]. and holds on to it, freeing the oxygen in the form of O2.
The nitrogen atoms bond with other nitrogen atoms that are
also stuck to the catalyst forming N2 [18].

2NO N2 + O2 (3)

3) The three-way catalytic converter (TWCs)

TWCs have the advantage of performing the oxidation


of carbon monoxide (CO), hydrocarbons (HC) and the
reduction of nitrogen oxides (NOx) simultaneously. Noble
Fig. 1. Catalytic Converter Position in a Vehicle [20] metals are usually used as the active phase in TWCs. Pd
catalysts are especially attractive since Pd is by far the
cheapest noble metal in the market and has better selectivity
III. HISTORY OF CATALYTIC CONVERTER and activity for hydrocarbons. Rhodium the other essential
The catalytic converter was invented by Eugene Houdry, a constituent of three-way catalysts is widely recognized as the
French mechanical engineer who lived in the United States most efficient catalyst for promoting the reduction of NO to
[17],[18]. In 1950, when the results of early studies of smog in N2. The TWCs performance in the emission control can be
Los Angeles were published, Houdry became concerned about affected by operating the catalyst at elevated temperatures (>
the role of automobile exhaust in air pollution and founded a 600 C).
special company, Oxy-Catalyst, to develop catalytic converters Reactions occurring on the automotive exhaust catalysts
for gasoline engines - an idea ahead of its time for which he are very complex as listed below. The major reactions are the
attained a patent (US2742437). But, until the extremely oxidation of CO and HC and the reduction of NOx. Also,
effective anti-knock agent tetra-ethyl lead was eliminated from water gas shift and steam reforming reaction occur.
most gasoline over environmental concerns, it would "poison" Intermediate products such as N2O and NO2 are also found.
the converter by forming a coating on the catalyst's surface, The NOx storage concept is based on incorporation of a
effectively disabling it. The catalytic converter was later on storage component into the three-way catalyst (TWCs) to
further developed by John J. Mooney and Carl D. Keith at the store NOx during lean conditions for a time period of minutes
Engelhard Corporation creating the first production catalytic [18].
converter in 1973. Beginning in 1979, a mandated reduction in
NOx required the development and use of a three way catalyst Reactions in Catalytic Converter
for CO, HC and NOx abatement [19]-[27].
2CO + O2 2CO2
Oxidation HC + O2 CO2 + H2O
IV. TYPES OF CATALYTIC CONVERTER
Reduction/three-way 2CO + 2NO 2CO2 + N2
1) The oxidization catalytic converter HC + NO CO2 + H2O + N2 2H2
+ 2NO 2H2O + N2
An oxidation catalyst is a device placed on the tailpipe of a
car. The oxidation catalyst is the second stage of the catalytic Water Gas Shift CO + H2O CO2 + H2
converter. It reduces the unburned hydrocarbons and carbon
monoxide by burning (oxidizing) them over a platinum and Steam reforming HC + H2O CO2 + H2
palladium catalyst. This catalyst aids the reaction of the CO
and hydrocarbons with the remaining oxygen in the exhaust
gas [18],[19].

HC O2 CO2 H2O (1)

2CO O2 CO2 (2)


2) The reduction catalytic converter

A reduction catalyst to control NOx can be used as a separate


system in addition to the oxidation catalytic converter. The
reduction catalyst is fitted upstream of the oxidation system. Fig. 2. Schematic diagram of Three way catalytic converter
The reduction catalyst is the first stage of the catalytic [18]
converter. It uses platinum and rhodium to reduce the nitrogen 4) Modern Three way catalytic converter
oxide emissions. When such molecules come in contact with the
INSTITUTE OF TECHNOLOGY, NIRMA UNIVERSITY, AHMEDABAD 382 481, 08-10 DECEMBER, 2011 3

A typical design of a modern three-way catalytic converter is thermal degradation, Superior cold start performance and low
a stainless steel container that incorporates a honeycomb deactivation caused by fuel sulphur [21].
monolith made of ceramic or metal. The monolith acts as the The noble metal are more expensive but the amount required
inert substrate coating with washcoat and active catalysts. for an automotive catalytic converter is small about 1 to 2 gm
Washcoat is a layer of mixture (mainly aluminum) which only. The noble metal loading typically varies from about 1.0
gives a further irregular and larger surface area also contains to 1.8 g/l (30 to 50 g/ft3) of catalytic converter volume. A
oxygen storage promoters and stabilizers. To prepare the mixture of platinum and palladium in 2:1 mass ratio is usually
active monolith, a layer of washcoat is first deposited on the employed as oxidation catalyst. Palladium has higher specific
substrate and the catalysts are then deposited on the washcoat activity than Pt for oxidation of CO, olefins and methane. For
or dipping the monolith into a slurry containing washcoat the oxidation of aromatics, Pd and Pt have similar activity
components and platinum group metals. The excess of the while for the oxidation of paraffin hydrocarbon (higher than
deposited material (washcoat) is removed using high-pressure propane) Pt is more active than Pd. Palladium has a lower
air or by applying a vacuum. Then the monolith is calcined to sintering tendency than platinum at high temperatures of about
obtain the finished catalyst. The monoliths geometrical 980 0C in the oxidizing atmosphere. Rhodium is primarily a
characteristics play a key role in effecting the distributions of NO reduction catalyst. The NO reduction activity of noble
temperature and species throughout the device and then metals is in the order Rh>Pd>Pt. when simultaneous
determining the efficiency of the converter. It combines the conversion of CO, HC and NOx is desired in the 3-way
requirements of compactness, high volumetric flow rates and catalytic converters, mixture of Pt + Pd is used with Rh in a
low back pressure [18], [19]. ratio of 5:1 to 10:1 [22].
The active metal in the automotive catalysts Pt, Pd and/or Rh
is very small (0.1 to 0.15 % by weight of monolith) and it is
highly dispersed on the surface of the catalyst support. The
particle size of the noble metal particles when fresh is around
50 nm or smaller. At high temperature the noble metals sinter
and particles may grow to a size of around 100 nm

Substrate or Support:

Pellets
The first catalytic converters of passenger cars in early 1970s
used a bed of spherical ceramic pellets. These are also known
Fig. 3. Schematic diagram of Catalytic Converter [20]
as packed bed catalytic converter. The spherical pellets made
of -alumina (-Al2O3) of 3-6 mm diameter were used. The
A catalytic converter besides its housing has three main material of pellets is selected to have a high mechanical
components [17]-[20]. strength against crush and abrasion even after exposure to
high temperature of around 1000 0C on the porous surface of
Catalyst: Pt, Pd, Rh pellets that provides a large surface area, the noble metal salts
are impregnated to a depth of about 250 m. The pellets are
Substrate or Support: Ceramic Honeycomb or Metallic then dried at about 120 0C and calcined to a temperature of
Honeycomb about 500 0C. The pellets catalysts were loaded with
approximately 0.05 % by weight of noble metals composed of
Intermediate coat or washcoat: Mixture of Si or Alumina Pt : Pd in 2.5 : 1 mass ratio [23],[25].

Catalyst: Monoliths

These include oxides of base metals e.g. copper, chromium, In our daily practice a monolith is a ceramic block consisting of a
nickel, cobalt etc. and the noble metals platinum (Pt), palladium large number of small straight and parallel channels. The
(Pd) and rhodium (Rh). Base metal oxides although found to be monoliths are made by extrusion. A special mixture of clay
effective at higher temperature but they sinter and deactivate binders and additives is pushed through a sophisticated dye to
when subjected to high-end exhaust gas temperature of create the monolith structure. The material is dried cut to the
conventional SI (Spark-Ignition) engine operation. Also, their required length and fired at high temperatures. The monolithic
conversion efficiency is severely inhibited by sulphur dioxide structure has a diameter of about 15 cm and can have different
resulting from sulphur in fuel. The base metal catalysts are shapes. The diameter of the channels ranges from 0.5 to 10 mm
required in a relatively large volume and consequently due to and the length of the monolith can be up to 1 meter long. On the
high thermal inertia they took longer to heat up to operating walls of the channels a catalytic active layer can be applied in
temperature. Therefore in practice only the noble metals are which chemical reactions can take place. Because of the large
used as they have high specific activity high resistance to number of channels the contact area between the catalytic layer
and the fluid that travels inside the channels is very large. Further
the channels are straight and parallel so that the flow is not
4 INTERNATIONAL CONFERENCE ON CURRENT TRENDS IN TECHNOLOGY, NUiCONE 2011

obstructed and the pressure drop across a monolith is extremely depends on catalyst formulation and engine operating
low [19]. conditions.
The ceramic and metallic monolithic allows high conversion
efficiencies at high gaseous throughput, provides a high
geometric surface area with lower pressure drop, excellent high
temperature and thermal shock resistance and can be
conveniently oriented in the exhaust train in any number of
directions. The monolithic catalyst is mounted in a stainless-
steel container with a matting material wrapped around it to
ensure resistance to vibration.

Fig. 5. Air fuel ratio [28].

Fig. 4. Different shapes and sizes of monolithic material [25]. 1) When the A/F ratio is leaner than stoichiometry

The size and shape of the final catalyst configuration varies The oxygen content of the exhaust stream rises and the
with each automobile company but typically, they are about 10- carbon monoxide content falls. This provides a high
12 cm in diameter and 7-10 cm in long with multiple efficiency operating environment for the oxidizing catalysts
honeycomb catalysts [25]. (platinum and palladium). During this lean cycle the catalyst
(by using cerium) also stores excess oxygen which will be
Washcoat: released to promote better oxidation during the rich cycle.

Ceramic and metallic monoliths have a geometrical surface area 2) When the A/F ratio is richer than stoichiometry
of 2.0-4.0 m2/l of substrate volume. A thin layer of inorganic
oxides known as wash coat is applied to the cells in monolith The carbon monoxide content of the exhaust rises and the
structure to increase effective surface area for dispersion of oxygen content falls. This provided a high efficiency
active catalyst that increase its contact with the reacting gases. operating environment for the reducing catalyst (rhodium).
The wash coat has pores of varying sizes ranging from 20 to The oxidizing catalyst maintains its efficiency as stored
100 . The ceramic monoliths generally have some wall oxygen is released [27], [28].
porosity or surface roughness that results in good adhesion of A closed loop feedback fuel management system with an
wash coat. The washcoat constitutes about 5 to 15 % of the oxygen sensor in the exhaust is used for precise control of
weight of ceramic monolith. Its thickness typically varies in the air-fuel ration. To obtain an efficient control of the A/F ratio
range 10-30 m on the walls and 60-150 m on the corners of the amount of air is measured and the fuel injection is
the square cells which reduces the open flow area of the controlled by a computerized system which uses an oxygen
catalyst. Wash coat increase surface area of the catalyst () sensor located at the inlet of the catalytic converter. The
substrate to 10000-40000 m2/l of monolith volume. The wash signal from this sensor is used as a feedback for the fuel
coat components support the catalyst function and to improve and air injection control loop. A second sensor is mounted
resistance of catalyst to thermal de-activation processes [26], at the outlet of the catalytic converter (Fig. 6.). This
[27]. configuration constitutes the basis of the so-called engine
on-board diagnostics (OBD). By comparing the oxygen
Air to fuel ratio: concentration before and after the catalyst, A/F fluctuations
are detected. Extensive fluctuations of A/F at the outlet
Conversion efficiency of NO, CO and HC as a function of the signal system failure. Effect of A/F ratio on the conversion
air-fuel in a three way catalytic converter. Fig.5 shows the efficiency of three-way catalysts narrow A/F window at the
conversion efficiency of NO, CO and HC as function of the air - stoichiometric point is the fingerprint of an effective TWC
fuel ratio. There is a narrow range of air- fuel ratio near system [29].
stoichimetry in which high conversion efficiencies for all three A simple closed loop feedback engine fuel management
pollutants are achieved. The width of this window is narrow system is shown schematically in fig. 6.
about 0.1 air-fuel ratio for catalyst with high mileage use and
INSTITUTE OF TECHNOLOGY, NIRMA UNIVERSITY, AHMEDABAD 382 481, 08-10 DECEMBER, 2011 5

Car and Driver magazine called the catalytic converter one of


the centurys 10 best automotive breakthroughs and the
Society of Automotive Engineers selected the catalytic
converter as one of the automobile industry's 10 greatest
achievements over the past 100 years [29].

VII. CONCLUSION
Fig. 6. A simple closed loop feedback control system for air/fuel ratio Environmental, ecological and health concern result in
control [20]
increasingly stringent emissions regulations of pollutant
emissions from vehicle engines. Among all the types of
V. LIMITATION OF CATALYTIC CONVERTOR technologies developed so far, use of catalytic converters is
In the harsh conditions experienced in the exhaust the best way to control auto exhaust emission.
stream with temperatures up to 1000 C the metal in the Three-way catalyst with stoichiometric engine control systems
catalyst is prone to deactivation by sintering, leading to a remain the state of art method for simultaneously controlling
reduction in surface area and hence catalytic activity. The hydrocarbon, CO and NOx emissions from vehicle.
conventional means to meet tightening legislative emissions The economical reasons, limited resources of platinum group
control targets is simply to increase the amount of PGM in (noble) metal and some operating limitations of platinum
the auto catalyst. The need to guarantee catalyst group metal based catalytic converters have motivated the
performance over the typical vehicle lifetime of 80,000 km investigation of alternative catalyst materials.
also means that excess metal must be added, since the
A. Abbreviations and Acronyms
performance of the catalyst drops off over time. In addition
rising PGM demand and costs are incentives towards
achieving lower metal loadings and higher activity [30]. TWC three way catalytic convertor
The compounds of the PGM are generally considered CO carbon monoxide
highly toxic while the Pd and Rh are carcinogenic in nature. HC hydrocarbons
Due to the fact that the PGM are produced due to the NOx nitrogen oxides
abrasion of automotive catalyst washcoat. That is why the PM particulates matter
road traffic is responsible for metallic and organic pollutant A/F air to fuel ratio
emissions which contaminate the environment [31]. Rh rhodium
The catalytic converters in the exhaust system become Pt platinum
deteriorated by several mechanisms e.g. thermal Pd palladium
deterioration and poisoning. Thermal deterioration occurs as
a result of exposure of the catalyst to high temperature
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