Jude vimal michael.

Children’s club lecture series

National Centre for Catalysis Research
IIT-Madras
27April 2009
The pollutants present in auto exhaust gas are
 Sulphur dioxide, SO2 (primary pollutant)
 Nitrogen oxides NOx (primary or secondary
pollutants)
 Particulate matter PM (primary and secondary
pollutants)
 Carbon monoxide, CO, (primary pollutant)
 (volatile) organic compounds, HC (or VOCs) (primary
and secondary pollutants), and photochemical
oxidants,
 PAN -peroxyacetyl nitrate(secondary pollutants).
 DE is a complex mixture of hundreds of constituents
in either a gas or particle form.
 Gaseous components of DE include carbon dioxide,
oxygen, nitrogen, water vapor, carbon monoxide,
nitrogen compounds, sulfur compounds, and
numerous low-molecular-weight hydrocarbons.
 Among the gaseous hydrocarbon components of DE
that are individually known to be of toxicological
relevance are the aldehydes (e.g., formaldehyde,
acetaldehyde, acrolein), benzene, 1, 3-butadiene, and
polycyclic aromatic hydrocarbons (PAHs) and nitro-
PAHs.
 DPM consists of fine particles (fine particles have a diameter <2.5µm),
including a subgroup with a large number of ultrafine particles
(ultrafine particles have a diameter <0.1µm). Collectively, these
particles have a large surface area which makes them an excellent
medium for adsorbing organics.
 Their small size makes them highly respirable and able to reach the
deep lung. A number of potentially 1-1 toxicologically relevant organic
compounds are on the particles.
 The particles present in DE (i.e., diesel particulate matter [DPM]) are
composed of a center core of elemental carbon and adsorbed organic
compounds, as well as small amounts of sulfate, nitrate, metals, and
other trace elements.
 The hazards include acute exposure-related
symptoms, chronic exposure related non-cancer
respiratory effects, and lung cancer.
 The health hazard conclusions are based on exhaust
emissions from diesel engines built prior to the mid-
1990s. With current engine use including some new
and many older engines (engines typically stay in
service for a long time)
 The health hazard conclusions, in general, are
applicable to engines currently in use. As new and
cleaner diesel engines, together with different diesel
fuels, replace a substantial number of existing
engines, the general applicability of the health hazard
conclusions will need to be reevaluated.
According to the pollutants exposure the
effects are classified as
 Acute (Short-Term Exposure) Effects
 Chronic (Long-Term Exposure) Non-cancer
Respiratory Effects
 And Chronic (Long-Term Exposure)
Carcinogenic Effects.
Standard Reference Date Region
India 2000 Euro 1 2000 Nationwide

Bharat Stage II Euro 2 2001 NCR*,Mumbai,

Kolkata, Chennai
2003.04 NCR*,10 Cities

2005.04 Nationwide

Bharat Stage III Euro 3 2005.04 NCR*,10 Cities

2010.04 Nationwide

Bharat Stage IV Euro 4 2010.04 NCR*,10 Cities

*
National capital Region()
10 cities- Mumbai, Kolkata, Chennai, Bengaluru, , Ahmedabad, Pune, , and Agra.
(Ref: wiki)
 The Globally automotive pollution is controlled by
various emission performance standards set by
countries according to their population and economic
considerations.
 The Emission Performance standard is the
requirements that set specific limits to the amount of
pollutants that can be released into the environment.
 Many emissions standards focus on regulating
pollutants released by automobiles (motor cars) and
other powered vehicles but they can also regulate
emissions from industry, power plants, small
equipment such as lawn mowers and diesel
generators.
*Did you notice the Tamil nadu pollution control notice
board in velachery gate-IITM*
 1991 - Idle CO Limits for Gasoline Vehicles and Free Acceleration Smoke
for Diesel Vehicles, Mass Emission Norms for Gasoline Vehicles.
 1992 - Mass Emission Norms for Diesel Vehicles.
 1996 - Revision of Mass Emission Norms for Gasoline and Diesel
Vehicles, mandatory fitment of Catalytic Converter for Cars in Metros on
Unleaded Gasoline.
 1998 - Cold Start Norms Introduced.
 2000 - India 2000 (Eq. to Euro I) Norms, Modified IDC (Indian Driving
Cycle), Bharat Stage II Norms for Delhi.
 2001 - Bharat Stage II (Eq. to Euro II) Norms for All Metros, Emission
Norms for CNG & LPG Vehicles.
 2003 - Bharat Stage II (Eq. to Euro II) Norms for 11 major cities.
 2005 - From 1 April Bharat Stage III (Eq. to Euro III) Norms for 11 major
cities.
 2010 - Bharat Stage III Emission Norms for 4-wheelers for entire country
whereas Bharat Stage - IV (Eq. to Euro IV) for 11 major cities. Bharat
Stage IV also has norms on OBD (similar to Euro III but diluted)
 The European Union standards for emission
limits of automotive exhaust gases (values in
g km-1) are given in the Table previous slide.
 The typical concentration of the various
pollutants are listed out and when our
(Bharat stage –IV) compared to the European
standards we lag behind nearly 5 years.
 Modification of engine design (e.g., the fuel
management system) and the engine calibration
(e.g., the ignition timing) to decrease the engine
output (also called raw emission)
 Aftertreatment of the engine exhaust by solid
catalysts, to convert the engine raw emission
 A combination of engine exhaust after
treatment by solid catalysts with engine design
modification and/or controlled engine operation,
to allow optimal functioning of the
aftertreatment device.
Retrofit:
 Diesel retrofit involves the addition of an emission control device
to remove emissions from the engine exhaust.
 Retrofits can be very effective at reducing emissions, eliminating
up to 90 percent of pollutants in some cases.
 Some examples - Diesel oxidation catalysts, diesel particulate
filters, NOx catalysts, selective catalytic reduction, and exhaust gas
recirculation. Devices to control crankcase emissions also exist.
Repower:
 Repowering involves replacing an existing engine with a new
engine. This strategy is most effective for use in diesel-powered
equipment with a useful life longer than that of the engine.
Rebuild:
 All diesel equipment requires periodic maintenance. Routine
maintenance and repairs help to ensure that engines operate at
maximum performance and emission rates do not exceed the
designed standard.
Refuel:
 A variety of alternative fuels can be used in diesel engines.
Some require little or no modification to the engine while
others require engine conversion or replacement.
 Some of the alternative fuels include emulsified diesel,
biodiesel, natural gas, propane and ethanol. In addition to
these fuels, use of diesel fuel with lower sulfur content can
help to reduce emissions.
Replace:
 Replacement involves retiring higher polluting equipment
from service before it would otherwise be retired. Newer
equipment that meets more stringent emission standards is
purchased to replace the retire equipment.
 Reducing the base emissions from the engine by
improvements to the combustion process and fuel
management, addition of air injection or exhaust gas
recycle or by changes to the type of fuel or its
composition.
 Decreasing the time taken for the catalytic converter to
reach its full operating efficiency.
 Increasing the conversion efficiency of catalysts at their
working temperature.
 Store pollutants during the cold start for the release when
the catalyst is working.
 Device catalysts or strategies to destroy nitrogen oxides
under lean (oxygen rich) operation.
 Devise reliable ways to regenerate particulate filters.
 Increase the operating lifetime during which autocatalysts
and their supporting systems efficiently convert pollution.
Typical automotive exhaust converters. The one on the left has been cut
open to reveal the monolith. The insert shows a blow up of the upper
part of the monolith where a part has been chipped off
 Five basic catalytic concepts have been used
in the development of catalytic emission
control they are
 Closed loop control catalyst
 Open loop catalyst
 Dual bed catalyst
 Oxidation catalyst
 Lean oxidation catalyst
 In the closed-loop-controlled three-way catalyst, one type of
catalyst, which is placed in the exhaust gas stream, is able to
promote all the main reactions that lead to the simultaneous
removal of CO, HCs and NOx.
 To balance the extent of the oxidation and the reduction
reactions, the composition of the engine-out exhaust gas is
maintained at or around stoichiometry.
 This is achieved by a closed-loop engine operation control, in
which the oxygen content of the engine-out exhaust gas is
measured upstream of the catalyst with an electrochemical
oxygen sensor, also called the lambda sensor.
 This component is used by the engine management system to
regulate the amount of fuel fed into the engine, and so to
regulate the engine operation around the stoichiometric A/F
ratio.
 The extent of the secondary reactions is minimal under these
conditions. The feedback control of the engine causes a
small cyclic variation of the engine exhaust gas composition.
 This variation occurs in a second, which means a frequency
of 1 Hz, and with amplitude of 5–10% of the A/F set point.
This transient operation of the catalyst, however, has a
significant effect upon its performance, as will be described
below.
 There exists a multitude of engine management systems
with various degrees of complexity and refinement, affecting
the speed and the amplitude range of control of the engine
A/F ratio at each of the engine load and speed operation
conditions.
 The refinement of the engine management system affects
both the performance and the durability of the emission
control catalyst.
 This concept is a simplification of the first, as again a
multifunctional catalyst is used, that is able to
promote all of the reactions that lead to the removal
of CO, HCs and NOx.
 The composition of the exhaust gas is not controlled
and therefore varies over a wide range. This wider
operation range results in an overall lower
simultaneous conversion of the three exhaust gas
constituents
 This concept is used if the legislative limits can be
reached with a conversion of about 50%, or for the
retrofitting of engines that were not designed to be
equipped with catalytic emission control devices.
 Two different types of catalyst are used. The first catalyst
is either multifunctional, or is at least of capable of
promoting NOx reduction reactions.
 The engine is calibrated so as to guarantee a net reducing
exhaust gas composition. Under these conditions, the first
catalyst will lead to an elimination of the nitrogen oxides.
The second catalyst is an oxidation catalyst.
 Extra air is injected in front of the second catalyst to assist
the removal of CO and HCs. The secondary air can be
added either by mechanically or by electrically driven air
pumps.
 The dual-bed concept allows for a wider engine A/F range
and also maintains high conversion efficiency for the three
exhaust gas constituents under these conditions.
Therefore, a less-sophisticated engine management
system can be used.
 In this emission control concept, secondary
air is added to the exhaust gas to ensure a
lean composition, independent of the engine
operation condition. The catalyst is designed
to promote reactions between oxygen and
both CO and HCs, which can be removed to a
great extent, but NOx cannot be removed in
this manner.
 The fifth concept is also an oxidation catalyst, but it is
applied to engines that operate under lean conditions, the
so-called lean-burn engines. The A/F ratio of these engines
reaches values up to 26, corresponding to a lambda value
of about 1.8.
 The function of the catalyst could be limited to converting
CO and HCs. Because of the dilution effect in lean
combustion, the exhaust gas is colder than for closed-loop
controlled engines, and therefore special catalysts with
good low-temperature activity for the oxidation reactions
are needed.To date, however, this concept has not
achieved widespread application.
 The latest generation of lean-burn gasoline engines
applies the direct fuel injection principle, which enables
different catalytic exhaust gas after treatment concepts to
be used, such as the NOx-adsorber systems
 The three-way catalyst, consisting of Pt and Rh
particles supported on a ceramic monolith, represents
a remarkably successful piece of catalytic technology.
It enables the removal of the three pollutants CO, NO
and hydrocarbons
 Additionally, NO is reduced by H2 and by
hydrocarbons. To enable the three reactions to
proceed simultaneously – notice that the two first are
oxidation reactions while the last is a reduction – the
composition of the exhaust gas needs to be properly
adjusted to an air-to-fuel ratio of 14.7
 At higher oxygen content, the CO oxidation reaction
consumes too much CO and hence NO conversion
fails.
 If, however, the oxygen content is too low,
the entire NO is converted, but hydrocarbons
and CO are not completely oxidized.
 An oxygen sensor (λ-probe) is mounted in
front of the catalyst to ensure the proper
balance of fuel and air via a microprocessor-
controlled injection system.
 It is a simple oxygen sensor made in a similar
manner to the solid oxide fuel cell. An oxide
that allows oxygen ions to be transported is
resistively heated to ensure sufficiently high
mobility and a short response time (~1 s.).
 The oxygen content in the exhaust is
measured against a suitable reference, in this
case atmospheric air.
 The response is given by the Nernst equation:
 The λ-probe relies on the diffusion of atomic oxygen
through a solid electrolyte and, therefore, it will have a
certain response time.
 Reducing the thickness of the oxide membrane and
increasing the temperature both shorten the response
time, but a certain delay cannot be avoided.
 For example, if the driver suddenly steps on the gas pedal
the exhaust becomes reducing. Consequently, sulfur
deposited in the catalyst becomes hydrogenated to H2S,
causing the characteristic “rotten eggs” smell (this smell
sometimes arises during the startup of a cold engine).
 New types of sensors with faster response are therefore
being explored to avoid these effects. Ideally these should
be placed immediately after each cylinder and therefore
they should be capable of withstanding high
temperatures.
The Performance of the catalyst depends upon
the various factors such as
 the chemistry of the catalyst (e.g., the wash
coat, precious metals, age and preparation),
 the physics of the catalyst (e.g., support and
converter design) and
 the chemical engineering aspects of the
catalyst (e.g., reaction temperature,
residence time, gas composition and dynamic
conditions)
 The catalytic converters have three important layers. First is a
wash coat, which increases the surface area that the catalysts are
on: a large surface area is essential for high-efficiency exhaust
emission reductions.
 Next, a layer of noble metals like platinum and palladium are
vaporized on to the wash coat; these encourage carbon monoxide
and hydrocarbons to react into water vapor and carbon dioxide.
 Then there is a third layer of platinum and rhodium that reduces
nitrogen oxides (the third layer is what makes the converter
'three-way').
 These reactions seem contradictory: the oxidation process is more
efficient when large amounts of oxygen are present, but reduction
happens more efficiently in a low oxygen environment. But there
is a small window of exhaust stoichiometry, called the lambda
window, which creates favorable conditions for both reactions to
take place. Maintaining the air/fuel ratio to keep exhaust gasses in
this window is extremely important, hence the requirement of
oxygen sensor monitoring.
 Ceria is well known for his Oxygen storage
capacity and redox properties and these
properties are the key for the three-way catalyst
development.
 The major problem for the catalyst to stay active
is that to have adequate contact points between
the pollutant soot and the catalyst.
 When these catalysts are used through fuel
borne then this increases the contact points
between the soot and the catalyst and in turn
decreases the temperature of oxidation from
600 C to 400 C.
 CeO2 is one of the extensively used catalytic
components in many of the above described
after-treatment technologies due to its high
activity in the redox reactions
 . CeO2 is used in a well- known three-way
catalyst for CO, HC, and NOx abatement, as a
fuel-borne catalyst, and in the catalysed soot
filters in elimination of the soot particulates.
 The fuel-borne ceria catalyst leads to the
formation of the CeO2 nano-particles trapped
within the soot particle.
 Improving the cold-start performance
 HC adsorbers into the aftertreatment system-like activated
carbon, zeolites etc.,
 usage of precious metals should be limited to achieve cost
reduction
 future development will be the exchange of a substantial
portion of the platinum by palladium in high performance
oxidation catalyst
 In order to cope with the changing boundary conditions, and
especially the further reduction in exhaust gas temperature,
it is highly probable that at least a portion of the catalyst
volume will be moved closer to the engine outlet.
Thanks