UNIT III ENGINE EXHAUST EMISSION CONTROL

Formation of NOx, HC/CO mechanism , Smoke and

Particulate emissions, Green House Effect , Methods
of controlling emissions , Three way catalytic converter
and Particulate Trap, Emission (HC,CO, NO and
NOx ,) measuring equipments, Smoke and Particulate
measurement, Indian Driving Cycles and emission
norms

Pollution Control

Pollution
Air pollutionis the introduction into
theatmosphereofchemicals,particu
lates,
orbiological
materialsthat
cause discomfort, disease, or death
to humans, damage other living
organisms such as food crops, or
damage
thenatural
environmentorbuilt environment.

Pollutants in Exhaust Gases of

I.C. Engine
The exhaust gases of IC engines
have following pollutants
Hydrocarbons
Carbon Monoxide (CO)
Nitrogen Oxide (Nox)
Particulates

Hydrocarbons in SI engine
Hydrocarbons formed by incomplete
combustion of fuel.
The quantity of un - burnt hydrocarbons
depend upon the turbulence and
combustion chamber design.
The oil film and deposit on cylinder
walls absorb fuel during intake and
compression and fuel vapour is
desorbed into the cylinder during the
expansion and exhaust.

Hydrocarbons in CI Engine
The diesel fuel component contain higher
molecular weights on average than the S.I.
engine fuel, resulting in higher boiling and
condensing temperature. HC Particles condense
on the surface of the solid carbon soot generated
during combustion.
A:F ratio is heterogeneous causes local spot of
rich and lean mixture. The fuel mixture do not
find oxygen to react causes in complete
combustion.
A small amount of liquid fuel is trapped at the tip
of the injector nozzle when fuel injection stop.

Carbon Monoxide (CO)

Carbon monoxide is an odorless, colorless and toxic
gas.
CO Formed as a result of cold flame reaction and rich
fuel ratio in combustion chamber local deficiency of
oxygen which causes incomplete combustion create CO.
The percentage of CO increases in Idle range and
decreases with the speed. In a passenger car CO
percentage has been found to be as high as 7% with the
rich mixture and 1.25% with near stiochiometric
mixture.
The complete emission of CO is not possible. Where as
0.5% CO should be considered as reasonable goal

Nitrogen Oxide (Nox)

In S.I engine if ignition spark is
advanced the cylinder temperature
will be increased and more NOx will
be produced.
In
C.I.
engine
with
divided
combustion chamber and indirect
injection tends to generate higher
level of NOx.

Particulate
In S.I. Engine particulates are
lead,
organic
particulates
including soot and sulphates.
Fuel containing Sulphur which
oxidized within engine cylinder
form SO2.
Leaded
fuel
emit
lead
compounds.
Soot
emissions(Black smoke) Is a
result of rich mixture.
In C.I. engine, carbonaceous
material (Soot) which some
organic compounds have been
absorbed.
Most
particulates
generate due to incomplete
combustion of fuel.

Effect of Pollutants on
Environment

FORMATION OF POLLUTANTS
There are some unburned or partially burned
hydrocarbons in the exhaust.
The amount is insignificant from an energy
standpoint, but it is objectionable from the viewpoint
of its odor, its photochemical smog, and from the
standpoint of its having a carcinogenic effect.
The products of photochemical smog cause watering
and burning of the eyes, and affect the respiratory
system, especially when the respiratory system is
marginal for other reasons.

HYDROCARBON EMISSIONS FROM SI ENGINES

The most widely accepted causes for hydrocarbon
emissions in exhaust gases of spark ignition engines
are:
1.Flame quenching at the combustion chamber walls,
leaving a layer of unburned fuel-air mixture adjacent to
the walls.
2. Crevices in the combustion chamber, small volumes
with narrow entrances, which are filled with the
unburned mixture during compression, and remains
unburned after flame passages, since the flame cannot
propagate into the crevices. The main crevice regions
are the spaces between the piston, the piston rings and
the cylinder walls. The other crevice regions are the
threads around the spark plug, the space around the
plug centre electrode, crevices around the intake and
exhaust valve heads, and the head gasket crevice.

FORMATION OF POLLUTANTS
4. Incomplete combustion, either partial burning or complete
misfire, occurring when the combustion quality is poor, e.g.
during engine transients when air-fuel, exhaust gas
recirculation, and spark timing may not be adequately
controlled.
All these processes, except misfire, result in unburned
hydrocarbons close to the combustion chamber walls. Mixing
of unburned hydrocarbons with the bulk cylinder gases occurs
during expansion and the exhaust blow down processes.
During the blowdown process a high concentration of
hydrocarbons is released from the cylinder through the
exhaust valve.
During the exhaust stroke the piston pushes most of the
remaining fraction of the cylinder mass with its high
hydrocarbon concentration into the exhaust.
The residual gases in the cylinder thus contain a high
concentration of hydrocarbons.

FORMATION OF POLLUTANTS

Hydrocarbon emissions from CI engines

The CI engines operate with an overall fuel-lean equivalence ratio,
therefore they emit only about one-fifth of the hydrocarbon
emissions of an SI engine. The following are the major causes for
hydrocarbon emissions in the exhaust of CI engines:
1.The diesel fuel contains components of higher molecular weights
on average than those in a gasoline fuel, resulting in higher boiling
and condensing temperatures.
This causes some hydrocarbon particles to condense on the
surface of the solid carbon soot generated during combustion.
Most of this is burned as mixing continues and the
combustion process proceeds but a small amount is exhausted out
of the cylinder.
2. The air-fuel mixture in a CI engine is heterogeneous with fuel
still being added during combustion. It causes local spots to range
from very rich to very lean and many flame fronts exist at the same

FORMATION OF POLLUTANTS
Hydrocarbon emissions from CI engines
Incomplete combustion may be caused by under-mixing or overmixing.
With under-mixing, in fuel-rich zones some fuel particles do not
find enough oxygen to react with, and in the fuel-lean zones
some local spots will be too lean for combustion to take place
properly.
With over-mixing, some fuel particles may be mixed with burned
gases and it will therefore lead to incomplete combustion.
3. A small amount of liquid fuel is often trapped on the tip of the
injector nozzle even when injection stops. This small volume of
fuel is called sac volume.
This sac volume of liquid fuel is surrounded by a fuel-rich
environment and therefore it evaporates very slowly causing
hydrocarbon emissions in the exhaust.

FORMATION OF POLLUTANTS
Carbon Monoxide (CO)

Carbon monoxide is toxic. The haemoglobin in the blood, which

carries oxygen to the different parts of the body, has a higher
affinity for carbon monoxide than for oxygen. The percent
carboxy haemoglobin gradually increases with time to an
equilibrium value which depends upon the carbon monoxide
concentrations.
Carbon monoxide is generated in an engine when it is operated
with a fuel-rich equivalence ratio as there is not enough oxygen
to convert all carbon to carbon dioxide. For fuel-rich mixtures,
CO concentrations in the exhaust increase steadily with the
increasing equivalence ratio. The engine runs rich when it is
started or when it is accelerated under load. For fuel-lean
mixtures, CO concentrations in the exhaust are very low and
are of the order 10-3 mole fraction.
Poor mixing, local rich regions, and incomplete combustion
create some CO. The SI engines often operate close to
stoichiometric at part load and operate fuel rich at full load.

FORMATION OF POLLUTANTS
Oxides of Nitrogen (NOx)
The oxides of nitrogen tend to settle on the haemoglobin in the
blood. The most undesirable toxic effect of oxides of nitrogen is
their tendency to join with the moisture in the lungs to form dilute
nitric acid. NOx is one of the primary causes of photochemical
smog (smoke + fog). Smog is formed by the photochemical
reaction as follows:
NO2 + energy from sunlight
NO + 0 + Smog
Monoatomic oxygen reacts with O2 to form ozone (03) as follows:
O + O2
O3
Ozone is harmful to lungs and other biological tissues. It is
harmful to crops and trees. It reacts with rubber, plastics and other
materials causing damage.
Most of the oxides of nitrogen comprise nitric oxide (NO), a small
amount of nitrogen dioxide (NO2) and traces of other nitrogen
oxides. These are all grouped together and the group is called NOx.
NOx is mostly formed from atmospheric nitrogen. There are a

FORMATION OF POLLUTANTS
Some of the NO forming reactions are:
N, O, OH are formed from the dissociation of N2, O2 and H2O vapour at high
temperatures that exist in the combustion chamber (2500-3000 K).
The higher the combustion reaction temperature, the more diatomic nitrogen (N2) will
dissociate to monatomic nitrogen (N) and more NOx will be formed.
At low temperatures, a very small quantity of NOx is created. The flame temperature is
maximum at the stoichiometric equivalence ratio (0 = 1.0) but maximum NOx, is formed
slightly at a lean equivalence ratio (0 = 0.95). At this condition the flame temperature
remains very high but excess oxygen helps in the formation of more NOx. The most
important engine variables that affect NOx emission are the fuel/air equivalence ratio, the
burned gas fraction (EGR and residual gas fractions) and combustion duration within the
cylinder. NOx is reduced in modem engines with fast-bum combustion chambers.
If ignition spark is advanced, the cylinder temperature will be increased and more NOx
will be produced. CI engines with divided combustion chambers and indirect injection
(DI) tend to generate higher levels of Nox.

 This causes the electron go to the burner

jet and positive ions go on collector. The
flow of ion on collector and the flow of
electron to the burner complete electrical
circuit.
The D.C. signal produced is proportional to
the number of ion formed and the number
of ion is proportional to the carbon atom in
flame. The D.C. signal modulated and fed
to amplifier and demodulator.
The signal recorded on a meter.

Catalytic Converter

Catalytic Converter
The main aim of catalytic converter is to
convert the harmful gases into the harmless
gases.
The catalytic converter converts harmful
gases like NOx, HC and CO into compounds
like N2, H2 and CO2.
Rhodium is used as reducing catalyst for
converting NOx in the exhaust has into
nitrogen and oxygen.
Platinum and Palladium are used as
oxidation catalyst which changes HC and
CO into Water and CO2.

Types of Catalytic Converter

Two Way Catalytic Converter
Which is used to control only CO and HC
emission by oxidation.

Three Way Catalytic Converter

Which control CO and HC by oxidation
as well as NOx by reduction.

Two Way Catalytic Converter

 It consist cylindrical unit like silencer and

it is installed into the exhaust system of a
vehicle such as motor cycle, car etc.
Inside the cylindrical tube there is honey
comb structure of ceramic or metal.
Which will be coated with alumina based
material with second coat of precious
metals like platinum, palladium or
rhodium.
this second coating serves as a catalyst
which causes the chemical reaction of
exhaust gases with coating material.

Three Way Catalytic

Converter
This is installed in the exhaust line
between manifold and muffler.
The converter have mesh or
honeycomb metal construction inside.
The catalyst is coated on mesh or
honeycomb.
It is commonly used in petrol engines.

 Stage 1 Reduction Catalyst:

The exhaust gases are first sent over the reduction catalyst (which is
made of platinum and rhodium). It converts oxides of nitrogen (NO x)
to nitrogen (N2) and oxygen (O2). The following reactions take place
when the exhaust gases pass over the reduction catalyst.
2NO N2+ O2
2NO2 N2+ 2O2
The reduction catalyst simply rips off nitrogen and oxygen from the
oxides of nitrogen. As you might know, nitrogen and oxygen are
harmless gases while oxides of nitrogen are really harmful to the
environment.

Stage 2 Oxidation Catalyst:

Exhaust gases that are free of oxides of nitrogen (NO x) are then sent
over the oxidation catalyst (made of platinum and palladium). The
oxidation catalyst coverts carbon-monoxide (CO) and hydrocarbons
(HC) in the gases into carbon-di-oxide (CO 2) and water (H2O).
The following reactions takes place when the exhaust gases pass
over the oxidation catalyst:
2CO + O2 2CO2
HC + O2 CO2+ H2O

FORMATION OF POLLUTANTS
PARTICULATES
The particulates from SI engines are lead, organic particulates including
soot and sulphates. Gasoline may contain some sulphur, which is
oxidized within the engine cylinder to form SO2.
is oxidized to SO3 which combines with water to form a sulphuric acid
aerosol.
Leaded gasolines emit lead compounds. Soot emissions (black smoke)
can result from combustion of overly rich mixtures. In properly adjusted
spark-ignition engines, soot in the exhaust is not a significant problem.
Diesel particulates consist mainly of combustion generated
carbonaceous material (soot) on which some organic compounds have
been absorbed.
Most particulates are generated in the fuel rich zones within the
cylinder during combustion due to incomplete combustion of fuel
hydrocarbons; some particulate matter is contributed by the lubricating
oil.
These are undesirable odorous pollutants. Maximum particulate
emissions occur when the engine is under load. At this condition,
maximum amount of fuel is injected to obtain maximum power from the
engine. It results in a rich mixture and poor fuel economy.

FORMATION OF POLLUTANTS
PARTICULATES
As the temperature decreases below 500C during expulsion, the particles become coated with HC
and with traces of other components.
The words particulates and soot are often used synonymously, but there is a difference in nature
between these two emissions.
Dry soot is usually the carbon that is collected on a filter paper in the exhaust of an engine.
The unit of measurement of soot is usually the Bosch Smoke Number, which is assessed by the
reflectance of a filter paper on which the soot has been collected.
Particulates contain more than simply the dry soot; they are the soot particles on which the other
compounds, often the polycyclic aromatic hydrocarbons (PAH), have condensed.
The PAH compounds have a tendency to be carcinogenic.
The level of particulates increases with the sulphur content in the fuel. Particulates are measured by
trapping the particles on glass-fibre filter papers placed in a dilution tunnel, and then weighing the
quantity.

MEASUREMENT OF POLLUTANTS
The measurement of exhaust emissions is very important for the control of air pollution
from IC engines.
CO concentrations are measured by infrared absorption,
NO concentrations are measured by chemi-luminescence and
Unburned HC are measured by flame ionization detector.
Non-dispersive Infra-red (NDIR) Analyzer
The NDIR analyzers are used for measuring the concentrations of carbon monoxide and
carbon dioxide. This device is based on the principle that the infrared energy of a
particular wavelength, peculiar to a certain gas, will be absorbed by that gas. The
infrared energy of other wavelengths will be transmitted by that gas.
Carbon dioxide absorbs infrared energy in the wavelength band of 4 to 4.5 microns (m)
and transmits the energy of the surrounding wavelengths. The carbon monoxide
absorption band is between 4.5 and 5 microns (gm).

Non-dispersive Infra-red (NDIR) Analyzer

Nitric oxide (NO) has also a weak absorption band,
allowing it to be analyzed by NDIR, but lack of
sensitivity and interference by water vapour do not give
high accuracy with low concentrations.
A schematic arrangement of the IR analyzer is shown in
Figure.
A wideband infrared radiation source consists of a heated
wire, which is placed in a quartz tube mounted in the
source block.
Radiation from the source is reflected within the
mounting block and passes out of a symmetrical pair of
rectangular apertures as two parallel beams into the two
separate cells a sample cell and a reference cell.
These cells are internally highly polished and gold plated
to ensure high transmission of radiation.
After passing through these cells the infrared radiation is
received in two separate detector cells, which are full of
the gas whose concentration is to be measured.

Non-dispersive Infra-red (NDIR) Analyzer

The two detector cells contain equal amounts of this gas
and are separated by a flexible diaphragm.
The sample cell is a flow-through tube that receives a
continuous stream of the mixture of gases to be analyzed.
When the particular gas to be measured is present in the
sample, it absorbs the infrared radiation at its characteristic
wavelengths. The percent of radiation absorbed is
proportional to the molecular concentration of the
component of interest in the sample.
The sample cells may be divided by quartz windows into
various lengths to give different ranges of sensitivity.
The quartz windows do not absorb infrared energy in the
region of interest. Low concentrations are best measured by
longer cells so that more molecules of interest are present.
The unused sample cells are generally flushed with a noninfrared absorbing gas such as oxygen or nitrogen, or with a
gas free of the components being measured, e.g. fresh air
for carbon monoxide analyzers.

Non-dispersive Infra-red (NDIR) Analyzer

The reference cell is sealed and is physically identical to the
sample cell. It is filled with an inert gas (usually nitrogen)
which does not absorb the infrared energy of the characteristic
wavelength of the species of interest.
The radiant energy, after passing through the cells, heats the
gas in the corresponding chamber of the detector. Since no
radiant energy is absorbed in the reference cell, the
corresponding chamber in the detector is heated more and its
pressure becomes higher than that in the other chamber.
This pressure differential causes the diaphragm to move and
vary the capacitance. Therefore, the variation in the
capacitance is proportional to the concentrations of the species
of interest in the exhaust sample.
The radiation from the source is interrupted by a rotating twobladed shutter driven by a synchronous motor.
The shutter is placed between the infrared source and the cells.

Non-dispersive Infra-red (NDIR) Analyzer

When the shutter blocks the radiation, the pressure in
the two compartments of the detector is equal because
there is no energy entering either of the chambers of
the detector.
This allows the diaphragm to return to its neutral
position. As the shutter alternatively blocks and
unblocks the radiation, the diaphragm fluctuates
causing the capacitance to charge cyclically.
This sets up an ac signal, which is impressed on a
carrier wave provided by a radio-frequency oscillator
(amplifications of ac signals have better drift-free
characteristics than the amplifications of dc signals).
Additional electronic circuitry in the oscillator unit
demodulates and filters the resultant signal.
This signal is then amplified and rectified to a de
signal which is measured by a meter or recorder. The
final dc signal is a function of the concentration of the
species of interest in the exhaust sample.

Non-dispersive Infra-red (NDIR) Analyzer

To set the zero point, a non-infrared-absorbing
gas, e.g. dry air, is passed through the
instrument. For the other points on the scale,
calibrating gases with known concentrations
are passed through the analyzer.
An error in the NDIR readings may arise if the
exhaust sample contains other species that can
absorb radiation at the same frequencies that
the gas in the detector will absorb.
In order to minimize this interference, a large
concentration of the interfering gas is placed in
the filter cells.
The analyzer zero is then set with this large
concentration of the interfering gas.

FLAME-IONIZATION DETECTOR (FID)

Some hydrocarbons have an infrared absorption at
3.4 microns, but some others, notably aromatics,
have almost none. Only about 50 % of exhaust
hydrocarbons is measured by NDIR, therefore, this
method is not suitable for the measurement of HC
concentrations.
The flame ionization detector is mainly used to
measure the unburned hydrocarbon concentrations
in the exhaust gases. It is based on the principle that
pure hydrogen-air flames produce very little
ionization, but if a few hydrocarbon molecules are
introduced the flames produce a large amount of
ionization. The ionization is proportional to the
number of carbon atoms present in the hydrocarbon
molecules.
A schematic arrangement of the instrument is shown
in Figure. It consists of a burner assembly, an
ignitor, an ion collector and electric circuitry. The
burner consists of a central capillary tube.

FLAME-IONIZATION DETECTOR (FID)

Hydrogen, or a mixture of hydrogen and
nitrogen, enters one leg of the capillary tube
and the sample enters through another leg. The
length and bore of the capillary tubes are
selected to control the flow rates. The mixture
of H2 - N2 - CH, then flows up the burner
tube.
The air required for combustion is introduced
from around the capillary tube.
The combustible mixture formed in the mixing
chamber is ignited by a hot wire at the top of
the burner assembly and a diffusion flame
stands at the exit to the burner tube.
An electrostatic field is produced in the vicinity
of the flame by an electric polarizing battery.
This causes the electrons to go to the burner jet
and the positive ions go to the collector.

FLAME-IONIZATION DETECTOR (FID)

The collector and the capillary tube form part of
an electric circuit.
The flow of ions to the collector and the flow of
electrons to the burner complete the electrical
circuit.
The dc signal produced is proportional to the
number of ions formed and the number of ions is
proportional to the number of carbon atoms in the
flame.
The dc signal generated is attenuated by a
modulator and then fed to an ac amplifier and a
demodulator.
The signal is then recorded on a meter. The meter
is calibrated directly in amount of hydrocarbon
concentrations.
To calibrate, the samples of known concentration
of hydrocarbons are fed to the instrument and the
meter readings are adjusted accordingly.

CHEMILUMINESCENCE ANALYZERS (CLA)

The chemilutilinescent analyzer measures the nitric oxide (NO)
concentrations. This technique is based on the principle that NO reacts with
ozone (03) to give some NO2 in an electronically excited state. These excited
molecules on decaying to the ground state emit red light (photons) in the
wavelength region from 0.6 gm to 3 gm, i.e.
NO + 03

NO2* + 02

NO2* --> NO2 + hv

where h is Planck's constant and v represents a photon of light.
The oxides of nitrogen (NO) from the engine exhaust comprise mainly a
combination of nitric oxide (NO) and nitrous oxide (NO 2).
By converting any exhaust NO2 to NO in a thermo-catalytic converter before
supplying the exhaust gas to the analyzer, the value of total nitrogen oxides
(N0x) can be obtained.

CHEMILUMINESCENCE ANALYZERS (CLA)

CHEMILUMINESCENCE ANALYZERS (CLA)

A schematic arrangement of the chemiluminescent instrument is shown in Figure. The
vacuum pump controls the pressure in the reaction chamber and draws ozone and the
exhaust sample. The ozone is produced by an electric discharge in oxygen at low pressure.
An NO2-to- NO converter is also shown in the diagram. An arrangement is made by using a
bypass line, so that it may be possible to measure only the NO concentrations or NO + NO2,
i.e. NOx concentrations in the combustion engine exhaust.
A mixture of a gas sample and ozone enters a reaction chamber (reactor) which is maintained
at a very low absolute pressure. The reaction of the ozone and nitric oxide when heated
under vacuum at 600C produces some electronically excited molecules of NO 2.
The electronically excited molecules on decaying, emit light. The light can readily be
detected accurately by a photo- multiplier.
The signal is then amplified and fed to a recorder. Many parameters affect light emission in
the reactor, it is therefore essential to calibrate the analyzer regularly.
Pure nitrogen may be used for zero setting. The zero control is adjusted until the digital
voltmeter reads zero, the nitrogen gas is then disconnected and a standard NO / N 2, mixture
is connected.
The NO/NOx, switch is set to 'NO' mode and the span control is used to adjust the NO
reading to correspond with the standard. For the NOx reading the NO/NOx, function switch
is pressed to initiate the NOx mode.

MEASUREMENT OF PARTICULATES
A dilution tunnel is used to measure the amount of particulate
present in the exhaust gas from the diesel engine. In the dilution
tunnel, the exhaust gases are diluted with ambient air to a
temperature of 52C or less, and a sample stream from the
diluted exhaust is filtered to remove the particulate material.
The particulate is trapped after dilution because the particulate
gets condensed over the filter at this temperature. The amount of
particulate trapped is obtained by weighing the filter before and
after the experiment.

MEASUREMENT OF EXHAUST SMOKE

Smoke-meters are used to measure the intensity of exhaust

smoke. Smoke-meters may measure either the relative quantity
of light that passes through the exhaust gas (Hartridge smokemeter), or the relative smudge left on a filter paper (Bosch
smoke-meter).

HARTRIDGE SMOKE-METER
It is based on the principle that the intensity of a light beam is reduced by
smoke which is a measure of smoke intensity. A schematic diagram to
illustrate the principle of this smoke-meter is shown in Figure.
Light from a source is passed through a standard length of a tube where the
exhaust gas sample is continuously supplied from the engine and at the
other end of the tube the transmitted light is measured by a photo-electric
cell.
The photoelectric cell converts the light intensity to an electric signal, which
is amplified and recorded on a meter. The intensity of smoke is expressed in
terms of smoke density. It is defined as the ratio of electric output from the
photoelectric cell when an exhaust sample is passed through the tube to the
electric output when clean air is supplied.

BOSCH SMOKE-METER
It is based on the principle that when a certain quantity of exhaust gas passes
through a fixed filter paper, some smoke smudge is obtained on it, which is a
measure of smoke intensity.
A schematic diagram to illustrate the principle of this instrument is shown in
Figure.
A fixed quantity of the exhaust gas from the engine is introduced into a tube,
where it passes through a fixed filter paper. Depending upon the smoke density,
some quantity of smudge is deposited on the filter paper, which can be
evaluated optically.
A pneumatically-operated sampling pump and a photoelectric unit are used for
the measurement of the intensity of smoke smudge on the filter paper.