UNIT III

ENGINE EXHAUST EMISSION

CONTROL
1
 SI/CI ENGINE EMISSIONS
2

 Unburned Hydro Carbons

 Carbon monoxide
 Oxides of nitrogen
 Oxides of sulphur and
 Particulates including smoke
3 FORMATION OF NOX
 The chemical mechanism of NO x formation during
combustion obeys hundreds of elementary chemical
reactions.

 Depending on the temperature range, stoichiometric

ratio and type of nitrous species present in the
combustion zone the oxides of nitrogen formation
mechanism changes.
 MAJOR SOURCES OF NOX FORMATION DURING
4
COMBUSTION

 Air nitrogen (N2)

 Thermal NOx
 Prompt NOx

 Fuel nitrogen (NF)

 Fuel NOx
5 THERMAL NOx
 Thermal NO x refers to NO x formed through high
temperature oxidation of the diatomic nitrogen found in
combustion air.

 The formation rate is primarily a function of temperature

and the residence time of nitrogen at that temperature.

 At high temperatures, usually above 1700K molecular

nitrogen (N 2 ) and oxygen (O 2 ) in the combustion air
disassociate into their atomic states and participate in a
series of reactions.
6 THERMAL NOx
 It is necessary to limit residence time to control NO x
formation, which favours very short combustor designs.
 Thermal NO x production also increases with the square
root of operating pressure.
 The formation of thermal NO x is given by extended
Zeldovich mechanism.
N2 + O → NO + N
N + O2 → NO + O
N + OH → NO + H
 The above three reactions are reversible reactions.
7 PROMPT NOx
 Prompt NO x can be a major source on formation of NO x
at low-temperature combustion of oxygenated fuels
such as biodiesel.

 Radicals such as C, CH, and CH2 fragments derived from

fuel reacts with the atmospheric nitrogen at low
temperature when compared to thermal NOx.

 This results in the formation of fixed species of nitrogen

such as NH (nitrogen monohydride), HCN (hydrogen
cyanide), H 2 CN (dihydrogen cyanide) and CN- (cyano
radical).
8 FUEL NOx
 This type of NOx is produced when nitrogen-bearing fuels
such as certain coals and oil are used as fuel.

 During combustion, the nitrogen bound in the fuel is

released as a free radical and ultimately forms free N 2 ,
or NO.

 Fuel NO x can contribute as much as 50% of total

emissions when combusting oil and as much as 80%
when combusting coal.
9 HYDROCARBON EMISSION FORMATION

 Hydrocarbon emissions result from the presence of

unburned fuel in the engine exhaust.
 About 9% of the fuel supplied to the engine is not burned
during the normal combustion phase of the expansion
stroke.
 Only 2% ends up in the exhaust the rest is consumed
during the other three strokes.
 As a consequence hydrocarbon emissions cause a
decrease in the thermal efficiency , as well as being an
air pollutant.
10 HYDROCARBON EMISSION FORMATION

 There are six primary mechanisms believed to be

responsible for hydrocarbon emissions:
11 HYDROCARBON EMISSION FORMATION
 Crevices – these are narrow regions in the
combustion chamber into which the flame
cannot propagate because it is smaller than
the quenching distance.
 Crevices are located around the piston, head
gasket, spark plug and valve seats and
represent about 1 to 2% of the clearance
volume.
 The crevice around the piston is by far the
largest, during compression the fuel air
mixture is forced into the crevice (density
higher than cylinder gas since gas is cooler
near walls) and released during expansion.
12 HYDROCARBON EMISSION FORMATION
 Oil layers - Since the piston ring is not 100% effective in
preventing oil migration into the cylinder above the piston, an
oil layer exists within the combustion chamber that traps fuel.
 Deposits - Carbon deposits build up on the valves, cylinder
and piston crown . These deposits are porous with pore sizes
smaller than the quenching distance so trapped fuel cannot
burn.
 Liquid fuel - For some fuel injection systems there is a
possibility that liquid fuel is introduced into the cylinder past
an open intake valve.
 The less volatile fuel constituents may not vaporize (especially
during engine warm-up) and be absorbed by the crevices or
carbon deposits.
13 HYDROCARBON EMISSION FORMATION
 Flame quenching - It has been shown
that the flame does not burn
completely to the internal surfaces, the
flame extinguishes at a small but finite
distance from the wall.
 When the exhaust valve opens the
large rush of gas escaping the cylinder
drags with it some of the hydrocarbons
released from the crevices, oil layer
and deposits.
 During the exhaust stroke the piston rolls
the hydrocarbons distributed along the
walls into a large vortex that ultimately
becomes large enough that a portion
of it is exhausted.
14 CARBON MONOXIDE EMISSION FORMATION
 Carbon monoxide remains in the exhaust if the oxidation of
CO to CO2 is not complete.
 This is because carbon monoxide is an intermediate product
in the combustion process.
 Generally this is due to lack of sufficient oxygen.
 The emission levels of CO from gasoline engine are highly
dependent on A/F ratio.
 The amount of CO released reduces as the mixture is made
leaner.
 Better carburetion and fuel distribution are key to low CO
emission in addition to operating the engine at increased air-
fuel ratio.
15 DIESEL ENGINE SMOKE EMISSION

 Engine exhaust smoke is a visible indicator of the combustion

process in the engine.
 Smoke indicates that the combustion is incomplete.
 Smoke in diesel engine can be divided into following three
categories:
 Blue Smoke
 White Smoke
 Black Smoke
16 DIESEL ENGINE SMOKE EMISSION
 Blue smoke:
 It results from the burning of engine lubricating oil that reaches
combustion chamber due to worn piston rings, cylinder liners and
valve guides.

 White or cold smoke:

 It is made up of droplets of unburnt or partially burnt fuel droplets and is
usually associated with the engine running at less than normal
operating temperature after starting, long period of idling, operating
under very light load, operating with leaking injectors and water
leakage in combustion chamber.
 This smoke normally fades away as engine is warmed up and brought
to normal stage.
17 DIESEL ENGINE SMOKE EMISSION

 Black or hot smoke:

 It consists of unburnt carbon particles (0.5 - 1 microns in
diameter) and other solid products of combustion.
 This smoke appears after engine is warmed up and is
accelerating or pulling under load.
18 FORMATION OF SMOKE IN DIESEL ENGINES
 The main cause of smoke formation is known to be inadequate
mixing of fuel and air.
 Smoke is formed when the local temperature is high enough to
decompose fuel in a region where there is insufficient oxygen to
burn the carbon that is formed.
 The formation of over-rich fuel air mixtures either generally or in
localized regions will result in smoke.
 Large amounts of carbons will be formed during the early stage of
combustion.
 This carbon appears as smoke if there is insufficient air, if there is
insufficient mixing or if local temperatures fall below the carbon
reaction temperatures (approximately 100 °C) before the mixing
occurs.
19 PARTICULATES EMISSION
 Particulate matter comes from hydrocarbons, lead additives and
sulphur dioxide.
 If lead is used with the fuel to control combustion almost 70% of
the lead is airborne with the exhaust gasses.
 In that 30% of the particulates rapidly settle to the ground while
remaining remains in the atmosphere.
 Particulates when inhaled or taken along with food leads to
respiratory problems and other infections.
 Particulates when settle on the ground they spoil the nature of the
object on which they are settling.
20 SI ENGINE EMISSIONS WITH RESPECT TO AIR
FUEL RATIO
21 METHODS OF CONTROLLING EMISSIONS
 NOx is decreased by
(I) Decreasing the combustion chamber temperature
The combustion chamber temperature can be decreased by
1. Decreasing compression ratio
2. Retarding spark timing
3. Decreasing charge temperature
4. Decreasing engine speed
5. Decreasing inlet charge pressure
6. Exhaust gas recirculation
7. Increasing humidity
22 METHODS OF CONTROLLING EMISSIONS
 NOx is decreased by

(II) By decreasing oxygen available in the flame front

The amount of oxygen available in the chamber can be

controlled by

1. Rich mixture
2. Stratified charge engine
3. Divided combustion chamber
23 METHODS OF CONTROLLING EMISSIONS
 Hydrocarbon emission can be decreased by

1. Decreasing the compression ratio

2. Retarding the spark
3. Increasing charge temperature
4. Increasing coolant temperature
5. Insulating exhaust manifold
6. Increasing engine speed
7. Lean mixture
24 METHODS OF CONTROLLING EMISSIONS
 CO can be decreased by

1. Lean air fuel ratio

2. Adding oxygen in the exhaust
3. Increasing coolant temperature
25 GREENHOUSE EFFECT

 The greenhouse effect is a process caused by

greenhouse gases, which occur naturally in the
atmosphere.

 This process plays a crucial role in warming the Earth's

surface, making it habitable.

 However, human-generated greenhouse gas emissions

upset the natural balance and lead to increased warmth.
26 GREENHOUSE EFFECT

The following are the green house gases and their

constituents

 Water Vapour (36–70%)

 Carbon dioxide (9–26%)
 Methane (4–9%)
 Ozone (3–7%)
27 GREENHOUSE EFFECT
 The Sun emits energy that is
transmitted to Earth.
 The Sun is very hot, the
energy is emitted in high-
energy short wavelengths
that penetrate the Earth's
atmosphere.
 About 30% of the Sun's
energy is reflected directly
back into space by the
atmosphere, clouds, and
surface of the Earth.
28 GREENHOUSE EFFECT
 The rest of the Sun's energy
is absorbed into the Earth's
system.

 Because the Earth is cooler

than the Sun, the energy is
emitted in the form of
infrared radiation, at
wavelengths longer than
the incoming solar energy.
29 GREENHOUSE EFFECT
 Greenhouse gases in the
atmosphere absorb much of
the long-wave energy
emitted from the Earth's
surface, preventing it from
immediately escaping from
the Earth's system.

 The greenhouse gases then

re-emit this energy in all
directions, warming the
Earth's surface and lower
atmosphere.
30 GREENHOUSE EFFECT
 The atmospheric
concentration of green
house gases has increased
over the past two centuries,
largely due to human-
generated carbon dioxide
emissions from burning fossil
fuels.

 This change causes Earth's

surface temperature to
increase.
 THREE WAY CATALYTIC CONVERTER
31

 The exhaust gases from an engine contain harmful

substances such as oxides of nitrogen (NO x ), carbon
monoxide (CO) and Hydrocarbons (HC).
 These substances produce extreme environment
hazards.
 A 3-way catalytic converters convert these harmful
substances to less harmful nitrogen (N2), carbon-di-oxide
(CO2) and water (H2O).
 THREE WAY CATALYTIC CONVERTER
32

A three-way catalytic converter makes use of two

catalysts to convert harmful gases to harmless gases.
Reduction Catalyst and
Oxidation Catalyst

 The reduction catalyst is made of platinum and rhodium

 The oxidation catalyst is made of platinum and
palladium.
 Both the catalysts have a ceramic honeycomb structure.
 THREE WAY CATALYTIC CONVERTER
33
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 (N 2 ) and
oxygen (O2).
 The following reactions take place when the exhaust
gases pass over the reduction catalyst.

2NO → N2 + O2
2NO2 → N2 + 2O2
 THREE WAY CATALYTIC CONVERTER
34
Stage 1 – Reduction Catalyst

 The reduction catalyst simply rips off nitrogen and

oxygen from the oxides of nitrogen.

 The nitrogen and oxygen are harmless gases while

oxides of nitrogen are really harmful to the environment.
 THREE WAY CATALYTIC CONVERTER
35
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
 THREE WAY CATALYTIC CONVERTER
36

 For efficient working of a three way catalytic converter

the air fuel ratio must be maintained at stoichiometric air
fuel ratio (14.7 : 1).
 A catalytic converter will start working only when the
exhaust gases reaches the temperature of 250°C.
 When the fuel contains lead as an additive, it will poison
the catalyst.
37 DIESEL PARTICULATE FILTER (PARTICULATE
TRAP)

 A diesel particulate filter (or DPF) is a device designed to

remove diesel particulate matter or soot from the exhaust gas
of a diesel engine.
 The diesel particulate filters usually remove 85% or more of the
soot and under certain conditions can attain soot removal
efficiencies of close to 100%.
 Some filters are single-use , intended for disposal and
replacement once it is full of accumulated ash.
38 DIESEL PARTICULATE FILTER
(PARTICULATE TRAP)
 The others type is designed to
burn off the accumulated
particulate either passively
through the use of a catalyst or by
active means such as a fuel
burner which heats the filter to
soot combustion temperatures.
 when the filter is full the sensor
elevates exhaust temperature or
lets in high amounts of NO x to
oxidize the accumulated
particulate matters.
39 NON-DISPERSIVE INFRA- RED ANALYZER (NDIR)
 The NDIR analyser is used to measure the concentration of
carbon dioxide and carbon monoxide.
 This device is based on the principle that the infrared energy
of particular wavelength, peculiar to a certain gas will be
absorbed by the gas.
 The infrared energy of other wavelengths will be transmitted
by that gas.
 The carbon dioxide will absorb the infrared wavelength band
of 4 to 4.5 (μm) microns.
 The carbon monoxide will absorb the infrared wavelength
band of 4.5 to 5 (μm) microns.
 NON-DISPERSIVE INFRA- RED ANALYZER (NDIR)
40
 NON-DISPERSIVE INFRA- RED ANALYZER (NDIR)
41
 A wideband infrared radiation
source consist 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 two separate cells – a
sample cell and a reference cell.
 NON-DISPERSIVE INFRA- RED ANALYZER (NDIR)
42
 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.
 The two detector cells contain
equal amount of this gas and
are separated by a flexible
diaphragm.
 NON-DISPERSIVE INFRA- RED ANALYZER (NDIR)
43
 The sample cell is a flow –
through tube that receives a
continuous stream of mixture of
gases to be analysed.
 When the particular gas to be
measured is present in the
sample, it absorbs the infrared
radiation at its characteristic
wavelength.
 The percent of radiation
absorbed is proportional to the
molecular concentration of the
component of the interest in the
sample.
 NON-DISPERSIVE INFRA- RED ANALYZER (NDIR)
44
 The reference cell consist of inert
gases usually Nitrogen.
 No radiant energy is absorbed in
the reference cell, the
corresponding chamber in the
detector is heated more and its
pressure becomes higher than
the other chamber.
 This pressure differential causes
the diaphragm to move and
vary the capacitance.
 The variation of capacitance is
proportional to the
concentration of species of
interest in the sample cell.
45 FLAME – IONIZATION DETECTOR (FID)

 The FID is used to measure Unburned Hydrocarbon emission in

the exhaust gases.
 It is based on the principle that pure hydrogen air flames
produces very little ionization, but if a few hydrocarbon
molecules are introduced the flame produces a large amount
of ionization.
 The amount of ionization is proportional to the number of
carbon atoms present in the hydrocarbon molecules.
 FLAME – IONIZATION DETECTOR (FID)
46
 FLAME – IONIZATION DETECTOR (FID)
47
 It consist of a burner assembly,
an ignitor, an ion collector and
electric circuitry.
 The burner consist of a central
capillary tube.
 Hydrogen, or a mixture of
hydrogen and nitrogen, enters
one leg of the capillary tube.
 The sample gas enters from the
other leg of the capillary tube.
 The length and bore of the
capillary tubes are selected to
control the flow rate.
 FLAME – IONIZATION DETECTOR (FID)
48
 The mixture of H 2 – N 2 – C n H m
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 top of the burner
assembly.
 An electrostatic field is produced
in the vicinity of the flame by an
electric polarizing battery.
 FLAME – IONIZATION DETECTOR (FID)
49
 This causes the electrons to go to
the burner jet and positive ions
go to the collector.
 The flow of ions to collector and
flow of electrons to the burner
complete the electric 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.
 CHIMILUMINESCENCE ANALYZER (CLA)
50
 CHIMILUMINESCENCE ANALYZER (CLA)
51
 The CLA measures the nitric
oxide (NO) concentrations.
 This technique is based on the
principle that NO reacts with
ozone (O 3 ) to give some NO 2 in
an electrically excited state.
 These excited molecules on
decaying to ground state emit
red light (photons) in the wave
length region from 0.6μm to 3μm.
NO + O3 NO2* + O2
NO2* NO2 + hv
 H – Plank’s constant, v - Photon
 CHIMILUMINESCENCE ANALYZER (CLA)
52
 The oxides of nitrogen (NOx) from
the engine exhaust comprise
mainly the combination of nitric
oxide (NO) and nitrous oxide
(NO2).
 By converting any exhaust NO 2
to NO in a thermo catalytic
converter before supplying the
exhaust gas to the analyser, the
value of total nitrogen oxides
(NOx) can be obtained.
 CHIMILUMINESCENCE ANALYZER (CLA)
53
 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.
 The converter converts the NO 2
into NO
 In this device an arrangement is
made by using a bypass line, so
that it may be possible to
measure only the NO
concentration or NO+NO 2
concentration in the exhaust.
 CHIMILUMINESCENCE ANALYZER (CLA)
54
 A mixture of exhaust gas and
ozone enters into the reaction
chamber.
 In the chamber the gas mixture
is heated at a temperature of
600°C.
 When heated the mixture
produces some electronically
excited molecules of NO2.
 This on decaying emits light,
which is detected accurately by
a photomultiplier.
 The this signal is then amplified
and fed into a recorder.
 HARTRIDGE SMOKE METER
55
 It based on the principle that the
intensity of a light beam is reduced
by smoke which is the intensity of
smoke.
 The light from a source is passed
through a standard length of tube
where the exhaust gas sample is
continuously supplied from the
engine and at other end of the tube
the transmitted light is measured by
a photo electric cell.
 The photoelectric cell converts the
light intensity to an electrical signal.
 HARTRIDGE SMOKE METER
56

 The intensity of smoke is expressed

in the 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
57
 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 the
measure of smoke intensity.
 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.
58 INDIAN DRIVING CYCLES
59 INDIAN DRIVING CYCLES
Standard Reference YEAR Region
India 2000 Euro 1 2000 Nationwide
NCR*, Mumbai,
2001
Kolkata, Chennai
Bharat Stage II Euro 2
2003.04 NCR*, 13 Cities†
2005.04 Nationwide
2005.04 NCR*, 13 Cities†
Bharat Stage III Euro 3
2010.04 Nationwide
Bharat Stage IV Euro 4 2010.04 NCR*, 13 Cities†
Bharat Stage V Euro 5 (to be skipped)

Bharat Stage VI Euro 6 2020.04 (proposed) Entire country

* National Capital Region (Delhi)† Mumbai, Kolkata, Chennai, Bengaluru, Hyderabad,

Ahmedabad, Pune, Surat, Kanpur, Lucknow, Sholapur, Jamshedpur and Agra
60 INDIAN DRIVING CYCLES

Year Reference Test CO HC NOx PM

1992 – ECE R49 17.3–32.6 2.7–3.7 – –

1996 – ECE R49 11.20 2.40 14.4 –

2000 Euro I ECE R49 4.5 1.1 8.0 0.36*

2005† Euro II ECE R49 4.0 1.1 7.0 0.15

ESC 2.1 0.66 5.0 0.10

2010† Euro III
ETC 5.45 0.78 5.0 0.16

ESC 1.5 0.46 3.5 0.02

2010‡ Euro IV
ETC 4.0 0.55 3.5 0.03

* 0.612 for engines below 85 kW (buses and trucks)

61 INDIAN DRIVING CYCLES
Year Reference CO HC HC+NOx NOx

1991 – 14.3–27.1 2.0–2.9 –

1996 – 8.68–12.4 – 3.00–4.36
1998* – 4.34–6.20 – 1.50–2.18
2000 Euro 1 2.72–6.90 – 0.97–1.70
2005† Euro 2 2.2–5.0 – 0.5–0.7
2.3 0.20 0.15
2010† Euro 3 4.17 0.25 – 0.18
5.22 0.29 0.21
1.0 0.1 0.08
2010‡ Euro 4 1.81 0.13 – 0.10
2.27 0.16 0.11
* for catalytic converter fitted vehicles
† earlier introduction in selected regions