ENGINE EMISSIONS

AND
THEIR CONTROL

Prof. Dr. A.K.M. MOHIUDDIN

 INTRODUCTION
• Internal combustion engines generate undesirable
emissions during the combustion process. In this, both SI
and CI engines are equally responsible for the same. The
emissions exhausted into the surroundings pollute the
atmosphere and causes the following problems:
(i) global warming
(ii) acid rain
(iii) smog
(iv) odours
(v) respiratory and other health hazards.
• The major causes of these emissions are non-
stoichiometric combustion, dissociation of nitrogen, and
impurities in the fuel and air. The emissions of concern
are: unburnt hydrocarbon (HC), oxides of carbon (COx),
oxides of nitrogen (NOx), oxides of sulphur (SOx), and solid
carbon particulates.
 ENGINE EMISSIONS
Engine emissions can be classified into two categories:
(i) exhaust emissions and
(ii) non-exhaust emissions.
Exhaust Emissions
Major exhaust emissions are
(i) unburnt hydrocarbons, (HC)
(ii) oxides of carbon, (CO and CO2)
(iii) oxides of nitrogen, (NO and NO2)
(iv) oxides of sulphur, (SO2 and SO3)
(v) particulates
(vi) soot and smoke.
• The first four are common to both SI and CI engines and the
last two are mainly from CI engines. The main non-exhaust
emission is the unburned hydrocarbons from fuel tank and
crankcase blowby.
Figure 12.1 shows the variation of HC, CO and Nox emissions as a
function of equivalence ratio for an SI engine. As noticed from Fig.
12.1 that a rich mixture does not have enough oxygen to react
with all the carbon and hydrogen, and both HC and CO emissions
increase. For φ < 0.8, HC emissions also increase due to poor
combustion and misfire. The generation of nitrogen oxide
emissions is a function of the
combustion temperature, highest
near the stoichiometric conditions
when temperatures are at the
peak value. Maximum NOx
emissions occur at slightly lean
conditions, where the combustion
temperature is high and there is
an excess of oxygen to react with
the nitrogen. Fig. 12.1 Emissions as a Function of
Equivalence Ratio for an SI Engine
Figure 12.2 shows a qualitative picture of HC, CO and NOx
emissions with respect to equivalence ratio, φ for a four stroke DI
Diesel engine. As can be seen HC will decrease slightly with
increase in φ due to higher cylinder temperatures making it easier
to burn up any over-mixed (very lean) or under-mixed (rich) fuel-
air mixture. At high loads, however, HC may increase again if the
amount of fuel in regions too rich to
burn during primary combustion
process. CO emissions will be very
low at all equivalence ratio since
excess air is always available. NOx
emission will steadily increase as φ
increases due to increasing fraction
of cylinder contents being burnt
gases close to stoichiometric during Fig. 12.2 Emissions as a
combustion, and also due to higher Function of Equivalence Ratio
peak temperatures and pressures. for a CI Engine
 HYDROCARBON EMISSION
Fig. 12.1 shows the variation of HC emission levels with respect to
equivalence ratio for an SI engine. With a fuel-rich mixture there is
not enough oxygen to react with all the carbon, resulting in high
levels of HC and CO in the exhaust products. This is particularly
true during starting, when the air-fuel mixture is purposely made
very rich. It is also true to a lesser extent during rapid acceleration
under load. If air- fuel ratio is too lean poorer combustion occurs,
again resulting in HC emissions. The extreme of poor combustion
for a cycle is total misfire. This occurs more often as air-fuel ratio is
leaner.
The causes of hydrocarbon emissions from SI engine are:
(i) Incomplete combustion,
(ii) Crevice volumes and flow in crevices,
(iii) Leakage past the exhaust valve,
(iv) Valve overlap,
(v) Deposits on walls, (vi) Oil on combustion chamber walls.
Incomplete Combustion
Even when the fuel and air entering an engine are at the ideal
stoichimetric condition, perfect combustion does not occur and
some HC ends up in the exhaust. There are several reasons for
this. Complete and homogeneous mixing of fuel and air is almost
impossible. The incomplete combustion is due to:
(i) Improper mixing: Due to incomplete mixing of the air and fuel
some fuel particles do not find oxygen to react with. This causes
hydrocarbon emissions.
(ii) Flame quenching: As the flame goes very close to the walls it
gets quenched at the walls leaving a small volume of unreacted air
-fuel mixture. Another reason for flame quenching is expansion of
gases. As the piston moves down from TDC to BDC during power
stroke, expansion of the gases lowers both pressure and temp.
within the cylinders. This makes combustion slow and finally
quenches the flame somewhere late in the expansion stroke. This
leaves some fuel particles un-reacted and causes HC emission.
Crevice volumes and flow in crevices
The volumes between the piston, piston rings, and cylinder wall
are shown in Fig. 12.3. These crevices consist of a series of
volumes (numbered 1 to 5) connected by flow restrictions such as
the ring side clearance and ring gap. The geometry changes as
each ring moves up and down in its
ring groove, sealing either at the
top or bottom ring surface. The gas
flow, pressure distribution, and ring
motion are therefore coupled.
During the compression stroke and
early part of the combustion
process, air and fuel are
compressed into the crevice
volume of the combustion Fig. 12.3 Piston and Ring
chamber at high pressure. As much assembly in SI Engine Showing
as 3.5% of the fuel in the chamber Various Crevice Volume
can be forced into this crevice volume. Later in the cycle
during the expansion stroke, pressure in the cylinder is
reduced below crevice volume pressure, and reverse blow-by
occurs. Fuel and air, flow back into the combustion chamber,
where most of the mixture is consumed in the flame.
However, before the last elements of reverse blow-by occurs
flame will be quenched and un-reacted fuel particles come
out in the exhaust.
Crevice volume around the piston rings is greatest when the
engine is cold, due to the differences in thermal expansion of
the various materials. Up to 80% of all HC emissions can come
from this source.
Leakage Past the Exhaust Valve
As pressure increases during compression and combustion, some
amount of air-fuel mixture is forced into the crevice volume
around the edges of the exhaust valve and between the valve and
valve seat. A small amount even leaks past the valve into the
exhaust manifold. When the exhaust valve opens, the air-fuel
mixture which is still in this crevice volume gets into the exhaust
manifold . This causes a momentary increase in HC concentration
at the start of blowdown process.
Valve overlap
Valve overlap is a must to obtain satisfactory performance from
the engine. During valve overlap, both the exhaust and inlet valves
are open simultaneously creating a path where the fresh air-fuel
mixture can flow directly into the exhaust. A well-designed engine
minimizes this flow, but a small amount of fresh fuel-air mixture
escape is inevitable. The worst condition for this is at idle and low
speed operations when the overlap in terms of time is the largest.
Deposits on Walls
Gas particles, including those of fuel vapor are absorbed by the
deposits on the walls of the combustion chamber. The amount of
absorption is a function of gas pressure. The maximum absorption
occurs during compression and combustion. Later in the cycle,
when the exhaust valve opens and cylinder pressure gets reduced,
absorption capacity of the deposit material becomes lower. Gas
particles are desorbed back into the cylinder. Most gasoline blends
include additives to reduce deposit buildup in engines.
Oil on Combustion Chamber Walls
A very thin layer of oil gets deposited on the cylinder walls to
provide lubrication between the walls and the moving piston.
During compression and combustion, when cylinder pressure is
high, gas particles including fuel vapor are absorbed into the oil
film. When pressure is later reduced during expansion and
blowdown, the absorption capability of the oil is reduced and fuel
particles are desorbed back into the cylinder. Some of this fuel
ends up in the exhaust.
As an engine ages, the clearance between piston rings and cylinder
walls becomes greater, and a thicker film of oil is left on the walls.
Some of this oil film is scraped off the walls during the
compression stroke and gets burned during combustion.
Fig. 12.4 shows how HC emissions go up as oil consumption
increases. Oil consumption increases as the piston rings and
cylinder walls wear. In older engines,
oil being burned in the combustion
chamber is a major source of HC
emissions. In addition to oil
consumption going up as piston rings
wear, blowby and reverse blowby
also increase. The increase in HC
emissions is therefore both from Fig. 12.4 HC Exhaust
combustion of oil and from the added Emissions as a Function of
crevice volume flow. Engine Oil Consumption
 CARBON MONOXIDE (CO) EMISSION
Carbon monoxide (CO) is a colorless and odorless but a poisonous
gas. It is generated in an engine when it is operated with a fuel-
rich equivalence ratio as shown in Fig. 12.1. When there is not
enough oxygen to convert all carbon to CO2, some fuel does not
get burned and some carbon ends up as CO. Typically the exhaust
of an SI engine will be about 0.2 to 5% carbon monoxide. Not only
is CO considered an undesirable emission, but it also represents
lost chemical energy. CO is a fuel that can be combusted to supply
additional thermal energy:
1
CO  O 2  CO 2  heat (12.1)
2
Maximum CO is generated when an engine runs rich.
 OXIDES OF NITROGEN (NOX)
Exhaust gas of an engine can have up to 2000 ppm of oxides of
nitrogen. Most of this will be nitrogen oxide (NO), with a small
amount of nitrogen dioxide (NO2). There will also be traces of
other nitrogen- oxygen combinations. These are all grouped
together NOx, with x representing some suitable number. NOx is
very undesirable. Released NOx reacts in the atmosphere to form
ozone and is one of the major causes of photochemical smog.
NOx is created mostly from nitrogen in the air. There are a number
of possible reactions that form NO. All the restrictions are
probably occurring during the combustion process and
immediately after. These include but are not limited to:
O  N 2  NO  N (12.2)
N  O 2  NO  O (12.3)
N  OH  NO  H (12.4)
NO in turn can further react to form NO2 by various means,
including
NO  H 2 O  NO 2  H 2 (12.5)
NO  O 2  NO 2  O (12.6)
At very high temperatures that occur in the combustion chamber
of an engine , some diatomic nitrogen (N2) breaks down to
monatomic nitrogen (N) which is reactive:
N 2  2N (12.7)
Significant amount of N is generated in the temperature range of
2500-3000 K that can exist in an engine.
The higher the combustion reaction temperature, the more
diatomic nitrogen, N2, will dissociate to monatomic nitrogen, N,
and the more NOx will be formed. At low temperatures very little
NOx is created.
Photochemical Smog
NOx is one of the primary causes of photochemical smog, which
has become a major problem in many large cities of the world.
Smog is formed by the photochemical reaction of automobile
exhaust and atmospheric air in the presence of sunlight. NO2
decomposes into NO and monatomic oxygen:
NO2  energy from sunlight  NO  O  smog (12.8)
Monatomic oxygen is highly reactive and initiates a number of
different reactions, one of which is the formation of ozone:
O  O 2  O3 (12.9)

Ground-level ozone is harmful to lungs and other biological tissue.

It is harmful to plants and trees and causes very heavy crop losses
each year.
 PARTICULATES
The exhaust of CI engines contains solid carbon soot particles that
are generated in the fuel-rich zones within the cylinder during
combustion. These are seen as exhaust smoke and cause an
undesirable odorous pollution. Maximum density of particulate
emissions occurs when the engine is under load at WOT. At this
condition maximum fuel is injected to supply maximum power,
resulting in a rich mixture and poor fuel economy.
Soot particles are clusters of solid carbon spheres. These spheres
have diameters from 9 nm to 90 nm. The spheres are solid carbon
with HC and traces of other components absorbed on the surface.
 CATALYTIC CONVERTERS
The most effective after treatment for reducing engine emissions
is the catalytic converter found on most automobile and other
modern engines of medium or large size. CO and HC can be
oxidized to CO2 and H2O in exhaust systems if the temperature is
held at 600-700 ºC. If certain catalyst is present, the temperature
needed to sustain these oxidation processes is reduced to 250-300
ºC, making for a much more attractive system.
A catalyst is a substance that accelerates a chemical reaction by
lowering the energy needed for it to proceed. The catalyst is not
consumed in the reaction and so functions indefinitely unless
degraded by heat, age, contaminants, or other factors. Catalytic
converters are chambers mounted in the flow system through
which the exhaust gases pass through. These chambers contain
catalytic material, which promotes the oxidation of the emissions
contained in the exhaust flow.
Generally, catalytic
converters are called three-
way converters because they
are used to reduce the
concentration of CO, HC, and
NOx in the exhaust. catalytic
converter is usually a
stainless steel container
mounted somewhere along
the exhaust pipe of the
engine. Inside the container
is a porous ceramic structure
through which the exhaust
gas flows. In most converters,
the ceramic is a single honey-
comb structure with many
flow passages (Fig. 12.5). Fig. 12.5 Catalytic Converters for SI Engines
The surface of the ceramic passages contains small embedded
particles of catalytic material that promote the oxidation reactions
in the exhaust gas as it passes. Aluminum oxide (alumina) is the
base ceramic material used for most catalytic converters. Alumina
can withstand the high temperatures, it remains chemically
neutral, it has very low thermal expansion, and it does not
thermally degrade with age. The catalyst materials most
commonly used are platinum, palladium, and rhodium.
Palladium and platinum promote the oxidation of CO and HC as in
Eqs. 12.10 and 12.11, with platinum especially active in the
hydrocarbon reaction.
1
CO  O 2  CO 2 (12.10)
2
C x H y  z O 2  x CO 2  y H 2 O (12.11)
where z = x + 0.25y.
Rhodium promotes the reaction of NOx in one or more of the
following reactions:
1
NO  C O  N 2  CO 2 (12.12)
2
2NO  5CO  3 H 2 O  2NH 3  5CO 2 (12.13)
2NO  CO  N 2 O  CO 2 (12.14)
1
NO  H 2  N 2  H 2 O (12.15)
2
2NO  5H 2  2 NH 3  2H 2 O (12.16)
2NO  H 2  N 2 O  H 2 O (12.17)
Also often used is cerium oxide, which promotes the so-called
water gas shift CO  H 2 O  CO2  H 2 (12.18)
This reduces CO by using water vapor as an oxidant instead of O2, which
is very important when the engine is running rich.
 EXHAUST GAS RECIRCULATION (EGR)
The most effective way of reducing NOx emissions is to hold
combustion chamber temperatures down. Although practical, this
is a very unfortunate method in that it also reduces the thermal
efficiency of the engine.
Probably the simplest and practical method of reducing maximum
flame temperature is to dilute
the air-fuel mixture with a non-
reacting parasite gas. This gas
absorbs energy during
combustion without
contributing any energy input.
The net result is a lower flame
temperature. Any non-reacting
gas would work as a diluent, as
shown in Fig. 12.6.
Fig. 12.6 NOx reduction using Non-
combustible Diluent Gas to Intake Mixture
Those gases with larger specific heats would absorb the most
energy per unit mass and would therefore required the least
amount; thus less CO2 would be required than argon for the same
maximum temperature. However, neither CO2 nor argon is readily
available for use in an engine. The one non-reacting gas that is
available to use in an engine is exhaust gas, and this is used in all
modern automobile and other medium-size and large engines.
Adding any non-reacting neutral gas to the inlet air-fuel mixture
reduces flame temperature and NOx generation.
Exhaust gas recycle (EGR) is done by ducting some of the exhaust
flow back into the intake system, usually immediately after the
throttle. The amount of flow can be as high as 30% of the total
intake. EGR combines with the exhaust residual left in the cylinder
effectively reduce the maximum combustion temperature. The
flow rate of EGR is controlled by the engine Management System.
Not only does EGR reduce the max. temp. in the combustion
chamber, but it also lowers the overall combustion efficiency.
 NON-EXHAUST EMISSIONS
Apart from exhaust emissions there are three other sources in an
automobile which emit emissions. They are:
(i) Fuel tank: The fuel tank emits fuel vapors into the atmosphere.
(ii) Carburetor: The carburetor also gives out fuel vapors.
(iii) Crankcase: It emits blowby
gases and fuel vapors into the
atmosphere.
The fourth source is the tail pipe
which brings out exhaust
emissions. The contribution of
pollutants by source is shown in
Fig. 12.7.

Fig. 12.7 Distribution of

Emissions by Source (Petrol
Engine Powered Vehicle)
Thank You