Unit 6

EMISSION CONTROL

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 1

CONTENT
• Introduction
• Engine Emissions
• HC emission in S.I. engine and hydrocarbon emission in C.I
engine
• Emission of carbon monoxide
• kinetics of NOx formation, NO formation in S.I. engines, NOx
formation in C.I. engines
• Exhaust gas treatment: like Catalytic converter
08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 2
INTRODUCTION
• All IC engines produce undesirable emissions as a result of combustion.
• The emissions of concern are unburned hydrocarbons (UHC), carbon
monoxide (CO), oxides of nitrogen such as nitric oxide and nitrogen dioxide
(NOx), sulfur dioxide, and solid carbon particulates.
• These emissions pollute the environment and contribute to acid rain, smog
odors, and respiratory and other health problems.
• HC emissions from gasoline-powered vehicles include a number of toxic
substances such as benzene, polycyclic aromatic hydrocarbons (PAHs), 1,3-
butadiene and three aldehydes (formaldehyde, acetaldehyde, acrolein).
• Carbon dioxide is an emission that is not regulated but is the primary
greenhouse gas responsible for global warming.

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 3

• During the 1940s air pollution as a problem was first recognized in the Los
Angeles basin.
• Two causes of this were the large population density and the natural
weather conditions. Smoke and other pollutants combined with fog to
form smog.
• In 1966 HC and CO emission limits were introduced in California.
• All of North America usually follows California’s lead (all US in 1968).
• By making more fuel efficient engines and with the use of exhaust after
treatment, emissions per vehicle of HC, CO, and NOx were reduced by
about 95% during the 1970s and 1980s.
• Automobiles are more fuel efficient now (2x compared to 1970) but there
are more of them and the trend is to larger SUVs, as a result fuel usage is
unchanged over this period.
08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 4
ENGINE EMISSIONS
Classifications
• Exhaust emission: liberated at exhaust tail pipe.
• Non-exhaust emission
Exhaust emission
• Unburnt hydrocarbons(HC)
• Oxides of carbon (CO and CO2)
• Oxides if nitrogen (NO and NO2)
• Oxides of Sulphur (SO2 and SO3)
• Particulates, soot and smoke

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 5

EMISSIONS AND POLLUTANTS
• Engine emissions undergo chemical
reactions in atmosphere known
largely as ‘photochemical’
reactions and give rise to other
chemical species which are
hazardous to health and
environment. Linkage engine
emissions and air pollutants is
shown
• TSP = Total suspended particulate
matter in air
• PAN = Peroxy- acetyl nitrate

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 6

EMISSION SOURCES IN IC ENGINE
• SI Engines: CO, HC and Nox

• CI Engines : CO2, HC, NOx and

PM

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 7

ILL EFFECTS ON HEALTH

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 8

EMISSION FORMATION IN SI ENGINES

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 9

UNBURNT HYDROCARBON EMISSION
• Hydrocarbon emissions result from the presence of unburned fuel in the
engine exhaust.
• However, some of the exhaust hydrocarbons are not found in the fuel, but
are hydrocarbons derived from the fuel whose structure was altered due to
chemical reaction that did not go to completion. For example:
acetaldehyde, formaldehyde, 1,3 butadiene, and benzene all classified as
toxic emissions.
• 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.

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 10

HYDROCARBON EMISSION SOURCES FOR SI ENGINES
• There are six principal mechanisms believed to be responsible for
hydrocarbon emissions:
Source % fuel escaping during % HC emissions
normal combustion

Crevices 5.2 38
Oil layers 1.0 16
Deposits 1.0 16
Liquid fuel 1.2 20
Flame quench 0.5 5
Exhaust valve leakage 0.1 5
Total 9.0 100

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 11

HYDROCARBON EMISSION SOURCES
• 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.

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 12

HYDROCARBON EMISSION SOURCES
• Oil layers - Since the piston ring is not 100% effective in preventing oil migration
into the cylinder above the piston, oil layers exist within the combustion chamber.
This oil layer traps fuel and releases it later during expansion.
• Deposits – With continued use carbon deposits build up on the valves, cylinder
and piston head. These deposits are porous with pore sizes smaller than the
quenching distance so trapped fuel cannot burn. The fuel is released later during
expansion.
• 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.
• 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. Most of this gas eventually diffuses into the burned gas during
expansion stroke.
08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 13
HYDROCARBON EXHAUST PROCESS
• Exhaust valve leakage: 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
Blowdown Exhaust Stroke
becomes large enough that a
portion of it is exhausted.

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 14

HYDROCARBON EMISSION SOURCES FOR CI ENGINES

• Crevices - Fuel trapped along the wall by crevices, deposits, or oil due to
impingement by the fuel spray (not as important as in SI engines).
• Under mixing of fuel and air - Fuel leaving the injector nozzle at low velocity, at
the end of the injection process cannot completely mix with air and burn.
• Over mixing of fuel and air - During the ignition delay period evaporated fuel
mixes with the air, regions of fuel-air mixture are produced that are too lean to
burn. Some of this fuel makes its way out the exhaust. Longer ignition delay
more fuel becomes over mixed

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 15

PHOTOCHEMICAL SMOG
• Photochemical smog is a brownish-gray haze resulting from the
reactions caused by solar ultraviolet.
• Radiations between hydrocarbons and oxides of nitrogen in the
atmosphere.
• The air pollutants such as ozone, nitric acid, organic compounds like
peroxy- acetyl nitrates or PAN ( CH3CO-OO-NO2) are trapped near the
ground by temperature inversion experienced especially during
winter months.
• These chemical substances can effect human health and cause
damage to plants.
08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 16
• The photochemical reactions are initiated by nitrogen oxides emitted
by vehicles into atmosphere. A simple set of reactions leading to
Photochemical smog formation is as follows:
• Hv is energy of a photon and UV is ultraviolet light radiations .

• The above reactions form NO2 photolytic cycle. However, if only these
reactions are involved then, NO2 concentration in the atmosphere would
remain constant.

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 17

• But, volatile organic compounds (VOCs) that include unburned
hydrocarbons and their volatile derivatives also react with NO and O2
to form NO2

• The reactions between HC and NO do not necessarily involve ozone

and provide another route to form NO2 and thus, the concentration
of ozone and NO2 in the urban air rises.
• The most reactive VOCs in atmosphere are olefins i.e., the
hydrocarbons with C=C bond. The general reaction between
hydrocarbons (RH) and NO may be written as
08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 18
FORMATION OF NITROGEN OXIDES IN SI ENGINE
• Nitric oxide is the major component of NOx emissions from the
internal combustion engines. During combustion, three probable
sources of NO formation are:

• Thermal NO is the dominant source of nitrogen oxides in IC engines.

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 19

THERMAL NO
• NO is formed in the high
temperature burned gases behind
the flame front. The rate of
formation of NO increases
exponentially with the burned gas
temperature although, it is slower
compared to the overall rate of
combustion.
• The three reactions commonly
referred to as the extended
Zeldovich mechanism govern the
formation of thermal NO.
Kinetics and Modelling of Thermal NO Formation • NO Formation is a Function of
Temperature and O2
08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 20
EFFECT OF EQUIVALENCE RATIO ON EMISSIONS
• NOx and CO are formed in the burned gases in the cylinder.
• Unburned HC emissions originate when fuel escapes
combustion due to several processes such as flame
quenching in narrow passages present in the combustion
chamber and incomplete oxidation of fuel that is trapped or
absorbed in oil film or deposits
• NOx is formed by oxidation of molecular nitrogen. During
combustion at high flame temperatures, nitrogen and oxygen
molecules in the inducted air breakdown into atomic species
which react to form NO. Some NO2 is also formed and NO
and NO2 together are called as NOx.
• CO results from incomplete oxidation of fuel carbon when
insufficient oxygen is available to completely oxidize the fuel.
CO rises steeply as the air-fuel (A/F) ratio is decreased below
the stoichiometric A/F ratio.
• HC originates from the fuel escaping combustion primarily
due to flame quenching in crevices and on cold chamber
walls, fuel vapor absorption in the oil layer on the cylinder
and in combustion chamber deposits, and presence of liquid
fuel in the cylinder during cold start Air-fuel ratio is one of
the most important parameter that affect the engine exhaust
emissions.

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 21

EMISSION FORMATION IN CI ENGINES
Pollutant formation is strongly dependent
on the fuel-air ratio distribution in the spray
08-Oct-16
• NO is formed in the high temperature burned
gases in the flammable region. Maximum burned
gas temperatures result close to stoichiometric air-
fuel ratio and these contribute maximum to NO
formation.
• CO is formed in fuel rich mixtures in the flammable
region.
• Soot forms in fuel-rich spray core where fuel vapor
is heated by the hot burned gases
• Unburned HC and oxygenated hydrocarbons like
aldehydes originate in the region where due to
excessive dilution with air the mixture is too lean
at the spray boundaries. In excessive lean mixtures
combustion process either fails to begin or does
not reach completion.
• Towards the end of combustion, fuel in the nozzle
sac and orifices gets vaporized, enters the
combustion chamber and contributes to HC
emissions.
Sangamesh Bhure, Asst Prof, SIT Pune 22
NITROGEN OXIDES
• NOx includes nitric oxide (NO) and nitrogen dioxide (NO2)

• In SI engines the dominant component of NOx is NO Forms as a result of dissociation of molecular nitrogen and oxygen.

• Since the activation energy of the critical elementary reaction is high the reaction rate is temperature dependent
Therefore NO is only formed at high temperatures and the reaction rate is relatively slow.

O+N2→NO+N

• At temperatures below 2000K the reaction rate is extremely slow, so NO formation not important. Since the cylinder
temperature changes throughout the cycle the NO reaction rate also changes.

• Once the element temperature reaches 2000K the reaction rate becomes so slow that the NO concentration effectively
freezes at a value greater than the equilibrium value.
• increased residual gas
• exhaust gas recirculation (EGR)
• moisture in the inlet air

• In CI engines
08-Oct-16 the cylinder gas temperature is governed by the
Sangamesh Bhure, Asstload and
Prof, SIT injection timing
Pune 23
PARTICULATE MATTER
• A high concentration of particulate matter (PM) is manifested as visible smoke in the
exhaust gases.
• Particulates are any substance other than water that can be collected by filtering the
exhaust, classified as:
• solid carbon material or soot
• condensed hydrocarbons and their partial oxidation products
• Diesel particulates consist of solid carbon (soot) at exhaust gas temperatures below
500oC HC compounds become absorbed on the surface.
• In a properly adjusted SI engines soot is not usually a problem
• Particulate can arise if leaded fuel or overly rich fuel-air mixture are used. burning
crankcase oil will also produce smoke especially during engine warm up where the
HC condense in the exhaust gas.
08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 24
PARTICULATE MATTER
• Most particulate material results from incomplete combustion of fuel HC which
occurs in fuel rich mixtures.
• Based on equilibrium the composition of the fuel-oxidizer mixture at the onset of
soot formation occurs when x ≥ 2a (or x/2a ≥ 1) in the following reaction:
y
C x H y  aO2  2aCO  H 2  ( x  2a )C ( s )
2
• i.e. when the (C/O) ratio exceeds 1. Experimentally it is found that the critical
C/O ratio for onset of soot formation is between 0.5 and 0.8The CO, H2, and C(s)
are subsequently oxidized in the diffusion flame to CO2 and H2O via the following
second stage
1 1
CO  O2  CO2 C ( s )  O2  CO2 H2  O2  H 2O
2 2
• Any carbon not oxidized in the cylinder ends up as soot in the exhaust!
08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 25
PARTICULATES AND CI ENGINES
• Particulates are a major emissions
problem for CI engines. Exhaust
smoke limits the full load overall
equivalence ratio to about 0.7
• An outstanding problem for diesel
engine designers is that in order to
reduce NOx one wants to reduce
the AFT but this has the adverse
effect of decreasing the amount of
soot oxidized, or increases the
One technique for measuring particulate involves diluting the exhaust
amount of soot in the exhaust.
gas with cool air to freeze the chemistry before measurements

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 26

PARTICULATES AND CI ENGINES
• An example of this dilemma is
changing the start of injection,
e.g., increasing the advance
increases the AFT

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 27

CARBON MONOXIDE
• Carbon monoxide appears in the
exhaust of fuel rich running
engines.
• For fuel rich mixtures there is
insufficient oxygen to convert all
the carbon in the fuel to carbon
dioxide.

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 28

CARBON MONOXIDE
• The C-O-H system is more or less at equilibrium during combustion and
expansion.
• Late in the expansion stroke when the cylinder temperature gets down to
around 1700K the chemistry in the C-O-H system becomes rate limited and
starts to deviate from equilibrium.
• In practice it is often assumed that the C-O-H system is in equilibrium until
the exhaust valve opens at which time it freezes instantaneously.
• The highest CO emission occurs during engine start up (warm up) when the
engine is run fuel rich to compensate for poor fuel evaporation.
• Since CI engines run lean overall, emission of CO is generally low and not
considered a problem.

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 29

EMISSION CONTROL TECHNIQUES
• The current emission limits for HC, CO and NOx have been reduced to
4%, 4% and 10% of the uncontrolled pre-1968 values, respectively.
• Three basic methods used to control engine emissions:
• Engineering of combustion process - advances in fuel injectors,
oxygen sensors, and on-board computers.
• Optimizing the choice of operating parameters - two NOx control
measures that have been used in automobile engines since 1970s
are spark retard and EGR.
• After treatment devices in the exhaust system - catalytic
converter
08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 30
Catalytic Converter
• All catalytic converters are built in
a honeycomb or pellet geometry to
expose the exhaust gases to a large
surface made of one or more noble
metals: platinum, palladium and
rhodium.
• Rhodium used to remove NO and
platinum used to remove HC and
CO.
• Lead and sulfur in the exhaust gas
severely inhibit the operation of a
catalytic converter (poison).

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 31

THREE-WAY CATALYTIC CONVERTER
• A catalyst forces a reaction at a temperature lower than normally occurs. As the
exhaust gases flow through the catalyst, the NO reacts with the CO, HC and H2 via
a reduction reaction on the catalyst surface. e.g.,
NO+CO→½N2+CO2 , NO+H2 → ½N2+H2O, and others
• The remaining CO and HC are removed through an oxidation reaction forming
CO2 and H2O products (air added to exhaust after exhaust valve).
• A three-way catalysts will function correctly only if the exhaust gas composition
corresponds to nearly (±1%) stoichiometric combustion.
• If the exhaust is too lean – NO are not destroyed
• If the exhaust is too rich – CO and HC are not destroyed
• A closed-loop control system with an oxygen sensor in the exhaust is used to
determine the actual A/F ratio and used to adjust the fuel injector so that the A/F
ratio is near stoichiometric. Sangamesh Bhure, Asst Prof, SIT Pune
08-Oct-16 32
EFFECT OF MIXTURE COMPOSITION
• Since thermal efficiency is
highest for slightly lean
conditions it may seem that the
use of a catalytic converter is a
rather severe constraint.
• The same high efficiency can be
achieved using a near
stoichiometric mixture and
diluting by EGR

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 33

Effect of Temperature
• The temperature at which the
converter becomes 50% efficient
is referred to as the light-off
temperature.
• The converter is not very
effective during the warm up
period of the engine

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 34

CATALYTIC CONVERTER FOR DIESELS
• For Diesel engines catalytic converters are used to control HC and CO,
but reduction of NO emissions is poor because the engine runs lean
in order to avoid excess smoke.
• The NO is controlled by retarding the fuel injection from 20o to 5o
before TC in order to reduce the peak combustion temperature.
• This has a slight negative impact, increases the fuel consumption by
about 15%.

08-Oct-16 Sangamesh Bhure, Asst Prof, SIT Pune 35