Pollutant Formation & Control

Introduction

 All internal combustion engines produce undesirable

emissions as a result of combustion. 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 unburned hydrocarbons

(UHC), carbon monoxide (CO), oxides of nitrogen such as
nitric oxide and nitrogen dioxide (NOx), sulfur dioxide, and
solid carbon particulates.

 Both SI and CI engines are equally responsible for the

same.
 Pollutant Formation & Control

 The emissions exhausted into the surroundings pollute

the atmosphere and causes the following problems:
a. Global warming
b. Acid rain
c Smog
d. Odors
e. Respiratory and other health hazards.
 Pollutant Formation & Control

 It is the dream of engineers and scientists to develop

engines and fuels such that very few quantity of harmful
emissions are generated, and these could be let into the
surroundings without a major impact on the environment.

 However, with the present technology this is not

possible, and after-treatment of the exhaust gases as well as
in cylinder reduction of emissions are very important.
 Engine emissions can be classified into two categories:
a. Exhaust emissions and
b. Non-exhaust emissions.
 Engine Emissions

 Exhaust Emissions. Major exhaust emissions are

a. Un-burnt hydrocarbons (HC)
b. Oxides of Carbon (CO and CO2),
c. Oxides of Nitrogen (NO and N02)
d. Oxides of Sulphur (S02 and S03)
e. Particulates
f. Soot and smoke
 The first four are common to both SI and CI engines and
the last two are mainly from CI engines.
 Engine Emissions

 The main non-exhaust emission is the un-burnt

hydrocarbons from fuel tank and crankcase blow by.
 All the three emissions (HC, CO and NOx ) as a function
of equivalence ratio () for an S1 engine. A rich mixture does
not have enough oxygen to react with all the carbon and
hydrogen, and both HC and CO emissions increase.
 For < 0.8, HC emissions also increase due to poor
combustion and misfire.
 The generation of nitrogen oxide emissions is a function
of the combustion temp, highest near stoichiometric
conditions when temps are at the peak value.
 Engine Emissions

 Maxm NOx emissions occur at slightly lean conditions,

where the combustion temp is high and there is an excess of
oxygen to react with the nitrogen.

 In Diesel engine HC will decrease slightly with increase in

 due to higher cylinder temps making it easier to burn up
any over-mixed (very lean) or under-mixed (rich) fuel-air
mixture.
 SI Engine Emissions

  S.I. Engine Emissions

 
 

Evaporative Crankcase Exhaust

Fuel Carb. CO, HC, NOX, Part.

Tank Float Bowl

UBHC UBHC
For the S.I. Engine with carburetor:
Evaporative emissions account for approximately : 20%
Crankcase emissions account for approximately : 20%
Exhaust emissions account for the balance : 60%
 Non-exhaust Emissions

 Apart from exhaust emissions there are three other

sources in an automobile that emit emissions. They are

 Fuel tank. The fuel tank emits fuel vapours into

the atmosphere.

 Carburetor. The carburetor also gives out fuel

vapours.

 Crankcase. It emits blow-by gases and fuel vapours

into the atmosphere.
 Non-exhaust Emissions

 The fourth source is the tail pipe that brings out exhaust
emissions.

 Evaporative losses (both from fuel tank and

carburetor)
 Crankcase blow-by (from crankcase)
 Tail pipe (from the exhaust pipe)
 SI Engine Emissions

Pollution from S.I. Engine

 

Products of Complete Products of Incomplete

Combustion Combustion

NOx SOx Lead CO HC Parti- Lead

culates
 
 HC emissions from SI engine
The causes for HC emissions from SI engine are:
 Fuel vapor-air mixture is compressed into the
combustion chamber crevice volumes.
 Fuel compounds are absorbed into oil layers on the
cylinder liner.
 Fuel is absorbed by and/or contained within deposits
on the piston head and piston crown.
 Quench layers on the combustion chamber wall are left
as the flame extinguishes close to the walls.
 Fuel vapor-air mixture can be left unburned if the flame
extinguishes before reaching the walls.
 HC emissions from SI engine

 Liquid fuel within the cylinder may not evaporate and

mix with sufficient air to burn prior to the end of combustion
i.e improper mixing

 The mixture may leak through the exhaust valve seat.

 HC emissions from SI engine
The six principal mechanisms are believed to be responsible
for hydrocarbon emissions:
 HC Emission Formation Mechanisms

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.
 HC Emission Formation Mechanisms

 At peak pr, calculations suggest as much as 68% of the

mixture may be trapped in the crevices.
 During compression and combustion, these crevice
volumes are filled with unburned charge. During expansion, a
part of the UBHC-air mixture leaves the crevices and is
oxidized by the hot burned gas mixture.
 Crevices are estimated to cause roughly 40% of HC
emissions.
 HC Emission Formation Mechanisms

Oil layer
 A very thin layer of oil gets deposited on the cylinder
walls to provide lubrication between the walls and the moving
piston.

 During the intake and compression strokes, the

incoming air and fuel comes in contact with this oil film. This
oil layer traps fuel and releases it later during expansion.

 Oil layers are thought to cause roughly 10-30% of HC

emissions.
 HC Emission Formation Mechanisms

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.
 Deposits can absorb fuel in a manner similar to oil. The
fuel is released later during expansion. However, deposits
are not present on new engines but accumulate with
mileage.
 Deposit buildup rates depend on fuel and operating
conditions.
 HC Emission Formation Mechanisms

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.
 HC Emission Formation Mechanisms

Exhaust Valve Leakage

 As pr 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 that is still in this crevice volume gets carried into the
exhaust manifold. This causes a momentary increase in HC
concentration at the start of blow down process.
 HC Emission Formation Mechanisms

 HC emissions are also dependent on several other

parameters such as:
a. Spark advance,
b. A/F ratio,
c. and EGR.
 HC Emission Formation Mechanisms

 Spark Advance. High advance generally increases

HC emissions, primarily because the temp of the charge is
lower during the expansion stroke. This reduces oxidation
during expansion as the HC comes off the walls and out of
the crevices.

 A/F ratio. Lower A/F ratios (richer combustion)

cause more HC emissions because there is less O2 to
oxidize fuel. Very lean A/F ratios cause HC emissions to
increase due to misfires, partial burns, and reduced
temperature during expansion.
 HC Emission Formation Mechanisms

EGR

 High EGR causes an increase in HC emissions. The

increase is gradual at first, but the curve becomes steep as
the combustion degrades.

 In fast burn engines, the combustion degradation sets

in at higher EGR rates than in slow burn engines.
 HC Emission from CI Engines

 Because CI engines operate with an overall fuel-lean

equivalence ratio, CI engines have only about one-fifth the
HC emissions of an SI Engine.

 The components in diesel fuel have higher molecular

weights on average than those in a gasoline blend, and this
results in higher boiling and condensing temps. Therefore,
soot formation is more in CI engines.

 Some HC particles condenses onto the surface of the

solid carbon soot that is generated during combustion. Most
of this is burned as mixing continues and the combustion
process proceeds.
 HC Emission from CI Engines

 Only a small percentage of the original carbon soot that

is formed comes out of the cylinder. The HC components
condensed on the surface of the carbon particles, in addition
to the solid carbon particles themselves; contribute to the HC
emissions of the engine.

 In general, a CI engine has combustion efficiency of

about 98%.This means that only about 2% of the HC fuel
being emitted.
 HC Emission from CI Engines

The two main mechanisms causing HC emissions in diesel

engines are:
a. Over-mixing (or over-leaning). This occurs in the
periphery of the fuel jet especially at idle and light loads
where ignition delays are long.
b. Under mixing. This may be caused by late or after
injection or dribble from the fuel that may escape from the
nozzle sac volume (so sac volume should be kept very
small), another reason for under-mixing may be due to
excess fuel entering the cylinder under over-fueling
conditions that are usually encountered during transient
operation.
 Carbon Monoxide (CO) Emission

 CO generated in an engine
when it is operated with a fuel rich
equivalence ratio.

 When there is not enough O2 to

convert all carbon to CO2, some
fuel does not get burned and then
some carbon ends up, as CO.

 The amount of CO, for a range

of fuel composition and C/H ratios,
is a function of the relative air-fuel
ratio.
 Carbon Monoxide (CO) Emission

 Even when enough oxygen is present, high peak temps

can cause dissociation-chemical combustion reactions in
which CO2 and water vapor separate into CO, H2, and O2.
Conversion of CO to CO2 is governed by reaction.
CO + OH CO2+ H
Dissociated CO may freeze during the expansion stroke.

 Typically the exhaust of an SI engine will be about 0.2 to

5% carbon monoxide.
 Oxides of Nitrogen (NOX) Emission

 Nitric oxide(NO) and nitrogen dioxide (NO2) are usually

gp together as NOX emission, nitric oxide is predominant
oxide of nitrogen produced inside the engine cylinder.
 The principal source of NO is the oxidation of
atmospheric N2.
 If the fuel contain significant N2, the oxidation of the fuel
N2 containing compounds is an additional source of NO.
 Gasoline's contain negligible amounts of N2; although
diesel fuels contain more N2.
 NO forms in both the flame front and the post flame
 Oxides of Nitrogen (NOX) Emission

 Basics of NO formation. Sources of NO includes:

a. Thermal,
b. Prompt, and
c. Fuel bound
 Thermal NO

 The NO that is formed in high temp burned (post flame) gases is

known as thermal NO and is usually considered to follow the extended
Zeldovich mechanism:
 
O + N2 = NO + N
N + O2 = NO + O
N + OH = NO + H

Thermal NO formed in the flame zone is usually very small because the
flame residence times are very short. From the above mechanisms high
temps and oxygen concentrations lead to high NO formation rates.
 
 Imp observation: Lean fuel-air mixtures lead to low NO if and only
if they are accompanied with reduced temps.
 Prompt NO
This is usually formed only in hydrocarbon flames under,
relatively rich ( > 1.0) conditions. The path way for prompt
NO formation starts from:
 
CH + N2  HCH + N .
HC + N2  CN + N

Then N reacts with O2 and /or CN reacts with O2 or O to from

NO. Since CH is a very important flame constituent, the
prompts NO formed in rich flames can be the order of or
even greater than the thermal NO arising from the flame
zone.
 Fuel bound NO

This arises from any nitrogen contained in the fuel

molecules, which may thermally decompose (during
combustion) forming intermediates like, NH3, HCN, CN, etc.
This NO is significant under lean conditions and is weakly
dependent on local temps (unlike thermal NO). Also, typically
diesels have higher nitrogen content than gasoline's.
 Effects of different operating
conditions on NO formation

 Injection timing. This has a similar effect on NO

emissions as spark timing has an SI engines .
 
Retarded BOI = NO emissions decrease

Advanced BOI = NO emissions increase (up to say 40

BTDC)

which is typical max advance in conventional diesel engines

 Effects of different operating
Conditions on NO formation
 Ignition delay. This is a very important parameter
affecting NO emissions. Generally, longer ignition delay
periods lead to greater amount of prepared fuel-air mixture at
the time of ignition, higher initial energy release rates, higher
local temps and thus, higher NO emissions.
 EGR. As EGR , NO

 . As  , NO but less rapidly in diesels than SI.

 Load. As load , Pmax  = Tmax (local)  and larger

regions of  = 1.0 are formed = NO .
 Effects of different operating
Conditions on NO formation
 No emissions are approximately, directly related to the
mass of fuel injected.

 Most NO in IDI engines forms in pre-chamber and NO

freezes soon after the hot gases, flow in to the main chamber
and mix with cooler air.
 
 EGR has different compositions at different loads in
diesel engines and thus different effects on NO at different
loads.
 Emission Control Mechanisms

Automotive emissions are controlled in three ways:

 To promote more complete combustion so that there

are less by products.

 To reintroduce excessive HCs back into the engine for

combustion and

 To provide an additional area for oxidation or

combustion to occur. This additional area is called a catalytic
converter.
 Evaporative Emission Control:

 Positive Crankcase Ventilation (PCV) System

(for crankcase emissions)

 Charcoal Canister System

(for Fuel tank and carburetor float bowl emissions)
 Positive Crankcase Ventilation (PCV)
System
 The purpose of the (PCV)
system, is to take the vapors
produced in the crankcase
during the normal combustion
process, and redirecting them
into the air/fuel intake system to
be burned during combustion.

 These vapors dilute the

air/fuel mixture so they have to
be carefully controlled and
metered in order to not affect the
performance of the engine.
 Positive Crankcase Ventilation (PCV)
System
 This is the job of the (PCV)
valve.

 At idle, when the air/fuel

mixture is very critical, just a little
of the vapors are allowed in to the
intake system.

 At high speed when the

mixture is less critical and the prs
in the engine are greater, more of
the vapors are allowed in to the
intake system.
 Positive Crankcase Ventilation (PCV)
System
 When the valve or the system
is clogged, vapors will back up into
the air filter housing or at worst, the
excess pr will push past seals and
create engine oil leaks.

 If the wrong valve is used or

the system has air leaks, the
engine will idle rough, or at worst,
engine oil will be sucked out of the
engine.
Charcoal Canister System
 Charcoal Canister System

20% of all HC emissions from the automobile are from the

fuel tank. An evaporative control system was developed to
eliminate this source of pollution. The function of the fuel
evaporative control system is to trap and store evaporative
emissions from the fuel tank and carburetor. A charcoal
canister is used to trap the fuel vapors. The fuel vapors
adhere to the charcoal, until the engine is started, and engine
vacuum can be used to draw the vapors into the engine, so
that they can be burned along with the fuel/air mixture. This
system requires the use of a sealed gas tank filler cap.
 Charcoal Canister System
The tank has to have the space for the vapors to collect so
that they can then be vented to the charcoal canister. A purge
valve is used to control the vapor flow into the engine. The
purge valve is operated by engine vacuum. One common
problem with this system is that the purge valve goes bad and
engine vacuum draws fuel directly into the intake system.
This enriches the fuel mixture and will foul the spark plugs.
Most charcoal canisters have a filter that should be replaced
periodically. This system should be checked when fuel
mileage drops.
 Catalytic Converter

 The catalytic converter looks like a muffler. It is located in

the exhaust system ahead of the muffler. There are two types
of catalytic converter; a two way and a three way converter.
 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.

 The platinum or
palladium are used as a
catalyst ( a catalyst is a
substance used to speed up
a chemical process).
 Catalytic Converter

Lead and sulfur in the exhaust gas severely inhibit the operation of
a catalytic converter (poison).
 Catalytic Converter
 As HCs or CO in the
exhaust are passed over the
catalyst, it is chemically
oxidized or converted to
carbon dioxide and water.

 Rhodium used to remove

NO and platinum used to
remove HC and CO.

 As the converter works to

clean the exhaust, it develops
heat.
 Catalytic Converter

 The dirtier the exhaust, the harder the converter works

and the more heat that is developed. In some cases the
converter can be seen to glow from excessive heat.

 If the converter works this hard to clean a dirty exhaust it

will destroy itself. Also leaded fuel will put a coating on the
platinum or palladium and render the converter ineffective. 
This is why, in the U.S.A., all fuels designed for automobile
engines are now unleaded.
 Exhaust Gas Recirculation (EGR)

The EGR system, is

mainly used to reduce
nitrogen oxides (NOx)
which are formed in
the combustion
chamber at high
temps.
 Exhaust Gas Recirculation (EGR)

The EGR system re-circulates already combusted exhaust

from the exhaust manifold back to the air-fuel mixture and is
drawn into the cylinder chamber. This reduces the peak
combustion temp in the cylinder chamber. This temp
reduction in turn reduces NOx formation.

The EGR flow is directed by a solenoid valve that is

controlled by the Power train Control Module (PCM). The
PCM uses inputs such as engine speed, intake-manifold pr,
and engine temp to determine how much exhaust flow to
meter back to the air-fuel mixture.
 Exhaust Gas Recirculation (EGR)
The purpose of the exhaust gas recirculation (EGR) valve is to meter a
small amount of exhaust gas into the intake system, this dilutes the
air/fuel mixture so as to lower the combustion chamber temp. Excessive
combustion chamber temp creates oxides of nitrogen, which is a major
pollutant. While the EGR valve is the most effective method of controlling
oxides of nitrogen, in it's very design it adversely affects engine
performance. The engine was not designed to run on exhaust gas. For
this reason the amount of exhaust entering the intake system has to be
carefully monitored and controlled. This is accomplished through a series
of electrical and vacuum switches and the vehicle computer. Since EGR
action reduces performance by diluting the air /fuel mixture, the system
does not allow EGR action when the engine is cold or when the engine
needs full power.
 Air Injection
Since no internal combustion engine is 100% efficient, there
will always be some unburned fuel in the exhaust. This
increases HC emissions. To eliminate this source of
emissions an air injection system was created. Combustion
requires fuel, oxygen and heat. Without any one of the three,
combustion cannot occur. Inside the exhaust manifold there
is sufficient heat to support combustion, if we introduce some
oxygen than any unburned fuel will ignite. This combustion
will not produce any power, but it will reduce excessive HC
emissions. Unlike in the combustion chamber, this
combustion is uncontrolled, so if the fuel content of the
exhaust is excessive, explosions, that sound like popping, will
occur.
There are times when under normal conditions, such as deceleration,
when the fuel content is excessive. Under these conditions we would
want to shut off the air injection system. This is accomplished
through the use of a diverter valve, which instead of shutting the air
pump off, diverts the air away from the exhaust manifold. Since all
of this is done after the combustion process is complete, this is one
emission control that has no effect on engine performance. The only
maintenance that is required is a careful inspection of the air pump
drive belt.