Part II

Lecture # 9

NOx Formation and

Emissions Control in SIE
1
 Formation of Nitrogen Oxides

 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:
 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.
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 Kinetics and Modelling of Thermal NO Formation
 The following three reactions commonly referred to as the extended Zeldovich
mechanism govern the formation of thermal NO

(1)

(2)

(3)

 k1, k2 and k3 are the reaction rate constants for the forward reactions and k-1, k-2 and k-3 are
for the reverse reactions
 The original Zeldovich mechanism consisted of the first two reactions (1) and (2) and the
third reaction (3) was added by Lavoie.
 The forward part of the first reaction (1) is highly endothermic with high activation energy
of about 314 kJ /mol and is a rate determining reaction in NO formation 3
 Rate Constants for Zeldovich Mechanism
Rate of NO Formation

 The rate of formation of NO using the three reactions (1) to (3) can be
expressed by the following equation;

[NO] = k1 [O][N2] – k -1 [NO][N] + k2 [N][O2] – k -2 [NO][O] + k3 [N][OH] –

k -3 [NO][H] (4)

(1)

[ ] denotes the concentration of species

in moles/cm3. (2)

(3)

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 Rate Constants for Zeldovich Mechanism

(i) Steady – state approximation of [N]: Rate of formation and destruction of N is small relative
to its concentration. Concentration of atomic N is of the order of 10-8 mole fraction only,
which is much smaller compared to the other reacting chemical species.
(ii) O, OH, O2 and O concentrations are governed by chemical equilibrium considerations as
the reactions governing concentration of these species are very fast at the combustion
temperatures.

Steady state assumption of [N] leads to,

[N] = + k1 [O][N2] – k -1 [NO][N] – k2 [N][O2] + k -2 [NO][O] - k3 [N][OH] + k -3 [NO][H] = 0 (5)

Use of Eqs. 4 and 5 yield the rate of NO formation,

[NO] = 2 {k1 [O][N2] – k -1 [NO][N]}
5
and from Equation 5 steady state concentration of N,

(7)

From the assumption of equilibration of O, OH, H and O2,

(9)

Eliminating [N] and [H] using equations 7 and 8, the equation 6 gives,

(10)

where K = (k1/k –1)(k2/k -2) is equilibrium constant for the reaction

N2 + O2 ↔ 2NO.
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 The NO formation rates may be calculated by Eq. 10 using equilibrium concentrations of
O, O2, OH and N2.
 Most of NO formation takes place in the burned gases behind the flame front after
combustion is completed locally.
 The rate of NO formation being much slower than the combustion rates, the NO
formation process may be decoupled from combustion process and rate of formation of
NO can be calculated assuming equilibrium concentrations of O, O2, OH and N2 .
 By introducing equilibrium assumption in the calculations, the Eq. 10 is further
simplified by using the following notations;

where R1 is the reaction rate using equilibrium concentrations for the reaction (1).
Similarly,

Using the above notations the Eq. 10 is simplified to give rate of formation of NO as follows,
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 (11)
where w = R1/( R2+ R3)
NO Formation is a Function of Temperature and O2. From Eq. 11 the initial rate of NO
formation when [NO]/[NO]e<< 1;
(12)

The concentration of atomic oxygen at equilibrium, using reaction ½ O2 ↔ O is given by;

(13)
Equilibrium constant K p(O) is

(14)

Using value of k1 from Table 2 and, the Eqs. 13 and 14 the initial rate of NO formation then
reduces to

(15)

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 (15)

 Temperature being in exponential term in Eq. 15, it strongly influences NO

formation rates.
 The NO formation is maximized under the conditions of high temperature and
high oxygen concentrations. These conditions occur at fuel-air equivalence
ratios 5-10 % leaner than stoichiometric mixture.
 Typical combustion duration is about 1 to 2 ms in SI engines operating close to
stoichiometric conditions at 3000 -5000 rpm.
 NO formation at peak pressure and temperature conditions may reach close to
equilibrium [NO] concentrations

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 The characteristic time (tNO) necessary to reach equilibrium concentration of
NO may be approximated as,

(16)

 The mole fraction [NO]e can be estimated from the reaction

O2 + N2 ↔ 2NO, as

(17)

10
 KNO is given by

and mole fraction of N2 at equilibrium, x[N2]e ≈ 0.71

From the above,

(18)

Time (tNO) is in seconds, pressure, P is in atmospheres and temperature, T is in K.

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 Prompt NO
 In the flame reaction zone NO may be formed rapidly.
 The prompt NO is formed in the flame by reaction of intermediate chemical
species of CN group with O and OH radicals.
 The hydrocarbon radicals CH, CH2, C, C2 etc. formed in the flame front react with
molecular nitrogen to give intermediate species such as HCN and CN by the
reactions (19) to (21).
(19)

(20)

(21)

 Large concentrations of HCN near the reaction zone in fuel rich flames have been
observed and rapid formation of NO has been seen to be associated with rapid decay of
HCN.
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 Prompt NO
 The contribution of prompt NO in the stoichiometric laminar flames is
estimated to be about 5 to 10 % only.

 In the engines as the combustion occurs at high pressures, the thickness of

flame front is very small (~ 0.1 mm) and the residence time of chemical species
in this zone is very short.

 The formation of thermal NO in the burned gases behind the flame front is much
higher compared to any NO formation in the flame front.

 However, contribution of prompt NO may be significant under lean engine

operation or engine operation with high dilution such as use of exhaust gas
recirculation.

13
 Fuel NO
 Fuel NO is formed by combustion of fuels with chemically bound nitrogen.

 The fuel nitrogen produces at first intermediate nitrogen-containing

compounds and reactive radicals such as HCN, NH3, CN, NH etc.

 These species are subsequently oxidized to NO.

 Although petroleum crude may contain about 0.6 % nitrogen but gasoline has
negligible nitrogen.

 Diesel fuels have higher nitrogen content than gasoline, but this too is usually
less than 0.1 % by mass.

 The fuel nitrogen therefore, does not make significant contribution to NO

formation in automotive engines operating on gasoline, diesel, natural gas and
alcohols etc. 14
 Effect of Addition of Diluents on NO Formation
 Burned residual gases left from the previous cycle
act as charge diluents.
 A part of exhaust gas is also recirculated back to
the engine for diluting the intake charge to
reduce NO formation.
 This process is known as exhaust gas recirculation
(EGR).
 Dilution by the burnt residual gases is also called
as ‘internal EGR’. Effect of content of various diluents
in intake air on NO reduction in a SI
engine

 The combustion temperatures decrease as a result of charge dilution and the

lower combustion temperatures result in lower NO levels.
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 Effect of Addition of Diluents on NO Formation

 CO2 and H2O being tri-atomic gases have higher

specific heat and give larger NO reductions than
the same volume of N2, He or Ar.

 The specific heat of the exhaust gas is higher

than for air due to presence of substantial
fractions of CO2 and H2O.

 Hence, EGR results in lower combustion Effect of content of various diluents

in intake air on NO reduction in a SI
temperatures compared to those from dilution engine

by nitrogen alone or by leaning of mixture

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 Effect of Addition of Diluents on NO Formation

 A negative effect of charge dilution is:

 Reduction in oxygen concentration in the charge, slowing down

of flame propagation speed, slowing the rate of combustion.

 Further reduction in the burned gas temperature and beyond a

limit causes misfired combustion resulting in lower fuel
efficiency and higher unburned hydrocarbon emissions.

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 Catalytic Converter
 Reduction:

NOx + CO  N2 + CO2

 Oxidation:

HC + CO + O2  H2O + CO2

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 https://www.youtube.com/watch?v=W6dIsC_eGBI

Video for Exhaust system 19

 CO emissions in real engines:

 During cold start of engine and acceleration, rich mixtures are used
resulting in higher CO emissions
 Another contributing factor to higher CO emissions is non-uniform
mixture distribution within the cylinder.

 Overall, the air-fuel ratio is the most important engine parameter

affecting CO emissions. Other factors influence CO mostly indirectly
through changes in mixture composition and/or promotion of slow
oxidation reactions resulting in incomplete combustion.
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HC EMISSIONS FROM SI ENGINES
Main sources of hydrocarbon emissions in the four-stroke, homogeneous charge
spark ignition engines are:

In the vehicles, fuel evaporation from fuel tank and fuel system is another source
of unburned HC emissions.
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Flame Quenching in SI Engines
Photographic studies of flame region in a spark ignition engine immediately after arrival of flame close to
the combustion chamber walls have shown existence of a thin non-radiating layer adhering to the
combustion chamber. Flame propagates through unburned charge when the energy released on
combustion is able to maintain the reaction zone temperatures at a high enough level to sustain
the rapid combustion reactions. However, as the flame approaches combustion chamber walls, more
and more heat is lost from the flame to the walls. Due to heat transfer from the flame to the walls,
temperature of the reaction zone gets lowered that slows down combustion reactions reducing heat
release rate. Finally, as the flame reaches in close proximity of the walls, the gas temperature ahead of
flame falls below ignition point and the flame gets extinguished. This phenomenon is known as flame
quenching.
The flame propagating normal to the single wall will quench at some distance away. When the flame is
propagating through a tube it may not propagate if the tube diameter is smaller than a critical value.
Similarly, flame may not propagate between the two parallel plates if the distance between the plates is
below a critical limit. The normal distance from the wall where flame gets quenched, or the gap between
two parallel plates, or diameter of the tube in which flame is just unable to propagate under the given
charge conditions, is called quench distance or quench layer thickness. The wall-quenching effects are
primarily due to heat transfer and not due to diffusion of species.

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HC Emissions from Wall Quenching
Single wall quench layer thickness typically varies from 0.05 to 0.1 mm. It decreases with increase of
engine load as higher wall temperature results at higher engine loads, which reduces heat loss to the
walls from the reaction zone, and consequently a smaller quench layer thickness is obtained. However, at
top dead centre the surface to volume ratio of the combustion chamber is at its maximum and at this
point the wall quench layer may comprise of 0.1 to 0.2 percent of the total charge inducted into the
cylinder.
Studies on combustion of pre-mixed fuel air mixtures in combustion bombs show that when all the
crevices in the bomb are eliminated by filling with solid material, unburned HC concentrations were just
about 10 ppmC only. Such low concentrations result as after flame quenching the hydrocarbons in the
quench layer thickness on the single walls diffuse in the hot burned gas quite early and get oxidized.
Typically, most hydrocarbons would get oxidized on diffusion in the high temperature burned gases within
2-3 milliseconds of the flame quench. These studies showed that the contribution of single wall quench
layers to the total unburned HC emission is quite small.

Crevice HC
•Crevices in the combustion chamber are narrow regions into which fuel-air mixture can flow but flame
cannot propagate due to their high surface to volume ratio causing high heat transfer rates to walls.
•The largest crevice in the combustion chamber is between cylinder wall and piston top land, and second
land.
•Other crevices present are along the gasket between cylinder head and block, around intake and exhaust
valve seats, threads around spark plug and space around the central electrode of the spark plug.
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Total crevice volume is about 3 to 5 percent of the clearance volume and the piston and cylinder crevice constitutes around
70 to 80 percent of the total crevice volume.

Typical dimensions of piston top land crevices

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 Summary of HC Emission Processes in SI Engines
In a port fuel injection SI engine, typically:
•About 9 percent of the total fuel supplied escapes normal
combustion. Of this Approximately 3 percent escapes as fuel itself
through absorption in oil and deposits routes, and as liquid fuel films
deposited in the cylinder.
•About 5 percent as fuel-air mixture due to flame quenching on walls
and crevices, and leakage through exhaust valves.
•Around 1% of fuel –air mixture escapes as crankcase blow by.
•Of the fuel contained in crevices and quench layers about 2/3rd is
oxidized inside the cylinder.
•Of the fuel in oil layers, deposits and liquid fuel film only about
1/3rd is oxidized inside the cylinder.
•About 2.7 % of fuel exits the exhaust port and nearly 1 % is retained
in the residual burned gases.
•Of the hydrocarbons exiting the exhaust port about 1/3rd is further
oxidized in the exhaust system.
•Under warmed up operation, engine out HC emissions from a PFI
are approximately 1.8 percent of the fuel supplied. The balance 7.2
Different sources of hydrocarbon emissions in
percent fuel that does not leave the cylinder is either oxidized in the homogeneous charge SI engine.
cylinder or at exhaust port and manifold or recycled in the residual
gases and crankcase blow by gases.
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 Emission Control for SI Engines
 The emission control techniques may be grouped into the following broad
categories:
 Engine design and fuel system parameters
 Engine add-ons to enable reduction of engine-out emissions and
 Exhaust after-treatment
 Engine design parameters:
 Engine compression ratio,
 Combustion chamber design – low crevice volume, high turbulence
 Spark timing
 Air-fuel ratio
 Fuel system design: carburetor giving way to fuel injection
 Multivalves and variable valve actuation
 Engine temperature control 26
 Engine Compression Ratio
 Engine compression ratio affects:
 Surface to volume ratio of the combustion chamber
 Engine combustion temperature
 Thermodynamic efficiency
 Fuel octane number for knock free engine operation

 The combustion chamber with a lower CR has lower surface/volume ratio

resulting in a reduction in volume of quench layer on the combustion chamber
surface.
 For a low CR engine the crevice volume would also be proportionately lower.
These factors in turn would reduce HC emissions.
 Higher exhaust temperatures resulting with low CR would promote oxidation of
HC and CO in exhaust system.
 At low CR the peak combustion temperatures are lower and hence low NOx
formation.
 Low CR engine has a poorer fuel efficiency.
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 High Turbulence Combustion Chambers
 Small cylinders with hemispherical type
combustion chambers are now more commonly
used in SI engines.
 The chamber has a low surface to volume
ratio. The intake ports are provided with a suitably
curved geometry to generate high rate of air swirl.

 Small cylinder engines can be operated at higher speeds which increases

turbulence and tends to reduce HC emissions.
 More heat transfer takes place from the burned gases as the walls are
nearer to the bulk gases. It results in lower NOx.
 The compact hemispherical combustion chambers shape provides the
lowest surface to volume ratio and minimum tendency to engine knock.
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Fuel System

Trends in development of
fuel system technology for SI
(gasoline) engines

Comparison of engine-out emissions

from carburetor and open loop PFI
engine passenger cars.

PFI: multi-point port fuel injection system 29

 Valve Gear Design
Multiple Valves: Four valves (2 intake and two exhaust valves) per cylinder
are now common on the SI engines.
 The use of multiple valves:
 Increases valve flow area compared to two valves.
 Spark plug can be placed centrally reducing the maximum flame travel
distance hence faster and less knocking tendency combustion.
 Only one intake valve may be used at low speeds and low loads to
obtain high intake mixture velocity giving high turbulence and swirl that
improves combustion at light loads.
 At high speeds and high loads both valves are open.
 The two intake valves may be provided with different valve timings and
different valve lifts to obtain higher volumetric efficiency.
 The two valves may use different port designs to obtain the desired fluid
motion in the cylinder. 30
 Valve Gear Design
Variable Valve Timings and Lift:
 With increase in valve overlap, residual gas fraction
at low speeds increases giving lower NOx
emissions, but HC emissions increase.
 Ideally the valve timings should vary with the
engine speed.
 The intake gas flow velocity through the valves
governs the air motion and turbulence in the
engine cylinder and hence the rate of combustion
and performance
 Reductions of 30 to 70 % in NOx with variable valve
timing are observed.
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ADD-ON SYSTEMS FOR CONTROL OF ENGINE-OUT EMISSIONS
 Crankcase Emission Control
 When engine is running and intake charge is
throttled the intake manifold is at a lower
pressure than the crankcase.
 The blow-by gases mix with the intake charge to
be burned inside the engine cylinder to CO2 and
H2O.
 A tube connects crankcase or cylinder head cover
to the intake manifold below throttle valve,
which leads the blowby gases back to the engine.
 Due to suction effect of intake manifold as the
pressure in the crankcase falls, ventilation air
from the air cleaner is drawn into the crankcase
Schematic of a PCV system
that continuously purges it. 32
 ADD-ON SYSTEMS FOR CONTROL OF ENGINE-OUT EMISSIONS
 Evaporative Emission Control
 The evaporative emission control system consists of a device to store fuel vapors
produced in the fuel system due to evaporation.
 A canister containing activated charcoal is used to store the fuel vapors.
 The vapors produced in the fuel tank normally collect in the fuel tank itself and are
vented to the charcoal canister when fuel vapor pressure becomes excessive.
 The fuel vapors from the tank and carburetor led to and adsorbed into the
charcoal.

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ADD-ON SYSTEMS FOR CONTROL OF ENGINE-OUT EMISSIONS
 Evaporative Emission Control
 When engine is running, the vacuum created in the intake manifold is used
to draw fuel vapors from the canister into the engine. Purging air is sucked
through the canister which leads the fuel vapors from canister to the engine.
 An electronically controlled purge valve is used.
 During engine acceleration additional mixture enrichment can be tolerated and
under these operating conditions the stored fuel vapors are usually purged into
the intake manifold.

 This system is a fully closed system. A

sealed fuel tank filler cap is used and a
stable fuel tank pressure is maintained by
the purging process of the canister.

34
 ADD-ON SYSTEMS FOR CONTROL OF ENGINE-OUT EMISSIONS
 Exhaust Gas Recirculation
EGR is defined as a mass percent of total intake
flow:

 Typically, only about 5 to 10 % EGR rates

are employed.
 At higher EGR rates, frequency of partial
and complete misfire cycles increases
resulting in unacceptably higher HC
emissions and loss in fuel economy and
power.
 EGR systems are made to operate mostly in
the part-load range. EGR system mechanically controlled by
 These are deactivated at engine idle, intake manifold pressure
because large amount of residual gas is
35
already present in the cylinder.
 ENGINE EXHAUST AFTERTREATMENT
 Devices were developed to treat exhaust gas for conversion of engine emissions to
harmless gases.
 Conversion of pollutants present in the exhaust gas is termed as ‘exhaust
aftertreatment’.
 Two basic types of exhaust treatment systems were considered;
 Thermal reactors
 Catalytic reactors or converters
 Initially, thermal reactors for oxidation of HC and CO to CO2 and H2O were
developed.
 However, as high conversion rates of pollutants could not be obtained in the
thermal reactors these did not find widespread application and very soon the
catalytic converters became a standard exhaust aftertreatment device for the
spark ignited engine vehicles. 36
 ENGINE EXHAUST AFTERTREATMENT
 Thermal reactors:
 For 50% oxidation of CO and HC temperatures
in excess of 500 and 600 oC, respectively are
required.
 For conversion of 80 percent, temperatures
required are about 600 and 750 oC for HC and
CO, respectively.
 The thermal reactor has to be located as
close to the exhaust port as possible.
Conversion efficiency versus
 In fact, the exhaust manifold is modified to temperature for thermal oxidation of
act as thermal reactor. HC and CO
 Exhaust manifold is made as a two wall design with an air gap in between to
reduce cooling of the exhaust gases.
 Volume of the manifold is increased to increase residence time for the gases to
undergo oxidation reactions.

37
 ENGINE EXHAUST AFTERTREATMENT
 Catalytic Reactors

 Catalytic converters are now a standard fitment to SI engine powered

vehicles.
 The exhaust gas flows over a bed of catalyst where pollutants are
converted to harmless gases.
 The catalyst lowers the reaction temperature and hence high conversion
rates are obtained compared to thermal reactors.
 A catalytic converter consists of the following main elements besides
housing:
(i) Catalyst
(ii) Catalyst substrate or support
(iii) Intermediate coat or washcoat

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Conceptual model of catalytic sites dispersed on a high surface-area Al2O3 washcoat.