AU330 Internal Combustion Engines

Pollutant Formation and Control

Snunkhaem Echaroj
 Thammasat University,
2017

Pollutant Formation Pollutant Formation and Control

 Thammasat University,
2017

Pollutant Formation Pollutant Formation and Control

• 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.

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 Thammasat University,
2017

Pollutant Formation Historical Perspective

• 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.
 Thammasat University,
2017

Pollutant Formation Ontario Drive Clean Program

In Ontario every vehicle must undergo a tail pipe emission test every other
year to check compliance with regulation:

• Nitrogen Oxide – 984 ppm @ 3000 rpm

• Carbon Monoxide – 0.48% @ 3000 rpm and 1.0% @ 800 rpm

• Unburned hydrocarbons – 86 ppm @ 3000 rpm and 200 ppm @ 800 rpm

• Particulates (diesels only at present) – 30% opacity

• Evaporative Emissions (SI only at present)

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 Thammasat University,
2017

Pollutant Formation Ontario Drive Clean Program Stats

Test results between 1999 and March 2004

Light-Duty Program*: 14.6% failed test

Heavy-Duty Diesel**: 4% failed test

Heavy-Duty Non-Diesel**: 27.3% failed test

* 6 million vehicles (automobiles, vans, SUVs, pick-ups) in program

** 200,000 vehicles in program

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 Thammasat University,
2017

Pollutant Formation 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 O+N2→NO+N

is high the reaction rate is very temperature dependent, w''′ ~ exp (-E/RT)

• Therefore NO is only formed at high temperatures and the reaction rate is

relatively slow.

• At temperatures below 2000K the reaction rate is extremely slow, so NO

formation not important.
 Thammasat University,
2017

Pollutant Formation SI Engine In-cylinder NO Formation

• Since the cylinder temperature changes throughout the cycle the NO reaction
rate also changes.

• Each fluid element burns to its AFT based on its initial temperature, elements
that burn first near the spark plug achieve a higher temperature.

• Since the chemistry is not fast enough the actual NO concentration tends
toward but never achieves the equilibrium value.
If NO concentration is lower than equilibrium value – NO forms
If NO concentration is higher than equilibrium value – NO decomposes

• 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.

• The total amount of NO that appears in the exhaust is calculated by summing

the frozen mass fractions for all the fluid elements: x   x dx
1
NO 0 NO
 -15o (x = 0) 25o (x = 1)
(assuming no mixing of fluid elements)

Equilibrium concentration:
based on the local temperature, pressure,
equivalence ratio, residual fraction

Actual NO concentration:
based on kinetics
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2017

Pollutant Formation Effect of Equivalence Ratio on NO Concentration

One would expect the peak NO concentrations to coincide with highest AFT.

Typically peak NO concentrations occur for slightly lean mixtures – that

corresponds to lower AFT but higher oxygen concentration.

Lean Rich
More than Less than
100% air 100% air

Less than More than

100% fuel 100% fuel
 Thammasat University,
2017

Pollutant Formation Effect of Various Parameters on NO Concentration

Pi= 658 mm Hg Pi= 354 mm Hg

Increased spark advance and intake

manifold pressure both result in higher
cylinder temperatures and thus higher
Nitric oxide concentration (ppm)

NO concentrations in the exhaust gas

= 0.97

= 0.96

= 1.31 = 1.27
 Thammasat University,
2017

Pollutant Formation Exhaust NO Concentration Reduction

Since the formation of NO is highly

dependent on cylinder gas
temperature anymeasures taken to
reduce the AFT are effective:

• increased residual gas

• exhaust gas recirculation (EGR)
• moisture in the inlet air

In CI engines the cylinder gas

temperature is governed by the load
and injection timing

IDI/NA – indirect injection naturally aspirated

DI/NA – direct injection naturally aspirated
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2017

Pollutant Formation Hydrocarbons

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 do 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.
 Thammasat University,
2017

Pollutant Formation Hydrocarbon Emission Sources for SI Engines

There are six principal mechanisms believed to be responsible for

hydrocarbon emissions:

% fuel escaping
Source normal combustion % HC emissions

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

 Thammasat University,
2017

Pollutant Formation 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.

Crevice
Piston ring
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2017

Pollutant Formation 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
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from the wall. Most of this gas eventually diffuses into the burned gas during
 Thammasat University,
2017

Pollutant Formation Hydrocarbon Exhaust Process

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
Blowdown Exhaust
large vortex that
Stroke
ultimately becomes large
enough that a portion of it
is exhausted.
 Thammasat University,
2017

Pollutant Formation Hydrocarbon Exhaust Process

The first peak is due to blowdown and the second peak is due to vortex roll up
and exhaust (vortex reaches exhaust valve at roughly 290o)

Exhaust Exhaust
valve valve
opens closes

BC TC
 Thammasat University,
2017

Pollutant Formation 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).
Undermixing 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.
Overmixing 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 overmixed.

Exhaust HC, ppm C

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 Thammasat University,
2017

Pollutant Formation Hydrocarbon Emission Sources for CI Engines

Note for the direct injection diesel the hydrocarbon emission are the worst at
light load (long ignition delay)

IDI/NA – indirect injection naturally aspirated

DI/NA – direct injection naturally aspirated
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2017

Pollutant Formation Particulates

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:
1) solid carbon material or soot
2) 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.
 Thammasat University,
2017

Pollutant Formation Particulates (soot)

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 0.8

The 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 H 2  O2  H 2O
2 2
Any carbon not oxidized in the cylinder ends up as soot in the exhaust!
 Thammasat University,
2017

Pollutant Formation Particulates and CI Engines

Particulates are a major emissions

problem for CI engines.
 = 0.7

Exhaust smoke limits the full load

overall equivalence ratio to about 0.7

 = 0.5
 = 0.3
One technique for measuring particulate
involves diluting the exhaust gas with
cool air to freeze the chemistry before
measurements
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 amount of
soot in the exhaust.
 Thammasat University,
2017

Pollutant Formation Particulates and CI Engines

An example of this dilemma is changing the start of injection, e.g., increasing

the advance increases the AFT

Crank angle bTC for

start of injection
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2017

Pollutant Formation Carbon Monoxide

C8H18-air • 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.

Lean Rich
More than Less than
100% air 100% air

Less than More than

100% fuel 100% fuel
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2017

Pollutant Formation 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.
 Thammasat University,
2017

Pollutant Formation Emission Control (Catalytic convertor)

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:

1) Engineering of combustion process - advances in fuel injectors, oxygen

sensors, and on-board computers.

2) Optimizing the choice of operating parameters - two NOx control measures

that have been used in automobile engines since 1970s are spark retard and
EGR.

3) After treatment devices in the exhaust system - catalytic 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. 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).
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2017

Pollutant Formation 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.
 Thammasat University,
2017

Pollutant Formation 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
 Thammasat University,
2017

Pollutant Formation 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
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2017

Pollutant Formation 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%.