Pollutant Formation

and Control

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.

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 Californias 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 as a result fuel usage is unchanged
over this period.

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)

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+N2NO+N
is high the reaction rate is very temperature dependent, '' ~ 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.

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 NO 01 x NO dx

x=0

x=1

-15o (x = 0)

25o (x = 1)

(assuming no mixing of fluid elements)

x=0

x=1

Equilibrium concentration:
based on the local temperature, pressure,
equivalence ratio, residual fraction
Actual NO concentration:
based on kinetics

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.

Effect of Various Parameters on NO Concentration

Increased spark advance and intake manifold pressure both result in higher
cylinder temperatures and thus higher NO concentrations in the exhaust gas
Pi= 658 mm Hg

Pi= 354 mm Hg

= 0.97

= 0.96

= 1.31
= 1.27

Exhaust NO Concentration Reduction

Since the formation of NO is highly dependent on cylinder gas temperature any
measures 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

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.

Hydrocarbon Emission Sources for SI Engines

There are six principal mechanisms believed to be responsible for
hydrocarbon emissions:
Source

% fuel escaping
normal combustion

% HC emissions

Crevices
Oil layers
Deposits
Liquid fuel
Flame quench
Exhaust valve leakage

5.2
1.0
1.0
1.2
0.5
0.1

38
16
16
20
5
5

Total

9.0

100

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

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.

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 large vortex that ultimately becomes large enough that a portion of
it is exhausted.

Blowdown

Exhaust
Stroke

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
valve
closes

Exhaust
valve
opens

BC

TC

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.

Exhaust HC, ppm C

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.

17

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

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.

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:
C x H y aO2 2aCO

y
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
CO O2 CO2
2

C ( s ) O2 CO2

1
H 2 O2 H 2O
2

Any carbon not oxidized in the cylinder ends up as soot in the exhaust!

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

= 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
21
the amount of soot oxidized, or increases the amount of soot in the exhaust.

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

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.
C8H18-air