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Emissions
Section 7
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 SUVs, as a result fuel usage is
unchanged over this period.
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Heavy-Duty Diesel**:
4% failed test
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.
x=0
x=1
-15o (x = 0)
25o (x = 1)
x=0
x=1
Equilibrium concentration:
based on the local temperature, pressure,
equivalence ratio, residual fraction
Actual NO concentration:
based on kinetics
Pi= 354 mm Hg
= 0.97
= 0.96
= 1.31
= 1.27
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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.
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% 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
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16
16
20
5
5
Total
9.0
100
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Crevice
Piston ring
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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.
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Blowdown
Exhaust
Stroke
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Exhaust
valve
closes
Exhaust
valve
opens
BC
TC
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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.
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Note for the direct injection diesel the hydrocarbon emission are the worst at
light load (long ignition delay)
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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.
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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!
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= 0.7
= 0.5
= 0.3
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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
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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.
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Emission Control
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
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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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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
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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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This has a slight negative impact, increases the fuel consumption by about 15%.
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IC Engine Fuels
Crude oil contains a large number of hydrocarbon compounds (25,000).
The purpose of refining is to separate crude oil into various fractions via a
distillation process, and then chemically process the fractions into fuels and
other products.
A still is used to heat a sample, preferentially boiling off lighter components
which are then condensed and recovered.
The group of compounds that boil off between two temperatures are referred
to as fractions.
The order of the fractions as they leave the still are naptha, distillate, gas oil,
and residual oil. These are further subdivided using adjectives light, middle,
and heavy.
The adjectives virgin or straight run are often used to signify that no chemical
processing has been done to a fraction.
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Distillation Process
Refining Process
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Gasoline
Light virgin (or straight run) naptha can be used as gasoline.
Gasoline fuel is a blend of hydrocarbon distillates with a range of boiling points
between 25 and 225oC (for diesel fuel between 180 and 360oC)
Chemical processing is used to:
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Reformulated Gasoline
In order to reduce CO and HC the oxygen content of gasoline is increased to
about 3% by weight (U.S. oxygenated fuels program, winter only).
The U.S. reformulated gasoline program is a year-round program used
to reduce ozone by requiring a minimum oxygen content of 2% by weight and
maximum benzene content of 1%.
The primary oxygenates are MTBE (CH3)OC(CH3)3 and ethanol (C2H5OH)
Also as part of the reformulated gasoline program sulfur is restricted to 31 ppm
Note: gasoline with 10% ethanol by volume also marketed as gasohol
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