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IC Engine Exhaust Emissions
IC Engine Exhaust Emissions
Emissions
Section 7
1
Pollutant Formation and Control
• These emissions pollute the environment and contribute to acid rain, smog
odors, and respiratory and other health problems.
2
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.
• 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.
3
Ontario Drive Clean Program
In Ontario every vehicle must undergo a tail pipe emission test every other
year to check compliance with regulation:
• Unburned hydrocarbons – 86 ppm @ 3000 rpm and 200 ppm @ 800 rpm
4
Ontario Drive Clean Program Stats
5
Nitrogen Oxides
6
SI Engine In-cylinder NO Formation
• 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.
x NO 01 x NO dx 7
x=0
x=1
-15o (x = 0) 25o (x = 1)
(assuming no mixing of fluid elements)
Equilibrium concentration:
x=0 based on the local temperature, pressure,
equivalence ratio, residual fraction
One would expect the peak NO concentrations to coincide with highest AFT.
9
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
= 0.97
= 0.96
= 1.31
= 1.27
10
Exhaust NO Concentration Reduction
11
Hydrocarbons
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.
12
Hydrocarbon Emission Sources for SI Engines
% 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
13
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
14
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. 15
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 16
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 17
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.
18
Note for the direct injection diesel the hydrocarbon emission are the worst at
light load (long ignition delay)
19
Particulates
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
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.
20
Particulates (soot)
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!
21
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
23
Carbon Monoxide
• For fuel rich mixtures there is insufficient oxygen to convert all the carbon in
the fuel to carbon dioxide.
C8H18-air
24
Carbon Monoxide
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.
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.
25
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.
26
Catalytic Converter
Lead and sulfur in the exhaust gas severely inhibit the operation of a catalytic
converter (poison). 27
Three-way Catalytic Converter
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
A three-way catalysts will function correctly only if the exhaust gas composition
corresponds to nearly (±1%) stoichiometric combustion.
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 29
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
30
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.
This has a slight negative impact, increases the fuel consumption by about 15%.
31
IC Engine Fuels
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.
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.
32
Distillation Process
Refining Process
33
Gasoline
34
Reformulated Gasoline
35