Engine Exhaust

Emissions

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 Exhaust Emission Control

9 Particulates (very challenging)

• Chamber symmetry and shape
• Injection characteristics (mixing rates)
• Oil control
• Catalyst (soluble fraction)
• Particulate trap

9 Odor (oxidation catalyst)

9 CO2 (global warming)

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 Exhaust Aftertreatment
ECU

EGR AIR FLOW

VALVE METER
THROTTLE

DOC

NOx PARTICLE
DOC DEVICE FILTER

VAPORIZER

TEMPERATURE
PRESSURE DROP
SENSORS SENSOR 3
 Diesel Engines
Advantages:
• Efficiency (most efficient prime mover)
• Emissions (low CO, CO2, good durability)
• Very high torque and performance
Disadvantages:
• Emissions -- more challenging to control NOx, particulates
• Higher cost
• Heavier
• Noisier

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 Pollutant Formation and Control

ƒ All IC engines produce undesirable emissions as a result of combustion.

ƒ The emissions are unburned hydrocarbons (UHC), carbon monoxide (CO),

oxides of nitrogen NO and nitrogen dioxide (NO2), sulfur dioxide, and solid
carbon particulates.

ƒ 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). These
emissions pollute the environment and contribute to acid rain, smog odour
and create other health problems.

ƒ Carbon dioxide is an emission that is the primary greenhouse gas responsible

for global warming.

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 Ontario Drive Clean Program

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

9 Nitrogen Oxide – 984 ppm @ 3000 rpm

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

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

9 Particulates for diesels at present – 30% opacity

9 Evaporative Emissions for SI at present

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 Nitrogen Oxides

¾ NOx includes nitric oxide (NO) and nitrogen dioxide (NO2). In SI engines the
dominant component is NO, which forms as a result of dissociation of
molecular nitrogen and oxygen.

¾ Since the activation energy of the elementary reaction O+N2→NO+Nis

high the reaction rate is very temperature dependent - recall W ~ exp (-E/RT)

¾ 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 that NO formation not important. Recall Ya.B. Zel’dovich or thermal
mechanism (Ch.12) named is "thermal" because the reaction has very high
activation energy due to the strong bond in the N2-molecule.

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SI Engine: In-cylinder NO Formation
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=0

x=1

-15o (x = 0) 25o (x = 1)

(no mixing of fluid elements)

Equilibrium concentration: based on the

x=0 local temperature, pressure, equivalence ratio,
residual fraction
Actual NO concentration: based on kinetics
x=1

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 Effect of Equivalence Ratio on NO Concentration
ƒ The peak NO concentrations almost coincides with highest adiabatic flame
temperature (AFT).
ƒ Typically peak NO concentrations occur for slightly lean mixtures – that corresponds
to lower AFT but higher oxygen concentration.

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 Effect of Other 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

φ= 0.97

φ= 0.96

φ= 1.31

φ= 1.27

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 Methods to Reduce Exhaust NO Concentration
The formation of NO is highly dependent on cylinder gas temperature
therefore any measures taken to reduce the AFT are effective. These are:
¾ increased residual gas
¾ exhaust gas recirculation (EGR)
¾ 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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 Hydrocarbon emissions

Hydrocarbon emissions caused by the presence of unburned fuel in the engine exhaust.

Some of the exhaust hydrocarbons are not found in the fuel, but derived from the fuel
whose structure was altered due to chemical reaction that did not go to completion.
These are: acetaldehyde, formaldehyde, 1,3 butadiene etc - all toxic emissions.

Typically, 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.

The hydrocarbon emissions cause a decrease in the thermal efficiency, as well as an air
pollutant.

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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

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 Hydrocarbon Emission Sources

Crevices – are narrow regions in the combustion

chamber into which the flame cannot propagate Crevice
Piston ring
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.

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 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.

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 Hydrocarbon Emission Sources for CI Engines

Crevices - Fuel trapped along the wall by crevices, deposits, or oil due to impingement by
the fuel spray.

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. As longer ignition delay - more fuel becomes
overmixed.

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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:
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.

Smoke especially produced during engine warm up where the HC condense in the
exhaust gas.

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 Particulates (soot)
Most particulates result from incomplete combustion which occurs in fuel rich mixtures.
Any carbon not oxidized in the cylinder ends up as soot in the exhaust!

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 + aO 2 → 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 + O 2 → CO 2 C(s) + O 2 → CO 2 H2 + O 2 → H 2O
2 2

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 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

φ = 0.7

φ = 0.5 One technique for measuring particulate

involves diluting the exhaust gas with
φ = 0.3 cool air to freeze the chemistry before
measurements

The problem for diesel design 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. 19
 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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 Carbon Monoxide

Carbon monoxide appears in the exhaust of fuel rich running engines, when there
is insufficient oxygen to convert all the carbon in the fuel to carbon dioxide.

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 3%, 2% , >10%.

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
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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 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.

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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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 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%.

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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, 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:

¾ Produce gasoline from a fraction other than light virgin, or

¾ Upgrade a given fraction (e.g. increases octane number of fuel: produce isooctane
by reacting butene with isobutane in the presence of a catalyst.

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 Reformulated Gasoline

9 In order to reduce CO and HC the oxygen content of gasoline is increased to

about 3% by weight

9 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%.

9 The primary oxygenates are MTBE (CH3)OC(CH3)3 and ethanol (C2H5OH)

9 As part of the reformulated gasoline program sulfur is restricted to 31 ppm

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