IC Engine Exhaust

Emissions
Section 7

Pollutant Formation and Control

All IC engines produce undesirable emissions as a result of combustion,
including hydrogen fuelled engines.
The emissions of concern are: unburned hydrocarbons (HC), carbon
monoxide (CO), nitric oxide and nitrogen dioxide (NOx), sulfur dioxide (SO2),
and solid carbon particulates (particulate matter).
These emissions pollute the environment (smog, acid rain) that contribute
to 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 (CO2) is an emission that is not regulated but is one of the
primary greenhouse gases, water vapour and methane are the others,
believed to be responsible for global warming.
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Global Warming vs Climate Change

Global warming occurs because the greenhouse gases are transparent to
the high frequency solar radiation that heat up the earths surface but
absorb the lower frequency radiation from the earths surface.

Carbon Dioxide and Global Warming

CO2 is a gas in earths atmosphere and is currently at a globally averaged
concentration of approximately 383 ppm by volume
Atmospheric concentration of CO2 has increased by about 31% since the
beginning of the industrial revolution (mid1700s).
About three-quarters of this is due to the burning of fossil fuel, the other
quarter is mainly due to deforestation
Transportation accounts for about 14% of global greenhouse gas emissions
and 19% of the CO2 emissions

Carbon Dioxide and Global Warming

In the US a new law requires automakers to increase the average fuel

economy of their entire fleets by 40% by 2020 (motor vehicles would be
required to meet an average 6.7 L/100 km within 12 years). Canadian
govt will soon follow suit.

Emissions - Historical Perspective

During the 1940s air pollution as a problem was first recognized in the Los
Angeles basin. Problem is due to the large population density, geography,
natural weather pattern and Californians affinity to cars.
Classic smog results from large amounts of coal burning in an area and is a
mixture of smoke and sulfur dioxide (London). Photochemical smog is due to
chemical reaction of sunlight, NOx and HC in the lower troposphere producing
airborne particles and ground-level ozone (O3)
In 1966 California introduced HC and CO emission limits for new vehicles.
These limits were set nationally for vehicles in 1968 as part of Clean Air Act.
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 in 2000s was toward larger SUVs (e.g. Hummer,
Navigator, Escalade) as a result fuel usage is unchanged over this period.6

Photochemical Smog
Recipe for smog: sunlight (h), NO, HC
NO (small amount of NO2) and hydrocarbons generated by combustion
leads to the formation of many biological irritants

Peroxylacetyl Nitrate (PAN) Production

NO2 + hv NO + O
O + O2 + M O 3 + M
NO + O3 NO2 + O2

Produce O,
O3

O + H2O 2OH
RH - hydrocarbon
R* - HC radical
R - methyl CH3

O
PAN CH3

NO2
O O

RC(O)O2NO2

North American Emission Standards (g/mile)

* Phased in by 2009, NLEV - National Low Emission Vehicle voluntary program

EU Emission Standards for Passenger Cars (g/km)

Diesel

Date

CO

HC

HC+NOx

Euro 1

1992.07

2.72 (3.16)

0.97 (1.13)

0.14 (0.18)

Euro 2, IDI

1996.01

1.0

0.7

0.08

Euro 2, DI

1996.01

1.0

0.9

0.10

Euro 3

2000.01

0.64

0.56

0.50

0.05

Euro 4

2005.01

0.50

0.30

0.25

0.025

Euro 5

2009.09

0.50

0.23

0.18

0.005

Euro 6

2014.09

0.50

0.17

0.08

0.005

NOx

PM

e
e

Petrol (Gasoline)
Euro 1

1992.07

2.72 (3.16)

0.97 (1.13)

Euro 2

1996.01

2.2

0.5

Euro 3

2000.01

2.30

0.20

0.15

Euro 4

2005.01

1.0

0.10

0.08

Euro 5

2009.09

1.0

0.10

0.06

0.005

Euro 6

2014.09

1.0

0.10

0.06

0.005

d,e
d,e

Values in brackets are conformity of production (COP) limits

a - until 1999.09.30 (after that date DI engines must meet the IDI limits)
b - 2011.01 for all models
c - and NMHC = 0.068 g/km
d - applicable only to vehicles using DI engines
e - proposed to be changed to 0.003 g/km using the PMP measurement procedure

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Regulation on Sulphur Content of Diesel Fuels

The average sulphur content in Canadian Diesel fuel in 2000 was 350
parts per million (ppm)
Starting 2009 ultra-low sulphur diesel (ULSD) with 15 ppm sulphur is
mandatory in North America for highway vehicles. This is a critical
complement to the stringent new Tier II emission standards.
Since 2005 EU standards require diesel fuel to have less than 50 ppm
sulphur content. Since 2009 all vehicles run on Sulphur-free 10 ppm
sulphur diesel, including off-road.
EU also requires that diesel fuel have a minimum Cetane number of 48

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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 emission regulations:
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 from gas refuelling cap (SI only at present)

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13

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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Nitrogen Oxides (NOx)

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

O+N2NO+N
N+O2NO+O

N 2 + O2 2( NO )

since the activation energy (E) of the first reaction is very high the reaction
rate, '' ~ exp (-E/RT), is very temperature dependent
NO is only formed at high temperatures (>2000K) and the reaction rate
is relatively slow.

15

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.

-15o (x 0)

25o (x 1)

(assuming no mixing of fluid elements)

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SI Engine In-cylinder NO Formation

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 cools to 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

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x0
x1

-15o (x 0)

25o (x 1)

(assuming no mixing of fluid elements)

x0

x1

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

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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.

19

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

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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 fraction
exhaust gas recirculation (EGR)
moisture in the inlet air
run fuel lean
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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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 due 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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Hydrocarbon Emission Sources for SI Engines

There are six primary 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

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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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Hydrocarbon Emission Sources

Oil layers - Since the piston ring is not 100% effective in preventing oil
migration into the cylinder above the piston, an oil layer exists within the
combustion chamber that traps fuel.
Deposits - Carbon deposits build up on the valves, cylinder and piston
crown. These deposits are porous with pore sizes smaller than the
quenching distance so trapped fuel cannot burn.
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.

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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
(near BC)

Exhaust
Stroke

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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

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Hydrocarbon Emission Sources for CI Engines

Crevices - Fuel trapped in wall crevices, deposits, or oil due to impingement
by the fuel spray (not as important as in SI engines).
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.
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

air

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Note for the direct injection diesel the hydrocarbon emission are worse 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 properly adjusted port injection SI engines soot is not usually a problem,
however, particulate can arise in direct injection SI engines.
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 for
fuel rich mixtures.
Based on equilibrium the composition of the fuel-oxidizer mixture 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 of reactants exceeds 1.

Experimentally the critical C/O ratio for onset of soot formation is 0.5 - 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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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

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Particulates and CI Engines

In order to reduce NOx one wants to reduce the AFT but that has the adverse
effect of decreasing the amount of soot oxidized and thus increases the
amount of soot in the exhaust.
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, 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 engine control unit (ECU).
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
A catalytic converter uses a reduction catalyst and an oxidation catalyst to
remove CO, NO, and HC from the exhaust stream
Both consist of a ceramic honeycomb coated with a metal catalyst, usually
platinum, rhodium and/or palladium.

Lead and sulfur in the exhaust gas severely inhibit the operation of a catalytic
Converter, they are considered a poison.
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Three-way Catalytic Converter

A three-way catalysts will function properly only if the exhaust gas composition
corresponds to nearly (1%) stoichiometric combustion.
If the exhaust is too lean NO is not destroyed
If the exhaust is too rich CO and HC are not destroyed

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Three-way Catalytic Converter

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 with EGR to reduce NOx
Reduction catalyst:
In the first stage platinum and rhodium are used to remove NOx. The NO
molecule dissociates on the catalyst surface producing molecular oxygen
and nitrogen that are released
2NO N2 + O2 or

2NO2 N2 + 2O2

Oxidation catalyst:
In the second stage platinum and palladium are used to oxidize the CO
and the unburned hydrocarbon (HC) using the oxygen produced by reduction.
2CO + O2 2CO2
2CxHy + (2x+y/2)O2 2xCO2 + yH2O

39

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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Emission Control
A closed-loop control system with an oxygen (lamda) sensor in the exhaust is
used to control the fuel delivery so that the A/F ratio is near stoichiometric.
The narrow-band oxygen sensor when hot (800oC) produces a voltage that
varies according to the amount of oxygen in the exhaust compared to the
ambient oxygen level in the outside air.
Sensor output is very nonlinear ranging from 0.2 VDC (lean) to 0.8 VDC (rich),
a stoichiometric mixture gives an average reading of around 0.45 Volts.
The sensor can contain a heater to bring it quickly up to temperature and is
located before the catalytic converter
Wide-band sensor output is linear and can
be used to measure the O2 in the gas stream.
Generally only used for tuning.

Bosche LSU-4 wide band sensor

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Diesel Exhaust Treatment

Diesel engines run fuel lean (reduce soot) so a 3-way catalytic converter is
not useful, also particulate matter (PM) consisting of C needs to be removed.
Oxidizer catalysts used for reducing HC and CO
Diesel Particulate Filters (DPF) are used for removing PM.
Active DPFs: raise temperature of the filter by periodically adding fuel to the
exhaust stream that combusts in the filter raising the DPF temp cleans the
DPF by oxidizing the collected PM with O2, requires >600oC (regeneration).
Passive DPF:

Non catalyst

(reaction requires > 250oC)

Johnson Matthey CRT

42

Diesel Exhaust Treatment

NO can be reduced by retarding fuel injection from 20o to 5o before TC in order
to reduce the peak combustion temperature at the expense of efficiency.
Selective Catalytic Reduction (SCR) used to convert NOx into N2 and H2O.
In a SCR a reductant like ammonia (NH3) is added to the gas stream to
enable the following reaction over a catalyst.
4NH3 + 4NO + O2 4N2 + 6H2O
2NH3 + NO + NO2 2N2 + 3H2O
8NH3 + 6NO2 7N2 + 12H2O
Typically an aqueous solution of urea (NH2)2CO is added to the exhaust
stream to produce ammonia:
(NH2)2CO HNCO + NH3
HNCO + H2O CO2 + NH3
Mercedes-Benz BlueTEC ML320 has a 7 gal urea based AdBlue tank
43

Diesel Cayenne Porche arrives in Canada

The Cayenne Diesel is built to meet strict emission standards, and includes
selective catalytic reduction (SCR) technology. The SCR system is comprised
of an AdBlue tank located in the car's spare-wheel well, a heating system for
this tank and the lines which carry the AdBlue, an injection valve for AdBlue
fluid and a selective catalytic reduction converter, all of which aid in the
reduction of NOx (oxides of nitrogen) emissions.
AUTOSERVICEWORLD.COM, April 3, 2012

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