Internal Combustion Engines

MAE 408
Pollutant Emissions in SI and CI Engines

Dr. Peter B. Corson, 3171 Broughton Hall

Slides courtesy of Dr. Tiegang Fang
Mechanical and Aerospace Engineering Department
North Carolina State University

1
Pollutant Emissions from Engines
 SI and CI engines are major sources of urban air pollution
 Pollutant emissions from SI engines include oxides of nitrogen (NO
and NO2, ~500-1000ppm), Carbon Monoxide (CO, ~1-2%), and
organic components of unburned or partially burned hydrocarbons
(HC, ~3000ppm)
 Pollutant emissions from CI engines include NOx (comparable to SI
engine), CO (< SI engine), HC (< SI engine), Particulate (soot or
smoke)
 Sulfur for both SI and CI engines: SO2 and SO3

2
Carbon Monoxide
 Produced by incomplete combustion (rich combustion)
 Toxic gas
Carbon Monoxide is a colourless, odorless, tasteless, toxic
gas that has the molecular formula CO. The molecule consists
of a carbon atom that is triply bonded to an oxygen atom.
Carbon Monoxide is produced by the incomplete combustion
of the fossil fuels - gas, oil, coal and wood used in boilers,
engines, oil burners, gas fires, water heaters, solid fuel
appliances and open fires.

Carbon monoxide is a significantly toxic gas and has no odor or color. It is the most common type of fatal
poisoning in many countries. Exposures can lead to significant toxicity of the central nervous system and
heart. Following poisoning, long-term effects often occur. Carbon monoxide can also have severe effects on
the fetus of a pregnant woman. Symptoms of mild poisoning include headaches and dizziness at
concentrations less than 100 ppm. Concentrations as low as 667 ppm can cause up to 50% of the body's
hemoglobin to be converted to carboxy-hemoglobin (HbCO). Carboxy-hemoglobin is very stable and after
hemoglobin has been changed to form carboxy-hemoglobin, this change is irreversible. This makes
carboxy-hemoglobin ineffective for delivering oxygen, resulting in some body parts not receiving oxygen
needed. As a result, exposures of this level can be life-threatening. In the United States, OSHA
(Occupational Safety & Health Administration) limits long-term workplace exposure levels to 35 ppm.

3
Emissions of Carbon Monoxide from SI and CI
Engines
Spark ignition or gasoline
engines can easily produce 7%
carbon monoxide, but Diesel
engines never produce as much
as 1% with liquid fuels.

 Gasoline engines run with an equivalence ratio close or higher than

1.0 with rich air-fuel mixtures
 Not much excess air available for SI engines to oxidize CO to CO2
 CI engines always run with lean mixtures, namely equivalence
ratios less than 1.0 with excess air to oxidize CO to CO2

4
Sulfur Dioxide and Sulfur Trioxide
Sulfur dioxide (SO2): Motor vehicles
create this pollutant by burning
sulfur-containing fuels, especially
diesel. It can react in the
atmosphere to form fine particles
and can pose a health risk to young
children and asthmatics.
SO2 can be further oxidized to SO3,
which combines with water to form
sulfuric acid aerosol. This leads to
acid rain.
In the gas phase sulfur dioxide is oxidized by
reaction with the hydroxyl radical via a
intermolecular reaction:
SO2 + OH· • HOSO2·
which is followed by:
HOSO2· + O2 • HO2· + SO3
In the presence of water sulfur trioxide (SO3) is
converted rapidly to sulfuric acid:
SO3(g) + H2O(l) • H2SO4(l)

Acid rain has been shown to have

adverse impacts on forests,
freshwaters and soils, killing off
insect and aquatic lifeforms as well
as causing damage to buildings and
having possible impacts on human
health.
5
Oxides of Nitrogen (NOx)
NOx is a generic term for mono-nitrogen
Time required for half
oxides (NO and NO2). These oxides are NO concentration in
NO to be oxidized to
produced during combustion, especially air (ppm)
NO2 (min)
combustion at high temperatures.
20,000 0.175
At ambient temperatures, the oxygen and
nitrogen gases in air will not react with each 10,000 0.35
other. In an internal combustion engine, 1,000 3.5
combustion of a mixture of air and fuel 100 35
produces combustion temperatures high
10 350
enough to drive endothermic reactions
between atmospheric nitrogen and oxygen in 1 3500
the flame, yielding various oxides of nitrogen.

In areas of high motor vehicle traffic, such as

in large cities, the amount of nitrogen oxides
emitted into the atmosphere can be quite
significant.

In the presence of excess oxygen (O2), nitric

oxide (NO) will be converted to nitrogen
dioxide (NO2), with the time required
depending on the concentration in air as Brown Gas
shown on the right table: 6
 Effects of Oxides of Nitrogen- Smog
 When NOx and Volatile Organic Compounds (VOCs) react in the
presence of sunlight, they form photochemical smog (smoky fog),
a significant form of air pollution, especially in the summer. Children,
people with lung diseases such as asthma, and people who work or
exercise outside are susceptible to adverse effects of smog such as
damage to lung tissue and reduction in lung function

Smog in
New
York
City

7
 Effects of Oxides of Nitrogen-Acid Rain
 Mono-nitrogen oxides eventually form nitric acid when dissolved in
atmospheric moisture, forming a component of acid rain. The
following chemical reaction occurs when nitrogen dioxide reacts
with water:
2NO2 + H2O • HNO2 + HNO3 (nitrogen dioxide + water • nitrous
acid + nitric acid).

 Nitrous acid then decomposes as follows:

3HNO2 • HNO3 + 2NO + H2O (nitrous acid • nitric acid + nitric
oxide + water), where nitric oxide will oxidize to form nitrogen
dioxide that again reacts with water, ultimately forming nitric acid:
4NO + 3O2 + 2H2O • 4HNO3 (nitric oxide + oxygen + water • nitric
acid).

 Mono-nitrogen oxides are also involved in tropospheric production

of ozone. NOx should not be confused with NOS, a term used to
refer to nitrous oxide (N2O) in the context of its use as a power
booster for internal combustion engines. 8
Adverse Effects of Acid Rain

Death of plants

Corrosion of Statute

9
 Formation of NOx
 There are three primary sources of NOx in combustion processes:
Thermal NOx, Fuel NOx and Prompt NOx
 Thermal NOx formation, which is highly temperature dependent, is
recognized as the most relevant source when combusting natural
gas.
 Fuel NOx tends to dominate during the combustion of fuels, such
as coal, which have a significant nitrogen content, particularly
when burned in combustors designed to minimize thermal NOx.
 The contribution of prompt NOx is normally considered negligible.
A fourth source, called feed NOx is associated with the combustion
of nitrogen present in the feed material of cement rotary kilns, at
between 300° and 800°C, where it is also a minor contributor.

10
 Thermal NOx (Extended Zeldovich Mechanism)
• Thermal NOx refers to NOx formed through high temperature
oxidation of the diatomic nitrogen found in combustion air. The
formation rate is primarily a function of temperature and the
residence time of nitrogen at that temperature. At high temperatures,
usually above 1600°C (2900°F), molecular nitrogen (N2) and oxygen
(O2) in the combustion air disassociate into their atomic states and
participate in a series of reactions. The three principal reactions
producing thermal NOx are (Extended Zeldovich Mechanism):
N2 + O • NO + N
N + O2 • NO + O
N + OH • NO + H
• All 3 reactions are reversible. Zeldovich was the first to suggest the
importance of the first two reactions. The last reaction of atomic
Nitrogen with the Hydroxyl radical, OH, was added by Lavovie,
Heywood and Keck to the mechanism and makes a significant
contribution to the formation of thermal NOx.
11
 Fuel and Prompt NOx
• Fuel NOx: The major source of NOx production from nitrogen-bearing
fuels such as certain coals and oil, is the conversion of fuel-bound
nitrogen to NOx during combustion. During combustion, the nitrogen
bound in the fuel is released as a free radical and ultimately forms free
N2, or NO. Fuel NOx can contribute as much as 50% of total emissions
when combusting oil and as much as 80% when combusting coal.
• Prompt NOx: This is attributed to the reaction of atmospheric nitrogen,
N2, with radicals such as C, CH, and CH2 fragments derived from fuel,
where this cannot be explained by either the aforementioned thermal or
fuel processes. Occurring in the earliest stage of combustion, this results
in the formation of fixed species of nitrogen such as NH (nitrogen
monohydride), HCN (hydrogen cyanide), H2CN (dihydrogen cyanide)
and CN- (cyano radical) which can oxidize to NO. In fuels that contain
nitrogen, the incidence of prompt NOx is especially minimal and it is
generally only of interest for the most exacting emission targets.

12
 Hydrocarbon Emission Effect – Ozone Formation
 Hydrocarbons are a precursor to ground-level
ozone, a serious air pollutant in cities across
the United States. A key component of smog,
ground-level ozone is formed by reactions
involving hydrocarbons and nitrogen oxides
in the presence of sunlight. Hydrocarbon
emissions result from incomplete fuel
combustion and from fuel evaporation.
Today's cars are equipped with emission
controls designed to reduce both exhaust and
evaporative hydrocarbon emissions.
Volatile organic compounds (VOCs)
 Ground-level ozone causes health problems are organic chemical compounds that
such as difficulty breathing, lung damage, and have high enough vapor pressures
under normal conditions to significantly
reduced cardiovascular functioning. A vaporize and enter the atmosphere. A
number of hydrocarbons are also considered wide range of carbon-based
toxic, meaning they can cause cancer or other molecules, such as aldehydes,
ketones, and hydrocarbons are VOC's.
health problems

13
 Black Smoke from Heavy Duty Diesel Engines
 Smoke is the main source of particulate matter emissions

Black smoke from heavy duty diesel

vehicles

14
 Particulate Matter
 Particle pollution (also called particulate matter or PM) is the term for
a mixture of solid particles and liquid droplets found in the air. Some
particles, such as dust, dirt, soot, or smoke, are large or dark enough
to be seen with the naked eye. Others are so small, they can only be
detected using an electron microscope.
 Particle pollution includes "inhalable coarse particles," with diameters
larger than 2.5 micrometers and smaller than 10 micrometers and
"fine particles," with diameters that are 2.5 micrometers and smaller.
 These particles come in many sizes and shapes and can be made up
of hundreds of different chemicals. Some particles, known as primary
particles are emitted directly from a source, such as construction
sites, unpaved roads, fields, smokestacks or fires. Others form in
complicated reactions in the atmosphere of chemicals such as sulfur
dioxides and nitrogen oxides that are emitted from power plants,
industries and automobiles. These particles, known as secondary
particles, make up most of the fine particle pollution in the country.

15
Particle Size Comparison

16
 Effects of Particulate Emissions- Health
Small particles less than10 micrometers in diameter
pose the greatest problems, because they can get deep
into your lungs, and some may even get into your
bloodstream.
Exposure to such particles can affect both your lungs and
your heart. Small particles of concern include "inhalable
coarse particles" (such as those found near roadways and
dusty industries), which are larger than 2.5 micrometers and
smaller than 10 micrometers in diameter; and "fine
particles" (such as those found in smoke and haze), which
are 2.5 micrometers in diameter and smaller.

Health Effects
Numerous scientific studies have linked particle pollution
exposure to a variety of problems, including: increased
respiratory symptoms, such as irritation of the airways,
coughing, or difficulty breathing, for example; decreased
lung function; aggravated asthma; development of chronic
bronchitis; irregular heartbeat; nonfatal heart attacks; and
premature death in people with heart or lung disease. Particle pollution is a significant health
People with heart or lung diseases, children and older concern and can aggravate respiratory
adults are the most likely to be affected by particle pollution conditions such as asthma and bronchitis.
exposure. However, even if you are healthy, you may
experience temporary symptoms from exposure to elevated
levels of particle pollution.
17
Effects of Particulate Emissions-Environment
Environmental Effects
Visibility reduction
Fine particles (PM2.5) are the major cause of reduced visibility (haze) in parts of the United States,
including many of our treasured national parks and wilderness areas.

Environmental damage
Particles can be carried over long distances by wind and then settle on ground or water. The effects of this
settling include: making lakes and streams acidic; changing the nutrient balance in coastal waters and
large river basins; depleting the nutrients in soil; damaging sensitive forests and farm crops; and affecting
the diversity of ecosystems.

Aesthetic damage
Particle pollution can stain and damage stone and other materials, including culturally important objects
such as statues and monuments.

Clear Day
Hazy Day

Great Smoky Mountains National Park, an example of one area with haze 18
 Pollutant Emissions Must Be Reduced
 Adverse effects of pollutant
emissions on environment
and health
 Numerous mobile vehicles
in the world result in
significant amounts of
pollutant exhaust in tons
everyday

Morning rush
hour traffic
waiting to pay
the toll to
cross the
Oakland Bay
Bridge in
August 1989
19
 Stringent Emission Regulations
 Emission standards
become more stringent
with technology
development and number
of vehicles
 Engine and vehicle
manufacturers must meet
emission standards before
their products go to market
 Emission standards for
engine and vehicle vary
 In the USA, the
Environment Protection
Agency (EPA) sets
emission regulations

Vehicle Emission Standard

(gram/mile) 20
 Stringent Emission Regulations Cont’d
 Emission standards are
different for different
regions in the world
 In the USA, the EPA defines
the Tiers of pollutant
emissions from engines
 In Europe and Asia,
European Standards are
used, called Euro I, II, III, IV,
and V standards

NOx and PM
emissions for
diesel engines
(g/hp-hr) or
(g/kW-hr)

21
 Emission
Formation in SI
Engines
 NO forms in high-
temperature burnt
gas and the
concentration is
frozen when the
mixture is cooled
 CO presents in fuel
rich zones
 HC occurs in
incomplete
combustion, from
wall deposit
absorption, and oil
layer absorption
22
Equivalence Ratio Effects on Emissions in SI
Engines
 Peak NO is formed in a
leaner mixture with the
equivalence ratio close to 1
 Lowest HC occurs in a
relatively lean mixture. Too
lean and too rich mixtures
make HC increase
 CO emissions increase with
the increase of the
equivalence ratio, especially
for rich mixtures

23
 Emission Formation in CI Engines
 NOx forms in the leaner side of the high flame temperature
layer
 CO, HC, and Particles are generated in the rich region with
relatively high flame temeprature

Conceptual model by John

Dec, 1997

24
 Particle Emission in CI Engines

 Particulates in diesel
engine exhaust have
different structures and
shapes
 The diameter of spherical
soot particles is about 10-
60 nm

25
 Soot Formation in CI Engines
 Soot formation occurs in diesel
engines at temperatures about Coagulation
1000-2800 K, at pressures of 50-
100 atm Surface
Growth and
 Soot formation includes particle Coagulation
nucleation, surface growth, and
Particle
agglomeration Inception
 PAH (Polycyclic Aromatic

Reaction Time
PAH formation
Hydrocarbon) is a precursor of
soot

Gas phase
Molecular zone

Fuel and Oxidizer

26
 Soot Oxidation
 A large fraction of soot
generated during diesel
combustion is oxidized by
the soot oxidation process
 Soot oxidation occurs
during the soot formation
process but becomes
dominant during the late
combustion phase
 Soot oxidation depends on
temperature, soot
concentration, and
available oxygen
concentration

27
 Soot Concentration Development
 The net soot generation during the diesel combustion process is a
balance of the soot formation and soot oxidation processes
 During the early combustion stage, soot formation rate is greater
than soot oxidation leading to soot concentration increase; soot
concentration peaks when the soot formation rate equals the soot
oxidation rate; soot concentration decreases when soot oxidation
dominates

28
Soot Formation and Oxidation in a Diesel Spray

29
 Soot and NOx Tradeoff in Conventional Diesel
Combustion
 Soot formation and NOx formation regions in
an Equivalence Ratio vs Temperature map
 For conventional diesel combustion,
measures reducing soot emission make the
NOx emission increase, and vice-versa.
 For example, EGR reduces NOx by lowering
the flame temperature, but soot is increased
due to less soot oxidation at lower flame
temperature

1000 1400 1800 2200 2600 3000

Temperature (K)

Piezoelectric injector helps

improve the PM and NOx
tradeoff curve

30