Engine Exhaust Emissions

Dhananjay Kumar Srivastava

Associate Professor
Department of Mechanical Engineering
Indian Institute of Technology Kharagpur
 Categorization
• Gaseous Emissions  Regulated Emissions
• Particulate Emissions  Unregulated Emissions

2
 Regulated Emissions
• THC (Total unburned hydrocabons)
• CO (Carbon Monoxide)
• NOx (Oxides of Nitrogen)
• CO2 (Carbon dioxide)
• Particulate Matter (PM)

3
 Unregulated Emissions
• Formaldehyde
• Benzene, Toluene, Xylene (BTX)
• Aldehydes
• SO2
• Methane
• Poly Cyclic Aromatic Hydrocarbons (PAH’s).
• CO2

4
Air Pollutants Affecting Human Health
•Fine Particulate Matter - Respiratory System
•Carbon Monoxide - Hemoglobin
•Oxides of Nitrogen - Lung Cleansing
•Sulfur Dioxide - Lung Cleansing
•Hazardous Pollutants
Attached to Particulates - Respiratory, Cardiovascular and
Other Organs
Emission Legislation

6
 Emission Specifications
• Emission Test Cycles
• Different units for different vehicles: For Cars generally g/km
• For heavy duty vehicles: g/kWh
• Emission Standards becoming more and more stringent
• Simultaneous increase in vehicle population
• Effectively no reduction in air pollution due to vehicles
• Most strict emission legislations are in California
• Some parts of the world still does not have emission legislations

7
INDIAN STANDARD OF EMISSION FOR
ON ROAD VEHICLE
 Vehicular Exhaust Emissions
Spark-ignition and diesel engines are a major source of
urban air pollution.
SI Engine exhaust gases contain
Oxides of nitrogen (collectively known as NOX) (of order: 500 to 1000 ppm
or 20 g/kg fuel)
Carbon monoxide (CO) (of order: 1 to 2 Percent or 200 g/kg fuel), and
Organic compounds which are unburned or partially Unburned
hydrocarbons (HC) ( or order: 3000 ppm (as C,) or 25 g/kg fuel ).

CI Engine Exhaust
NOx emissions are comparable to SI Engines.
Hydrocarbon Levels are significant though exhaust concentrations are
lower by a factor of 5 than typical SI engine levels.
Particulate emissions; between about 0.2 and 0.5 percent of the fuel mass
is emitted as small (~0.1 μm diameter).
Diesel engines are not a significant source of carbon monoxide.
Processes of Pollution Formation in SI Engine
NO Formation
Nitric oxide forms throughout the high-temperature burned gases behind
the flame through chemical reactions, involving nitrogen and oxygen atoms
and molecules
The higher the burned gas temperature higher the rate of formation of NO.

CO Formation
Forms during the combustion process
With rich fuel-air mixtures, there is insufficient oxygen to burn fully all the
carbon in the fuel to CO2
High-temperature products, even with lean mixtures, dissociation ensures
there are significant CO levels

HC Formation Sources
Crevices, or narrow volumes, connected to the combustion chamber
Combustion chamber walls.
Engine oil left in a thin film on the cylinder wall, piston and perhaps on the
cylinder head
Incomplete combustion due to bulk quenching of the flame
Emissions Variation with F/A Ratio (SI Engine)

11
Emissions as a Function of Equivalence Ratio for
a CI Engine

12
 Kinetics of NO Formation
Principle source of NO is oxidation of atmospheric nitrogen.

NO formation is through Extended Zeldovich Mechanism

The principal reactions governing the formation of NO from molecular

Nitrogen are:
 Formation of NO2
NO + HO2 NO2 + OH

Conversion of this NO2 to NO occurs via

NO2 + O NO + O2

• NO2 formed in the flame is quenched by mixing with cooler fluid.

• NO2/NO ratio is negligible in SI engine

• NO2 can be 10 to 30% of the total exhaust oxides of nitrogen emissions

Oxides of Nitrogen

SI Engine CI Engine
Exhaust Gas Recirculation (EGR)

EGR leads to a reduction of the

NOX emissions
 Reduction of NOx through EGR is
Mainly Thermal Effect

The primary effect of the burned gas diluent in the unburned mixture
on NO formation process is that it reduces the flame temperature by
increasing heat capacity of charge per unit mass of fuel.
Effect of Spark Timing on NO Emission
Spark timing significantly
affects NO emission levels

NO emission levels steadily

decrease as spark timing is
retarded from MBT timing and
moved closer to TC.
 Effect of Equivalence Ratio

Maximum burned gas temperature occurs at ɸ = 1.1

As the mixture is leaned out, increasing oxygen concentration initially

offsets the falling gas temperatures and NO emissions peak at ɸ = 0.9
 Carbon monoxide Emisisons
Carbon monoxide (CO) emissions from internal combustion engines
are controlled primarily by the fuel/air equivalence ratio.

For fuel-rich mixtures CO concentrations in the exhaust increase

steadily with increasing equivalence ratio, as the amount of excess
fuel increases.

For fuel-lean mixtures, CO concentrations in the exhaust vary little

with equivalence.

Since spark-ignition engines often operate close to stoichiometric at

part load and fuel rich at full load, CO emissions are significant and
must be controlled.

Diesel engines, however, always operate well on the lean side of

stoichiometric; CO emissions from diesel engines are low enough to
be unimportant.
Hydrocarbon emissions from SI engine

• Flame quenching at the wall

• Crevice HC mechanism

• Absorption and desorption of engine oil

• Poor combustion quality

21
Crevice Volume

22
Hydrocarbon Oxidation
Hydrocarbon Emissions from Diesel Engines
Hydrocarbon emission levels from diesels vary widely with operating
conditions, and different HC formation mechanisms are likely to be most
important at different operating modes.

Engine idling and light-load operation produce significantly higher

hydrocarbon emissions than full-load operation. However, when the engine is
over-fueled, HC emissions increase very substantially.

Over-mixing (over-leaning) is an important source of HC, especially under

light-load operation.

Under-mixing, resulting in over-rich mixture during the combustion period, is

the mechanism by which some of the fuel remaining in the injector nozzle sac
volume escapes combustion, and is also the cause of very high HC
emissions during over-fueling.

Wall temperatures affect HC emissions, suggesting that wall quenching is

important, and under especially adverse conditions very high cyclic variability
in the combustion process can cause an increase in HC due to partial burning
and misfiring cycles.
Hydrocarbon Emission Mechanism in
Diesel Engine

Fuel Injection during delay period Fuel Injection during Combustion

 Particulate Formation During Combustion
• In combustion process of diesel engines, it is inevitable that some fuel will
experience oxygen deprivation because, even though the global air–fuel ratio
is lean, the charge is heterogeneous.
• When hydrocarbons are subjected to high temperature but insufficient
oxygen is made available, they undergo a multiplicity of endothermic
reactions known collectively as ‘pyrolysis’: the combustion chemistry then
sets out in the direction of soot.
• Greatest sooting tendency is seen not in the complete absence, but in the
presence of some oxygen
• Pyrolytic and oxidation reaction pathways always compete with one another,
and the lower the local oxygen concentration, the more likely it becomes
that pyrolysis will prevail over oxidation
 Conceptual Scheme of Formation of Soot
• Pyrolytic reactions break down the organic fuel
molecules and construct soot precursors.

• These precursors undergo nucleation, to form

the first discernible particles, or nuclei, at less
than 3 nm.

• These nuclei undergo surface growth, during

which carbon is added, and hydrogen removed,
until spherules emerge at ∼20–50 nm.

• During this growth process the spherules

themselves agglomerate, with surface growth
occurring in parallel, until finally the particles
begin to assume their familiar identities.

• The fourth mechanism, oxidation, opposes the

other mechanisms, and in fact culls soot at any
stage: as precursors, nuclei, spherules or
agglomerates.
PM formation processes

28
 Emission Measurement

CO Non-dispersive infrared (NDIR) detectors

HC Flame ionization detector (FID)

NOx Chemi-luminescence detector (CLD)

PM Dilution Tunnel Mass Sampling

Particle Number-Size Measurement

Smoke Smoke Opacitymeter

 Non-dispersive infrared (NDIR)
detectors

Beer-Lambert's Law
Flame ionization detector (FID)
Chemi-luminescence detector (CLD)
Dilution Tunnel Mass Sampling
Particle Number-Size Measurement
Three Way Catalytic Reduction

Rhodium
Platinum
 Diesel Oxidation Catalyst

DOC is very effective in oxidising HC and CO emissions with very high

efficiency at sufficiently higher temperature.

Carbon monoxide, gas-phase hydrocarbon, soluble organic fraction (SOF) of

PM etc. can be oxidised to harmless products using DOC.

Hydrocarbons and CO oxidises to form CO2 and water vapour.

HC + O2 → CO2 + H2O
2CO+2O2 → CO2
Diesel Oxidation
Catalyst [Source:
DCL International Inc.]

DOC
OC
EC EC
 Diesel Oxidation Catalyst
• Reaction occur in three steps:
1. Oxygen molecules get attached to the catalytic sites.
2. CO, HC etc get attached to the oxygen.
3. Finally products formed as CO2 and water vapour which get
desorbed from surface and diffuse with the exhaust stream.
Diesel Particulate Filter

Diesel Particulate Filter

(Source: MECA)
Selective Catalytic Reduction
• Reference: J B Heywood’s Book