Part II

Lecture # 10

Emissions in CIE

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 Combustion in CI Engines
 In the compression ignition engines, rapid combustion of fuel and air that are
mixed occurs during delay period.
 This rapid combustion phase is termed as ‘premixed combustion’ and is followed
by mixing controlled diffusion combustion process.
 The diffusion combustion rates are controlled by the rate at which fuel and air mix
and hence the name ‘mixing controlled combustion’.
 Fuel-air equivalence ratio φ varies widely from very rich at the core of spray to very
lean at the spray boundaries and, the formation of emissions is governed by the
local air-fuel ratio besides other factors like temperature and pressure.
 In the premixed combustion phase, mixture formed within the flammable limits
burns spontaneously.
 On the other hand, in the mixing controlled combustion phase, it is believed that
combustion occurs in those regions of spray where equivalence ratio is close to
stoichiometric. 2
 NO Formation in CI Engines
 In the classical spray combustion models, formation of NO starts in
the burned gases produced on combustion of close to
stoichiometric and lean flammable mixtures during premixed
combustion phase.

 New combustion research on turbocharged/supercharged engines

suggests that most NO is formed in mixing controlled diffusion
combustion at spray boundaries and in the post combustion high
temperature gases.

 The diffusion combustion takes place at near stoichiometric

conditions.

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 NO Formation in CI Engines

 In the supercharged/turbocharged engines the delay period is

rather short and overall a significantly smaller fraction of fuel burns
in premixed phase.

 In the modern turbocharged, high-pressure direct injection engines

with retarded injection timing, more than half of NOx in the cycle is
produced in the post combustion gases after peak pressure.

 In the naturally aspirated engines with long ignition delays and

sufficient time available for premixing of fuel and air, the
contribution of premixed combustion to NO formation is considered
to be substantial.

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 NO Formation in CI Engines
 NO is formed at varying rates in the spray depending upon the local
equivalence ratio and temperature.
 As the combustion progresses, the already burned gases keep on mixing
with colder air and fuel vapor, changing its composition and temperature
and hence the NO formation chemistry.
 Temperature of the reacting gases also changes due to compression and
expansion.
 Sudden cooling of the burned gases due to mixing with cooler air may
result in freezing of NO kinetics, which results in NO concentration frozen
at higher levels compared to those in the SI engines.

𝑁2 + 𝑂 + 𝑀 𝑁2 𝑂 + 𝑀
𝑁2 𝑂 + 𝑂 2𝑁𝑂 5
 NO Formation in CI Engines

 NO formation index (EINOx) in diesel engines has been correlated with

the stoichiometric adiabatic flame temperature, Tf,φ using the following
Arrhenius type expression

EINOx = constant x exp (E/RTf,φ=1)

Tf,φ =1= Adiabatic flame temperature for stoichiometric mixture, K

E = overall activation energy, J/gmol
R = universal gas constant J/gmol.K

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 Summary of NO Formation in CI Engines

 In the CI engines, most NO is formed in the burned gases resulting from the
spray regions that burn in near stoichiometric conditions.

 Kinetically formed NO is frozen at higher levels compared to SI engines as

sudden cooling of the burned gases may be caused due to mixing with cooler
air or cylinder charge, thereby freezing the NO decomposition reactions

 The engine design and operating conditions also affect the NOx formation
process.

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 NO2 Formation in CI Engines

 In diesel engines, the NO2 emissions account generally for 10 to 30

% of the total NOx emissions.

 In diesel engines, NO2 concentration may be in the range of 200 to

400 ppm compared to NO concentrations typically in the range of
1500 to 3000 ppm.

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 NO2 Formation in CI Engines
 NO2 is rapidly formed in the combustion zone by reaction of NO with
HOO- radical.
N𝑂 + 𝐻𝑂𝑂− 𝑁𝑂2 + 𝑂𝐻 −
 Later in the post combustion gases NO2 on reaction with atomic O- is
converted back to NO and O2.

𝑁𝑂2 + 𝑂− 𝑁𝑂 + 𝑂2
 However, if the high temperature burned gases due to presence of high
turbulence mix rapidly with colder air or air-fuel mixture, the reactions
that decompose NO2 back to NO and oxygen are frozen and relatively
higher concentrations of NO2 result.

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 NO2 Formation in CI Engines
 As the engine load decreases the
air/fuel ratio increases and the
probability of high temperature
gases coming suddenly in contact
of cooler air/charge in the engine
cylinder also increases.
 Hence, there is a higher probability
of freezing of NO2 decomposition
reactions in diesel engines at
lighter loads.

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 HC Emissions from CI Engines
 The unburned hydrocarbons in diesel exhaust consist of original fuel
molecules, products of pyrolysis of fuel compounds and partially oxidized
hydrocarbons, in all numbering to almost 400 organic compounds ranging
from methane to heaviest fuel components.
 In diesel engines, several events like liquid fuel injection, fuel
evaporation, fuel-air mixing, combustion, and mixing of burned and
unburned gases may take place concurrently and combustion is
heterogeneous in nature.

Schematic of diesel fuel spray and fuel-air equivalence ratio distribution at the
time of ignition. Formation of pollutants in different spray regions is qualitatively
marked.

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 HC Emissions from CI Engines
 Thus, several processes are likely to contribute to unburned hydrocarbon
emissions as below:

 Overmixing of fuel and air beyond lean flammability limits during delay
period.

 Under-mixing of fuel injected towards the end of injection process

resulting in fuel-air ratios that are too rich for complete combustion.

 Impingement of fuel sprays on walls due to spray over-penetration.

 Poorly atomized fuel from the nozzle sac volume and nozzle holes after
the end of injection.

 Bulk quenching of combustion reactions due to cold engine conditions,

mixing with cooler air or during expansion. 12
 HC Emissions from CI Engines

 A longer ignition delay allows

more time for the fuel vapors
to diffuse farther into air

 A higher percentage of fuel

would be contained in the lean
flame blow out region (φ ≈ 0.3)

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 Soot and Particulate Emissions
 Soot is a carbonaceous particulate matter and is produced during
combustion of the rich fuel - air mixtures.
 Appearance of black smoke emissions in the exhaust indicates high
concentration of soot in the exhaust gases.
 Soot is mostly produced in the diffusion combustion systems, but
overly rich premixed combustion also produces soot.
 As the spark ignition engines generally operate close to
stoichiometric air-fuel ratio, soot emissions from these engines are
not significant.
 With the use of unleaded gasoline, lead particulates from the SI
engines have been eliminated. 14
 Particulate matter (PM) in the atmosphere

PM: 40 μg/m3 PM: 8 μg/m3

Soot: Sources and Impact

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 Soot and Particulate Emissions
 In the combustion process, PM formed initially as soot (mostly
carbon)

 partially oxidized fuel and lub oil condense on the particulates in the
expansion, exhaust processes and outside the engine

o PM has effective absorption surface area of 200 m2/g

 Soluble Organic Fraction (SOF) 10-30%

o (use dichloromethane as solvent)

Typical diesels PM composition for a Euro 3 engine. 18

Soot particle structure

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 Soot particle structure

High-Resolution TEM Images 20

Diesel NOx/PM regulation

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 Diesel Smoke
 Smoke emissions increase with increase in engine load due to overall richer fuel-
air ratios, the rated engine power was specified based on the maximum permitted
smoke density. The rated power was also known as ‘smoke limited power’.
 Poor control of fuel injection rate during acceleration also increases smoke.
 Use of EGR reduces combustion temperatures and oxygen concentration in the
burned gases. EGR also reduces oxidation of soot and hence overall effect of EGR
is to increase smoke.
 Smoke emissions can be reduced by accelerating combustion. Higher combustion
rates are obtained by increasing fuel air mixing through use of high swirl rates, by
increasing injection rate and improving fuel atomization. Advancing injection
timing increases combustion temperatures and allows more time for oxidation of
soot thereby reducing smoke emissions.
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 Diesel Emissions Reduction
1. Fuel injection: higher injection pressure; multiple pulses per
cycle, injection rate shaping; improved injection timing control.

2. Combustion chamber geometry and air motion optimization well

matched to fuel injection system.

3. Exhaust Gas Recycle (EGR) for NOx control (Cooled for impact).

4. Reduced oil consumption to reduce HC contribution to

particulates.

5. Exhaust treatment technology: NOx, PM

6. Cleaner fuels and fuel additives.

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 https://www.youtube.com/watch?v=aMKpo74P6SE

Video for Diesel Particulate Filter (DPF) 24

 https://www.youtube.com/watch?v=aMKpo74P6SE

Video for Diesel Particulate Filter (DPF) 25

Diesel Particulate Filter (DPF)

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